WO1993000382A1 - Liquid crystalline polyester - Google Patents
Liquid crystalline polyester Download PDFInfo
- Publication number
- WO1993000382A1 WO1993000382A1 PCT/US1992/004909 US9204909W WO9300382A1 WO 1993000382 A1 WO1993000382 A1 WO 1993000382A1 US 9204909 W US9204909 W US 9204909W WO 9300382 A1 WO9300382 A1 WO 9300382A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- molar ratio
- liquid crystalline
- crystalline polyester
- transition temperature
- isotropic transition
- Prior art date
Links
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
-
- 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
- This invention concerns certain liquid crystalline polyesters having a low isotropic transition temperature.
- liquid crystalline polyesters give anisotropic mechanical properties when injection molded or extruded. This behavior can be attributed to processing the LCP in its liquid crystalline or thermotropic state, resulting in the molded or extruded article being highly oriented with very high mechanical properties in the direction of flow and poorly oriented with low properties across the direction of flow. Such properties are said to be anisotropic.
- the isotropic transition temperature of a polymer is the temperature at which the polymer melt changes from an opaque, thermotropic, anisotropic state to a clear, isotropic state.
- polyester compositions were available which had isotropic transition temperatures low enough for them to be processed in their isotropic state. Such compositions should give much less anisotropic properties under certain processing conditions.
- U.S. Patent 4,067,852 broadly discloses certain melt processable, wholly aromatic polyesters, but no mention is made of low isotropic transition temperatures. Additionally, European Patent Application 0,356,226 discloses certain aromatic polyesters and polyester-amides, but again, no mention is made of low isotropic transition temperatures. Summary of the Invention
- the present invention relates to new LCP's which have surprisingly low isotropic transition temperatures.
- the invention further relates to a new process for preparing containers made from certain liquid crystalline polyesters which have more uniform properties.
- the present invention relates to molded objects comprising certain liquid crystalline polyesters.
- the present invention provides all—aromatic, liquid crystalline polyester compositions which have surprisingly low isotropic transition temperatures even though all chemical bonds between repeating units are either opposite and coaxial or opposite and parallel.
- the invention concerns all—aromatic, liquid crystalline compositions based on 2,6—naphthalenedicarboxylic acid, 4,4'—biphenol, hydroquinone, and p—hydroxybenzoic acid in molar amounts such that the isotropic transition temperatures of the resulting polyesters are less than 380°C and are typically equal to or less than 350°C.
- the chemical bonds extending from the 2,6—naphthalenedicarboxylic acid repeating units are opposite and parallel, and the bonds extending from the 4,4'—biphenol, hydroquinone, and p-hydroxybenzoic acid units are opposite and coaxial.
- the advantage of the bonds between repeating units being either opposite and parallel or opposite and coaxial is that a higher degree of crystallinity (and, therefore, higher heat distortion temperature) can be obtained than in compositions containing kinking units in the chain (such as isophthalic acid) .
- liquid crystalline polyesters of the invention comprise repeating units from: (a) 2, 6—naphthalenedicarboxylic acid,
- (d) p—hydroxybenzoic acid wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c) , and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of less than 380°C, provided that said liquid crystalline polyester is not a polyester consisting of: (a), at a molar ratio of 0.30, (b) , at a molar ratio of 0.15, (c) , at a molar ratio of 0.15, and (d) , at a molar ratio of 0.70.
- the LCP's of the invention typically have an inherent viscosity of at least 2, and preferably 2 to 6, as determined in a 60/40 weight/weight solution of pentafluorophenol/1,2,4—trichlorobenzene at 25°C at a concentration of 0.1 g polyester per 100 ml solvent.
- Preferred LCP's of the invention are as follows: wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.2, the molar ratio of (c) is 0.2, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.3, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.25, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.6, — A - wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.25, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the
- the LCP's of the invention can be prepared by conventional melt— and solid—state acidolysis methods, such as from the free acids and lower aliphatic monocarboxylic acid esters of the aromatic hydroxyl groups involved. Such methods are generally disclosed in U.S. Patent 4,169,933, incorporated herein by reference.
- the all—aromatic LCP's of the invention having isotropic transition temperatures of 350°C or less have utility in processes where they can be processed above their isotropic transition temperature in the isotropic state so that the mechanical properties of the finished item are more uniform (less anisotropic) in all directions.
- the present invention is also directed to a process for preparing a container comprising:
- (d) p—hydroxybenzoic acid wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus
- step (B) holding the parison formed by step (A) above its isotropic transition temperature for a time sufficient to relax the polyester to result in a parison less oriented than before relaxation
- step (C) blow molding a container from the parison of step (B) while the parison is in the isotropic state.
- This process for preparing a container is preferably performed at a temperature of 300°C to 350°C. It is further preferred that the container is a bottle.
- the term “relax 1 * and cognatic terms thereof is meant that the degree of polymer chain alignment, possibly introduced during initial stages of processing, assumes a less aligned (more random coil) configuration.
- Such molded objects comprise a liquid crystalline polyester comprising repeating units from:
- the molded object is a parison, or a container made from the parison such as a bottle.
- the inherent viscosities are determined in 60/40 w/w pentafluorophenol/1,2,4— trichlorobenzene at 25°C and 0.1 g/100 L in a Schott Gerate viscometer.
- the polymers are dissolved at 25°C.
- the isotropic transition temperatures are determined on a Fisher— ohns Hot—Stage apparatus and are defined as the temperature at which the molten polymer observably changes from an opaque, thermotropic, anisotropic state to a mostly clear, isotropic state. Films are melt- pressed using dry polymer in a Hannafin press at the final temperature used in the preparation of the polyester.
- This example illustrates the preparation of one liquid crystalline polyester which has an isotropic transition temperature less than 350°C.
- the flask is then evacuated and purged three times with nitrogen, a slow nitrogen sweep of the flask contents is begun, and the flask is partly immersed in a metal bath maintained at 280°C. After the starting materials are mostly melted, stirring is begun. The mixture is heated at 280°C for 65 minutes, at 300°C for 60 minutes, and at 340°C for 15 minutes. The polymerization mixture is an opaque, low melt viscosity material at this time. Vacuum is then applied from atmospheric to ⁇ 0.5 torr (0.067 kPa) during 10 minutes, and stirring is continued for 65 minutes to obtain a very high melt viscosity product. After being cooled to 25°C, the polymer is opaque-tan, gives a very tough melt—pressed film, and has an I. V. of 2.70. The isotropic transition temperature (T ⁇ ) of the polyester is 290-295°C.
- Comparative Example 2 This example illustrates the very high isotropic transition temperature obtained when the liquid crystalline polyester is prepared from four monomers (only one of which is different from the four monomers used to prepare the compositions of the invention) which give only opposite and coaxial or opposite and parallel bonds in the polyester chain; but, in contrast to the compositions of the invention, the isotropic transition temperature is still very high.
- Example 1 is repeated using a final buildup temperature of 370°C and the following starting materials:
- the polymer thus prepared has an I. V. of 7.66, has an isotropic transition temperature of >420°C, and gives a very tough, melt—pressed film.
- This example illustrates the very high isotropic transition temperature obtained when the polyester is prepared from only 2,6—naphthalenedicarboxylic acid, 4,4'—biphenol diacetate, and p—acetoxybenzoic acid (no p—phenylene dipropionate used) .
- Example 1 is repeated using 400°C as the final buildup temperature and the following starting materials:
- the polymer thus prepared has an I. V. of 7.48, has an isotropic transition temperature of >420°C, and gives a very tough melt—pressed film. Comparative Example 4
- This example illustrates the very high isotropic transition temperature obtained when the polyester is prepared from only 2,6-naphthalenedicarboxylic acid, p—phenylene dipropionate, and p—acetoxybenzoic acid (no 4,4'—biphenol diacetate used).
- Example l is repeated using 390°C as the final buildup temperature and the following starting materials:
- the polymer thus prepared has an I. V. of 5.96, has an isotropic transition temperature of >420°C, and gives a very tough melt—pressed film.
- Comparative Examples 5—9 illustrate other liquid crystalline polyesters outside the scope of the present invention which have high isotropic transition temperatures.
- the polyesters were prepared using techniques similar to those disclosed in Examples 1—4.
- Example 1 is repeated except using different amounts of the same starting materials and various final buildup temperatures between 340°C and 380°C, as required, to prepare various high—melt—viscosity, liquid crystalline polyesters having the T ⁇ 's indicated in Table 1.
- the data for the other examples are also given for comparison.
- Examples 10—15 illustrate that liquid crystalline polyester compositions having low isotropic transition temperatures can be prepared containing a certain range of monomer segments derived from 2,6—naphthalene— dicarboxylic acid, 4,4'—biphenol, hydroquinone, and p—hydroxybenzoic acid.
- 'T' mole ratio of repeat units derived from terephthalic acid.
Abstract
The present invention relates to liquid crystalline polyesters which have surprisingly low isotropic transition temperatures. The invention further relates to a new process for preparing containers which have more uniform properties made from certain liquid crystalline polyesters. Also, the present invention relates to molded objects comprising certain liquid crystalline polyesters. The liquid crystalline polyesters disclosed herein are derived from 2,6-naphthalenedicarboxylic acid, 4,4'-biphenol, hydroquinone, and p-hydroxybenzoic acid.
Description
LIQUID CRYSTALLINE POLYESTER
Field of Invention
This invention concerns certain liquid crystalline polyesters having a low isotropic transition temperature.
Background of the Invention
It is well known in the art that liquid crystalline polyesters (LCP's) give anisotropic mechanical properties when injection molded or extruded. This behavior can be attributed to processing the LCP in its liquid crystalline or thermotropic state, resulting in the molded or extruded article being highly oriented with very high mechanical properties in the direction of flow and poorly oriented with low properties across the direction of flow. Such properties are said to be anisotropic.
The isotropic transition temperature of a polymer is the temperature at which the polymer melt changes from an opaque, thermotropic, anisotropic state to a clear, isotropic state. For some applications, it would be highly advantageous if polyester compositions were available which had isotropic transition temperatures low enough for them to be processed in their isotropic state. Such compositions should give much less anisotropic properties under certain processing conditions.
U.S. Patent 4,067,852 broadly discloses certain melt processable, wholly aromatic polyesters, but no mention is made of low isotropic transition temperatures. Additionally, European Patent Application 0,356,226 discloses certain aromatic polyesters and polyester-amides, but again, no mention is made of low isotropic transition temperatures.
Summary of the Invention
The present invention relates to new LCP's which have surprisingly low isotropic transition temperatures. The invention further relates to a new process for preparing containers made from certain liquid crystalline polyesters which have more uniform properties. Also, the present invention relates to molded objects comprising certain liquid crystalline polyesters.
Detailed Description of the Invention
The present invention provides all—aromatic, liquid crystalline polyester compositions which have surprisingly low isotropic transition temperatures even though all chemical bonds between repeating units are either opposite and coaxial or opposite and parallel. The invention concerns all—aromatic, liquid crystalline compositions based on 2,6—naphthalenedicarboxylic acid, 4,4'—biphenol, hydroquinone, and p—hydroxybenzoic acid in molar amounts such that the isotropic transition temperatures of the resulting polyesters are less than 380°C and are typically equal to or less than 350°C. The chemical bonds extending from the 2,6—naphthalenedicarboxylic acid repeating units are opposite and parallel, and the bonds extending from the 4,4'—biphenol, hydroquinone, and p-hydroxybenzoic acid units are opposite and coaxial. The advantage of the bonds between repeating units being either opposite and parallel or opposite and coaxial is that a higher degree of crystallinity (and, therefore, higher heat distortion temperature) can be obtained than in compositions containing kinking units in the chain (such as isophthalic acid) .
The liquid crystalline polyesters of the invention comprise repeating units from:
(a) 2, 6—naphthalenedicarboxylic acid,
(b) 4,4'—biphenol,
(c) hydroquinone, and
(d) p—hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c) , and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of less than 380°C, provided that said liquid crystalline polyester is not a polyester consisting of: (a), at a molar ratio of 0.30, (b) , at a molar ratio of 0.15, (c) , at a molar ratio of 0.15, and (d) , at a molar ratio of 0.70.
The LCP's of the invention typically have an inherent viscosity of at least 2, and preferably 2 to 6, as determined in a 60/40 weight/weight solution of pentafluorophenol/1,2,4—trichlorobenzene at 25°C at a concentration of 0.1 g polyester per 100 ml solvent. Preferred LCP's of the invention are as follows: wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.2, the molar ratio of (c) is 0.2, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.3, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.25, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.6,
— A - wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.25, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.1, the molar ratio of (c) is 0.3, and the molar ratio of (d) is 0.6, wherein the molar ratio of (a) is 0.3, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.7, and wherein the molar ratio of (a) is 0.2, the molar ratio of (b) is 0.1, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.8.
The LCP's of the invention can be prepared by conventional melt— and solid—state acidolysis methods, such as from the free acids and lower aliphatic monocarboxylic acid esters of the aromatic hydroxyl groups involved. Such methods are generally disclosed in U.S. Patent 4,169,933, incorporated herein by reference. The all—aromatic LCP's of the invention having isotropic transition temperatures of 350°C or less have utility in processes where they can be processed above their isotropic transition temperature in the isotropic state so that the mechanical properties of the finished item are more uniform (less anisotropic) in all directions. Thus, the present invention is also directed to a process for preparing a container comprising:
(A) extruding a liquid crystalline polyester comprising repeating units from:
(a) 2,6—naphthalenedicarboxylic acid,
(b) 4,4'—biphenol,
(c) hydroquinone, and
(d) p—hydroxybenzoic acid,
wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus
(c) , and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380°C or less, above its isotropic transition temperature to form a parison,
(B) holding the parison formed by step (A) above its isotropic transition temperature for a time sufficient to relax the polyester to result in a parison less oriented than before relaxation, and
(C) blow molding a container from the parison of step (B) while the parison is in the isotropic state.
This process for preparing a container is preferably performed at a temperature of 300°C to 350°C. It is further preferred that the container is a bottle. By the term "relax1* and cognatic terms thereof is meant that the degree of polymer chain alignment, possibly introduced during initial stages of processing, assumes a less aligned (more random coil) configuration.
Although the above—described method for preparing a container is a preferred embodiment of the invention, the present invention is also directed to molded objects regardless of the specific methodology employed for their preparation. Such molded objects comprise a liquid crystalline polyester comprising repeating units from:
(a) 2,6—naphthalenedicarboxylic acid,
(b) 4,4'—biphenol, (c) hydroquinone, and
(d) p—hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c) , and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380°C or less. Of course, it is preferred that the molded object is a parison, or a container made from the parison such as a bottle.
This invention is illustrated by the following examples but should not be interpreted as a limitation thereon.
Examples In the examples, the inherent viscosities (I. V.'s) are determined in 60/40 w/w pentafluorophenol/1,2,4— trichlorobenzene at 25°C and 0.1 g/100 L in a Schott Gerate viscometer. The polymers are dissolved at 25°C. The isotropic transition temperatures are determined on a Fisher— ohns Hot—Stage apparatus and are defined as the temperature at which the molten polymer observably changes from an opaque, thermotropic, anisotropic state to a mostly clear, isotropic state. Films are melt- pressed using dry polymer in a Hannafin press at the final temperature used in the preparation of the polyester.
Example 1
This example illustrates the preparation of one liquid crystalline polyester which has an isotropic transition temperature less than 350°C.
To a 1000—mL, single—necked flask equipped with stainless steel stirrer, provisions for maintaining a
nitrogen atmosphere and applying vacuum, and a trap system for removing the volatiles from the polymeriza¬ tion are added 40.50 grams (0.15 mole) 4,4'—biphenol diacetate, 36.63 grams (0.165 mole) p—phenylene diacetate, 64.80 grams (0.30 mole) 2,6-naphthalene- dicarboxylic acid, and 81.00 grams (0.45 mole) p—acetoxybenzoic acid. The flask is then evacuated and purged three times with nitrogen, a slow nitrogen sweep of the flask contents is begun, and the flask is partly immersed in a metal bath maintained at 280°C. After the starting materials are mostly melted, stirring is begun. The mixture is heated at 280°C for 65 minutes, at 300°C for 60 minutes, and at 340°C for 15 minutes. The polymerization mixture is an opaque, low melt viscosity material at this time. Vacuum is then applied from atmospheric to <0.5 torr (0.067 kPa) during 10 minutes, and stirring is continued for 65 minutes to obtain a very high melt viscosity product. After being cooled to 25°C, the polymer is opaque-tan, gives a very tough melt—pressed film, and has an I. V. of 2.70. The isotropic transition temperature (T^) of the polyester is 290-295°C.
Comparative Example 2 This example illustrates the very high isotropic transition temperature obtained when the liquid crystalline polyester is prepared from four monomers (only one of which is different from the four monomers used to prepare the compositions of the invention) which give only opposite and coaxial or opposite and parallel bonds in the polyester chain; but, in contrast to the compositions of the invention, the isotropic transition temperature is still very high.
Example 1 is repeated using a final buildup temperature of 370°C and the following starting materials:
28.22 grams (0.170 mole) terephthalic acid
36.72 grams (0.170 mole) 2,6-naphthalenedicarboxylic acid
83.03 grams (0.374 mole) p—phenylene dipropionate
91.80 grams (0.510 mole) p—acetoxybenzoic acid
The polymer thus prepared has an I. V. of 7.66, has an isotropic transition temperature of >420°C, and gives a very tough, melt—pressed film.
Comparative Example 3
This example illustrates the very high isotropic transition temperature obtained when the polyester is prepared from only 2,6—naphthalenedicarboxylic acid, 4,4'—biphenol diacetate, and p—acetoxybenzoic acid (no p—phenylene dipropionate used) .
Example 1 is repeated using 400°C as the final buildup temperature and the following starting materials:
64.80 grams (0.300 mole) 2,6—naphthalenedicarboxylic acid
81.00 grams (0.300 mole) 4,4'—biphenol diacetate
81.00 grams (0.450 mole) p—acetoxybenzoic acid
The polymer thus prepared has an I. V. of 7.48, has an isotropic transition temperature of >420°C, and gives a very tough melt—pressed film.
Comparative Example 4
This example illustrates the very high isotropic transition temperature obtained when the polyester is prepared from only 2,6-naphthalenedicarboxylic acid, p—phenylene dipropionate, and p—acetoxybenzoic acid (no 4,4'—biphenol diacetate used).
Example l is repeated using 390°C as the final buildup temperature and the following starting materials:
69.12 grams (0.320 mole) 2,6—naphthalenedicarboxylic acid
78.14 grams (0.352 mole) p-phenylene dipropionate
86.40 grams (0.480 mole) p—acetoxybenzoic acid
The polymer thus prepared has an I. V. of 5.96, has an isotropic transition temperature of >420°C, and gives a very tough melt—pressed film.
Comparative Examples 5—9
Comparative Examples 5—9 illustrate other liquid crystalline polyesters outside the scope of the present invention which have high isotropic transition temperatures. The polyesters were prepared using techniques similar to those disclosed in Examples 1—4.
Examples 10-15
Example 1 is repeated except using different amounts of the same starting materials and various final buildup temperatures between 340°C and 380°C, as required, to prepare various high—melt—viscosity, liquid crystalline polyesters having the T^'s indicated in Table 1. The data for the other examples are also given for comparison.
Examples 10—15 illustrate that liquid crystalline polyester compositions having low isotropic transition temperatures can be prepared containing a certain range of monomer segments derived from 2,6—naphthalene— dicarboxylic acid, 4,4'—biphenol, hydroquinone, and p—hydroxybenzoic acid.
Table 1 uses the following nomenclature: 'N' = mole ratio of repeat units derived from 2,6— aphthalenedicarboxylic acid. 'HQ' = mole ratio of repeat units derived from hydroquinone. 'BP' = mole ratio of repeat units derived from
4,4'—biphenol. 'PHB' = mole ratio of repeat units derived from p—hydroxybenzoic acid.
'T' = mole ratio of repeat units derived from terephthalic acid.
NOTES: 1. 'N' + 'T' = 'HQ' + 'BP'. 2. 'N' + 'T' + 'PHB' = 1.0.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifica ions can be effected within the spirit and scope of the invention.
Claims
1. A liquid crystalline polyester comprising repeating units from:
(a) 2,6— aphthalenedicarboxylic acid,
(b) 4,4'—biphenol,
(c) hydroquinone, and (d) p—hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus
(c) , and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of less than 380°C, provided that said liquid crystalline polyester is not a polyester consisting of: (a), at a molar ratio of 0.30, (b) , at a molar ratio of 0.15, (c) , at a molar ratio of 0.15, and (d) , at a molar ratio of 0.70.
2. The liquid crystalline polyester of Claim 1 having an isotropic transition temperature of 350°C or less.
The liquid crystalline polyester of Claim 1 having an inherent viscosity of at least 2 as determined in a 60/40 weight/weight solution of pentafluoro— phenol/1,2,4—trichlorobenzene at 25°C at a concentration of 0.1 g polyester per 100 ml solvent.
The liquid crystalline polyester of Claim 1 having an inherent viscosity of 2 to 6 as determined in a 60/40 weight/weight solution of pentafluoro- phenol/1,2,4—trichlorobenzene at 25°C at a concentration of 0.1 g polyester per 100 ml solvent.
The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.2, the molar ratio of (c) is 0.2, and the molar ratio of (d) is 0.6.
The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.3, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.6.
The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.25, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.6.
The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.25, and the molar ratio of (d) is 0.6.
The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.4, the molar ratio of (b) is 0.1, the molar ratio of (c) is 0.3, and the molar ratio of (d) is 0.6.
10. The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.3, the molar ratio of (b) is 0.15, the molar ratio of (c) is 0.15, and the molar ratio of (d) is 0.7.
11. The liquid crystalline polyester of Claim 1 wherein the molar ratio of (a) is 0.2, the molar ratio of (b) is 0.1, the molar ratio of (c) is 0.1, and the molar ratio of (d) is 0.8.
12. A molded object comprising a liquid crystalline polyester comprising repeating units from:
(a) 2,6—naphthalenedicarboxylic acid,
(b) 4,4'—biphenol, (c) hydroquinone, and
(d) p—hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to 0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c) , and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380°C or less.
13. The molded object of Claim 11 which is a parison. '
14. The molded object of Claim 11 which is a container.
15. The molded object of Claim 12 wherein said liquid crystalline polyester has an isotropic transition temperature of less than 350°C.
16. A process for preparing a container comprising: (A) extruding a liquid crystalline polyester comprising repeating units from:
(a) 2,6—naphthalenedicarboxylic acid, (b) 4,4'-biphenol,
(c) hydroquinone, and
(d) p—hydroxybenzoic acid, wherein the molar ratio of (a) is 0.2 to 0.4, the molar ratio of (b) is 0.1 to 0.3, the molar ratio of (c) is 0.05 to
0.3, the molar ratio of (d) is 0.6 to 0.8, the molar ratio of (a) is equal to the molar ratio of (b) plus (c) , and the molar ratio of (a) plus (d) is equal to 1.0, and wherein said liquid crystalline polyester has an isotropic transition temperature of 380°C or less, above its isotropic transition temperature to form a parison, (B) holding the parison formed by step (A) above its isotropic transition temperature for a time sufficient to relax the polyester to result in a parison less oriented than before relaxation, and (C) blow molding a container from the parison of step (B) while the parison is in the isotropic state.
17. The process of Claim 16 carried out at a temperature of 300°C to 350°C.
18. The process of Claim 16 wherein said container is a bottle.
19. The process of Claim 16 wherein said liquid crystalline polyester has an isotropic transition temperature of less than 350°C.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92913524A EP0590028A1 (en) | 1991-06-21 | 1992-06-12 | Liquid crystalline polyester |
| KR1019930703970A KR940701416A (en) | 1991-06-21 | 1992-06-12 | Liquid crystalline polyester |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US718,692 | 1976-08-30 | ||
| US71869291A | 1991-06-21 | 1991-06-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993000382A1 true WO1993000382A1 (en) | 1993-01-07 |
Family
ID=24887111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1992/004909 WO1993000382A1 (en) | 1991-06-21 | 1992-06-12 | Liquid crystalline polyester |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0590028A1 (en) |
| JP (1) | JP3174330B2 (en) |
| KR (1) | KR940701416A (en) |
| CA (1) | CA2110708C (en) |
| WO (1) | WO1993000382A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5771449A (en) * | 1994-03-17 | 1998-06-23 | Endlink, Inc. | Sectorized multi-function communication system |
| EP1094085A2 (en) * | 1999-10-18 | 2001-04-25 | Polyplastics Co. Ltd. | Method for producing liquid crystalline polymer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2015349719A1 (en) | 2014-11-21 | 2017-07-13 | Occam Biolabs, Inc. | System and method for collecting a sample of nucleic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2721786A1 (en) * | 1976-05-13 | 1977-11-24 | Celanese Corp | IMPROVED MELT-PROCESSABLE FULLY AROMATIC THERMOTROPIC POLYESTERS AND METHOD FOR MANUFACTURING THEM |
| EP0356226A2 (en) * | 1988-08-24 | 1990-02-28 | Mitsubishi Chemical Corporation | Aromatic polyester, aromatic polyester-amide and processes for producing the same |
-
1992
- 1992-06-12 JP JP50151193A patent/JP3174330B2/en not_active Expired - Lifetime
- 1992-06-12 KR KR1019930703970A patent/KR940701416A/en active IP Right Grant
- 1992-06-12 WO PCT/US1992/004909 patent/WO1993000382A1/en not_active Application Discontinuation
- 1992-06-12 EP EP92913524A patent/EP0590028A1/en not_active Withdrawn
- 1992-06-12 CA CA002110708A patent/CA2110708C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2721786A1 (en) * | 1976-05-13 | 1977-11-24 | Celanese Corp | IMPROVED MELT-PROCESSABLE FULLY AROMATIC THERMOTROPIC POLYESTERS AND METHOD FOR MANUFACTURING THEM |
| EP0356226A2 (en) * | 1988-08-24 | 1990-02-28 | Mitsubishi Chemical Corporation | Aromatic polyester, aromatic polyester-amide and processes for producing the same |
Non-Patent Citations (1)
| Title |
|---|
| MAKROMOLEKULARE CHEMIE, RAPID COMMUNICATIONS vol. 3, no. 1, 1982, BASEL CH pages 23 - 27 BYUNG WOOK JO, ROBERT W. LENZ 'Thermotropic Polyesters with Main Chain Phenyl-1,4-phenylene, 4,4'-Biphenylene, and 1,1'-Binaphthyl-4,4'-ylene Units' * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5771449A (en) * | 1994-03-17 | 1998-06-23 | Endlink, Inc. | Sectorized multi-function communication system |
| US6052582A (en) * | 1994-03-17 | 2000-04-18 | Endlink Corporation | Sectorized multi-function communication system |
| EP1094085A2 (en) * | 1999-10-18 | 2001-04-25 | Polyplastics Co. Ltd. | Method for producing liquid crystalline polymer |
| EP1094085A3 (en) * | 1999-10-18 | 2002-01-30 | Polyplastics Co. Ltd. | Method for producing liquid crystalline polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3174330B2 (en) | 2001-06-11 |
| CA2110708C (en) | 1998-01-06 |
| JPH06508395A (en) | 1994-09-22 |
| KR940701416A (en) | 1994-05-28 |
| CA2110708A1 (en) | 1993-01-07 |
| EP0590028A1 (en) | 1994-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0044675B1 (en) | Processing of melt processable liquid crystal polymer by control of thermal history | |
| EP0133024B2 (en) | Improved process for forming thermally stable thermotropic liquid crystalline polyesters of predetermined chain length | |
| US5393871A (en) | Production of polyesters and polyester articles having good clarity | |
| JP3375964B2 (en) | Shrinkable copolyester film | |
| US3890256A (en) | Copolyester prepared by contacting acyloxy benzoic acid with a polyester of ethylene glycol and dicarboxylic acid | |
| CN109824876B (en) | Thermotropic liquid crystal polymer and preparation method and application thereof | |
| US3859251A (en) | Poly(ester-amide) | |
| EP0266497A1 (en) | Wholly aromatic polyester composition and process for producing it | |
| US4390681A (en) | Liquid crystal copolyesters | |
| CN110951060A (en) | High-fluidity wholly aromatic liquid crystal polyester and preparation method thereof | |
| US4814416A (en) | Molding compounds comprised of a thermotropic aromatic polyester | |
| CA2110708C (en) | Liquid crystalline polyester | |
| US5260409A (en) | Liquid crystalline polyester | |
| EP0102160A1 (en) | Anisotropic melt processable polyester comprising relatively low concentration of 6-oxy-2-naphthoyl moiety | |
| US3547888A (en) | Amorphous terpolyesters having high impact strength | |
| JPH0264123A (en) | Molded article of polyester having high modulus of elasticity | |
| EP0747415A2 (en) | Process for producing liquid crystal polymer | |
| US6409937B1 (en) | Melt processible thermotropic liquid crystalline terpolyesters and process for the preparation thereof | |
| JPH023413B2 (en) | ||
| JPH03217422A (en) | Treatment of polyester | |
| US5235025A (en) | Cross-linkable thermotropic liquid crystalline aromatic polyester | |
| US6419851B1 (en) | Melt processible liquid crystalline terpolyesters and process for the preparation thereof | |
| JPH03146529A (en) | Method for treating polyester | |
| GB2360777A (en) | Melt processible thermotropic liquid crystalline terpolyesters and process for the preparation thereof | |
| EP0383177A2 (en) | Cross-linkable thermotropic liquid crystalline aromatic polyesters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA JP KR |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 2110708 Country of ref document: CA |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 1992913524 Country of ref document: EP |
|
| WWP | Wipo information: published in national office |
Ref document number: 1992913524 Country of ref document: EP |
|
| WWW | Wipo information: withdrawn in national office |
Ref document number: 1992913524 Country of ref document: EP |