WO1995033803A1

WO1995033803A1 - Thermotropic liquid crystalline poly(esteramides)

Info

Publication number: WO1995033803A1
Application number: PCT/US1995/006364
Authority: WO
Inventors: Balaram Gupta; Matthew J. Bylicki
Original assignee: Hoechst Celanese Corporation
Priority date: 1994-06-06
Filing date: 1995-05-22
Publication date: 1995-12-14
Also published as: JPH10501277A; EP0764195A1

Abstract

A new class of thermotropic liquid crystalline poly(esteramides) consists essentially of monomer units derived from about 5 to about 80 mole % of 4-hydroxybenzoic acid, about 5 to about 35 mole % of 2,6-naphthalenedicarboxylic acid, about 3 to about 20 mole % of terephthalic acid, about 5 to about 35 mole % of 1,4-hydroquinone, about 2 to about 30 mole % of 4-aminophenol, and optionally up to about 10 mole % of 4,4'-biphenol. These poly(esteramides) have exceptionally high heat distortion temperatures compared with their melting temperatures.

Description

THERMOTROPIC LIQUID CRYSTALLINE POLY(ESTERAMIDES)

Field of the Invention

This invention relates generally to thermotropic liquid crystalline polymers, and more specifically to liquid crystalline poly(esteramides) that have a high heat distortion temperature.

Background of the Invention

Thermotropic liquid crystalline polymers are well known in the art. They have excellent properties that make them useful in the manufacture of molded parts. The strength of molded parts at elevated temperatures, as measured by the heat distortion temperature, is ultimately limited by the melting temperature of the polymers. Nevertheless, molded parts made from some polymers retain their physical integrity at temperatures close to the melting temperature. This may be characterized as the difference between the melting temperature of the polymer and the heat distortion temperature.

A class of poly(esteramides) derived from 2,6-naphthalenedicarboxylic acid

(NDA) has been found in which the HDT is very close to the melting temperature, so that a molded article can have a very high HDT. This property has not been observed in existing polymers derived from NDA, such as polyesters derived from NDA with some or all of the following comonomers: 1 ,4-hydroquinone (HQ), terephthalic acid (TA), 4- hydroxybenzoic acid (HBA), and 4,4'-biphenol (BP). These polymers have been reported in U. S. Patent Nos. 4,067,852, 4,169,933, 4,849,499, 5,110,896, 5,221,730, 5,237,038 and 5,260,409. Poly(esteramides) derived from HBA, NDA, TA, BP and 4- aminophenol (APAP) have been described in U. S. Patent No. 5,025,082. Finally, poly(esteramides) derived from HBA, NDA, HQ, APAP, and isophthalic acid (IA) have been described in U. S. Patent No. 4,355,132. This last patent claims the use of aromatic diacids more broadly, including TA, but uses only I A and NDA in the examples. None of these are known to exhibit the advantageous improvement in HDT relative to melting temperature exhibited by the polymers disclosed herein.

Summary Of The Invention

Thermotropic liquid crystalline poly(esteramides) that consist essentially of monomer repeat units I, II, III, IV, V and optional VI have an excellent combination of properties, where:

and VI is

In these polymers, X is NR', C=0, O, or a mixture thereof. In monomer repeat unit V, R and R' are alike or different and are selected from the group consisting of H, alkyl groups having 1 to 4 carbon atoms, fluoroalkyl groups having 1 to 4 carbon atoms, phenyl, and mixtures thereof. Some of the hydrogen atoms on the aromatic rings of monomer repeat units I, II, III, IV, V and VI optionally may be replaced with one or more substituents selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, fluoroalkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, Cl, Br, F, I, aromatic groups having up to 7 carbon atoms and mixtures thereof.

In the monomer repeat units described above, alkyl groups having 1 to 4 carbon atoms include linear and branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl and tert-butyl. Fluoroalkyl groups having 1 to 4 carbon atoms include linear and branched fluoroalkyl groups in which some or all of the hydrogen atoms have been replaced with fluorine. Alkoxy groups having 1 to 4 carbon atoms can be linear or branched, such as methoxy, ethoxy, n-propoxy or isopropoxy. Aromatic groups having up to 7 carbon atoms include phenyl and methyl substituted phenyl groups.

The liquid crystalline poly(esteramides) contain on a mole basis about 5% to about 80%) of monomer repeat unit I, about 5% to about 35%> of monomer repeat unit II, about 3%> to about 20%) of monomer repeat unit III, about 5% to about 35%) of monomer repeat unit IV, about 2%> to about 30%> of monomer repeat unit V, and 0 to about 10%> of monomer repeat unit VI. These polymers show an exceptionally high heat distortion temperature compared with their melting temperature as measured by differential scanning calorimetry. They also show excellent impact resistance, as measured by their high notched Izod impact strength values.

Detailed Description of the Invention

In preferred embodiments, monomer unit V is

rC

Preferably, the aromatic rings of monomer units I, II, III, IV, V and VI are not substituted. Monomer unit VI may be present in amounts up to about 10%>; its presence in the polymer is not necessary. Polymers that do not contain monomer unit VI, and are thus composed of monomer units I, II, III, IV and V, have excellent properties.

Preferred polymer compositions contain on a mole basis about 20% to about 60% of monomer repeat unit I, about 10% to about 30%> of monomer repeat unit II, about 5% to about 15%) of monomer repeat unit III, about 10% to about 30%o of monomer repeat unit IV, and about 5%> to about 20% of monomer repeat unit V. The preferred poly(esteramides) may optionally also include up to about 10% of monomer repeat unit VI. More preferred poly(esteramides) on a mole basis are composed of about 30%) to about 50%) of monomer repeat unit I, about 15%) to about 25%) of monomer repeat unit II, about 5% to about 15%» of monomer repeat unit III, about 20%> to about 30%> of monomer repeat unit IV, and about 5%> to about 10%> of monomer repeat unit V; monomer repeat unit VI is not present. An especially preferred composition on a mole basis consists essentially of about 40%) of monomer unit I, about 20%> of monomer unit II, about 10%) of monomer unit III, about 25%) of monomer unit IV, and about 5%> of monomer unit V.

Polymers having the compositions described above melt to form liquid crystalline melt phases. The polymers described above generally have melting temperatures as measured by differential scanning calorimetry in the range of about 275 °C to about

350°C. Preferred compositions generally melt in the range of about 300°C to about

340°C.

These liquid crystalline poly(esteramides) can be made by any of the methods already used in the art for making aromatic polyesters and poly(esteramides). These methods include: interfacial polymerization; the reaction of preformed phenyl esters of the aromatic acid groups with the phenolic groups of other monomers to yield polyester linkages and by-product phenol; and melt acidolysis polymerization, which is the preferred method. All of these polymerization methods involve the condensation of • reactive derivatives of the monomers rather than the free monomers, since the aromatic phenols and acids do not polymerize well.

In melt acidolysis polymerization, the phenolic reactants are acetylated to yield aromatic acetate groups, and these are then heated in the melt with the aromatic acids to yield acetic acid and polyester linkages. This method is described in numerous patents, including U. S. Patent No. 4,473,682. The melt acidolysis method is most conveniently carried out by acetylating the phenolic groups in situ and then heating the acetylated monomers to a high enough temperature to induce polymerization. The melt acidolysis method is also useful for aromatic amines, which are generally charged to the reaction as N-acetyl derivatives rather than being acetylated in situ. Thus, the preferred aromatic amine, 4-aminophenol, is generally charged to the polymerization reaction as N-acetyl-4- aminophenol (also referred to as 4-hydroxyacetanilide or acetaminophen). Examples of methods of synthesizing aromatic poly(esteramides) by this method can be found in numerous references, such as U. S. Patent Nos. 5,204,443, 4,330,457, 4,966,956, 4,355,132, 4,339,375, 4,351,917 and 4,351,918.

In the preferred melt acidolysis polymerization route, the phenolic groups are acetylated in situ by including an approximately stoichiometric amount of acetic anhydride relative to the phenolic groups. Actually, a slight excess of about 2.5% acetic anhydride is typically included in the "stoichiometric" reactions. It has surprisingly been found that the reaction is improved when a large excess of acetic anhydride is included in the reaction. Thus if an additional excess of about 20% acetic anhydride is included above the typical 2.5%> excess, so that a total of 23%) excess acetic anhydride is used, then the reaction rate increases and the polymeric product has a higher molecular weight, as shown by the increased inherent viscosity. Some of the physical properties, such as heat distortion temperature, are also consistently higher when excess acetic anhydride is used. The use of excess acetic anhydride is generally beneficial when the amount of excess acetic anhydride (above the 2.5%> excess that is normally used in "stoichiometric" reactions) is in the range of about 5% to about 50%, preferably in the range of about 10% to about 30%>, and most preferably is about 20% (i.e. about 23% above true stoichiometry).

The polymerization reaction is carried out until the polymer reaches a useful molecular weight, as indicated by the inherent viscosity measured at 25 °C of a 0.1 %> solution on a weight/volume basis in a mixture of equal volumes of pentafluorophenol and hexafluoroisopropanol. The inherent viscosity of the polymer generally is at least about 2 dl/g, preferably is at least about 3 dl/g, and ideally is at least about 5 dl/g.

The polymers of this invention are useful in the manufacture of shaped articles, such as fibers, films (e.g. extruded sheets or films) and molded articles. They are particularly useful for making molded articles in which a high heat distortion temperature or high impact resistance is desired. These polymers have an unusually high heat distortion temperature (HDT) in comparison with the crystalline melting temperature (Tm). This is desirable because molded articles with a high HDT can be made from these polymers at lower temperatures than from other polymers that have the same HDT. Therefore, the deleterious effects that are associated with processing the polymer at a high temperature in the molten phase, such as decomposition of the polymer, fillers, or other additives, are less likely to occur.

The differences between melting temperature and HDT of some of the polymers of this invention are tabulated in Table 3 as "Tm-HDT". There it can be seen that the difference between the melting temperature and HDT is generally less than about 40 °C for the polymers of this invention, whereas this same difference is generally greater for other polymers of similar composition. It can also be seen in Table 3 that this difference is generally smaller (and therefore better) when excess acetic anhydride is used in the synthesis of the polymer. Finally, it can also be seen in Table 3 that the notched Izod impact resistance values of these polymers appear to be generally higher than the notched Izod values of other polymers with similar monomer compositions.

In making compositions for injection molding, the polymers of this invention are generally blended with fillers and other additives at levels up to about 70%> by weight in order to achieve optimum properties. Fillers and additives that may be useful include one or more fillers or reinforcing agents selected from the following list, which is not a complete or exhaustive list: glass fiber, calcium silicate, silica, clays, talc, mica, polytetrafluoroethylene, graphite, alumina, sodium aluminum carbonate, barium ferrite, woUastonite, carbon fiber, polymeric fiber, aluminum silicate fiber, titanium fiber, rock wool fiber, steel fiber, tungsten fiber and woUastonite fiber. Other kinds of additives that may be used in addition to reinforcing fillers and reinforcing fibers include oxidation stabilizers, heat stabilizers, light stabilizers, lubricants, mold release agents, dyes, pigments, and plasticizers.

The polymers may also be melt spun into fibers having high strength and high modulus. After heat treatment, the fibers have tensile strengths up to about 20-25 gpd and modulus values up to about 500 gpd.

This invention is further illustrated by the following non-limiting examples.

Examples

A number of polymers were made in accordance with the invention described herein. Other polymers were made for comparison. All were made according to the basic procedures described below, except for changes in the monomers and the amounts of monomers. The compositions of the polymers are presented in Table 1. The physical properties of the polymers and mechanical properties of molded parts are presented in Tables 2 and 3. Polymers for which stoichiometric and excess amounts of acetic anhydride were used in synthesis are shown as (a) and (b) examples; e.g. Examples 8(a) and 8(b). Examples C-l to C-10 in the tables are comparative examples.

Typical Procedure using "Stoichiometric" Acetic Anhydride. The procedure for making the polymer having the composition of Example 10 is described below.

In a three-neck 4 liter glass reactor immersed in a sand bath and equipped with a nitrogen inlet, thermocouple, vigreux column attached to a condenser and receiver, and C-shaped 316 stainless steel mechanical stirrer were placed: (a) 552 grams (4 moles) of 4- hydroxybenzoic acid (HBA), (b) 432 grams (2 moles) of 2,6-naphthalenedicarboxylic acid (NDA), (c) 275 grams (2.5 moles) of 1,4-hydroquinone (HQ), (d) 166 grams (1 mole) of terephthalic acid (TA), (e) 75.5 grams (0.5 moles) of acetaminophen (AA), and (f) 0.203 grams of potassium acetate under a constant purge of nitrogen (30 to 40 cc/rnin). The reactor was evacuated to approximately 1 to 2 mbar followed by breaking the vacuum with nitrogen. The vacuum-nitrogen purging process was repeated twice and 1004.1 grams (9.74 moles, 2.5 mole %> excess, 99 mol %> purity) of acetic anhydride was introduced into the reactor through an addition funnel. The reactor was then heated in stages using a MicRIcon® controller. The temperature at each stage was increased to the final temperature of that stage during the elapsed time. Steps 1, 12 and 13 are isothermal. The program follows:

Heating Stage No. Temperature. °C Elapsed Time, minutes

1 25 1

2 125 50

3 140 40

4 150 20

5 200 45

6 210 5

7 220 6

8 275 50

9 310 70

10 340 30

11 360 20

12 360 15

13 360 60

The acetic acid began distilling off when the reactor was at 150°C. About 99% of the theoretical amount (1165 ml) had evolved at the end of segment 13. The nitrogen purge was then turned off and the reactor was evacuated to about 2 mbar. The torque on the stirrer that was needed to maintain constant stirring speed started to rise. The reaction was terminated when the voltage to the stirrer increased by 12 mvolts above the initial value. This time was usually about 60 minutes to 100 minutes. The reactor was cooled and broken to obtain the polymer. The polymer was then cut and ground into 11 chips. The yield was 1180 grams (87%>).

Typical Procedure With Excess Acetic Anhydride. The procedure was basically the same as described above using stoichiometric acetic anhydride, except that a larger excess of acetic anhydride was charged. Generally, a 23%> excess was used except as noted in Table 2. The last stage of the reaction was much faster when excess acetic anhydride was used. The reaction was usually complete within about 5 minutes to about 30 minutes after vacuum was applied, as measured by an increase in the voltage to the stirrer to maintain constant speed.

Physical Properties. The inherent viscosity (IN.) of each sample was measured at 25 °C as a 0.1%) solution (wt./volume) in equal parts by volume of pentafluorophenol and hexafluoroisopropanol. The melting temperature (T_m), heat of melting (ΔH_m), crystallization temperature on cooling from the molten state (T_c), and heat of crystallization (ΔH_C) were measured by differential scanning calorimetry (DSC; 20°C/min heating rate). The melt viscosity of the polymer was measured in a capillary viscometer at shear rates of 100 sec^"1 and 1000 sec"¹ . These properties are reported in Table 2.

Mechanical Properties. Samples of many of the polymers were compounded with 30%> by weight of glass fiber using a Werner Pfleiderer 28 mm ZSK twin screw extruder. The filled polymer samples were then made into specimens for physical testing by injection molding. For the sample of Example 10, the barrel temperature was 290° - 330°C and the mold temperature was 100°C. The following physical properties were measured using standard test methods: tensile properties (ASTM D638), flexural properties (ASTM D790), notched Izod (ASTM D256), and heat distortion temperature (ASTM D648). The test results are summarized in Table 3. The difference between the Tm measured by DSC and the heat distortion temperature are also shown in Table 3 as "Tm- HDT".

Fiber Properties. The molten polymer of Example 10(a) was extruded at about 340°C through a single hole spinneret (0.005 inch diameter and 0.007 inch length) at a rate of 0.15 g/min. The extruded filament was drawn down at a speed of 700 meters/minute and quenched in air at ambient conditions (about 25 °C and 65%> relative humidity). The tensile properties of the as-spun fiber were measured using ASTM test method D3822: tenacity, 6 gdp; elongation, 1.8%; modulus, 423 gpd. The as-spun fiber was then heat treated to obtain improved fiber properties as follows. Fiber in an unstressed state was heated from room temperature to 150°C over a period of 60 minutes. The fiber was held at 150°C for 60 minutes, then heated to 230°C over 60 minutes, held at 230°C for 3 hours, heated to 270°C over 60 minutes, and held at 270°C for 16 hours. The properties of the heat treated fibers were measured using ASTM test method D3822: tenacity, 16.3 gpd; elongation, 2.8%), modulus, 499 gpd.

For comparison, the polymer of Example 8(b) was spun at about 329 °C to yield a fiber (single filament) having an as-spun tenacity of 6.2 gpd; elongation, 1.6%; modulus, 440 gpd. After heat treatment, the fiber had tenacity, 22 gpd; elongation, 4.2%>; modulus, 463 gpd. A polymer having the same composition as Example 9 and an IN. - of 3.8 dl/g was spun at 340 °C through a single hole spinneret to yield a fiber having as- spun tenacity, 7.9 gpd; elongation, 2%; modulus, 450 gpd. After heat treatment, the fiber had tenacity, 23 gpd; elongation, 4.1%>; modulus, 500 gpd.

It is to be understood that the above described embodiments of the invention are illustrative only and that modification throughout may occur to one skilled in the art. Accordingly, this invention is not to be regarded as limited to the embodiments disclosed herein.

Table 1. POLYMERCOMPOSITIONS¹

Example HBA NDA TA HQ AA BP IA

1 20 20 20 32.5 7.5 - .

2 20 25 15 32.5 7.5 - -

3 20 30 10 32.5 7.5 - -

4 20 35 5 32.5 7.5 . _

5 30 20 15 27.5 7.5 - -

6 30 25 10 27.5 7.5 - -

7 40 15 15 22.5 7.5 - -

8 40 20 10 27.5 2.5 - -

9 40 20 10 26 4 - -

10 40 20 10 25 5 - -

11 40 20 10 22.5 7.5 - .

12 40 20 10 15 15 - -

13 40 20 10 10 20 - -

14 40 20 10 5 25 - -

15 40 25 5 25 5 - -

16 50 10 15 17.5 7.5 - -

17 50 15 10 17.5 7.5 - -

18 50 17.5 7.5 17.5 7.5 - -

19 50 20 5 17.5 7.5 - -

20 60 15 5 12.5 7.5 - -

21 40 20 10 15 5 10 -

¹ Expressed as mole% of monomer units derived from 4- hydroxybenzoic acid (HBA), 2, 6-naphthalenedicarboxylic acid (NDA), terephthalic acid (TA) , 1, 4-hydroquinone (HQ) , 4- aminophenol (AA) , 4, 4 ' -biphenol (BP) , and isophthalic acid (IA) Table 1. (cont'd POLYMER COMPOSITIONS

22 40 20 10 20 5 5 -

Example HBA NDA TA HQ AA BP IA

C-1² 60 20 - 15 5 - -

C-2 50 25 - 20 5 - -

C-3 35 5 - 27.5 5 - 27.5

C-4 50 15 - 20 5 - 10

C-5 60 15 - 15 5 - 5

C-6 40 20 10 30 - - -

C-7 60 6 14 8 - 12 -

C-8 60 3 17 - 5 15 -

C-9 50 10 15 - 5 20 -

C-10 40 20 10 - 5 25 -

Examples C-1 to C-10 are comparative examples Table2. PHYSICALPROPERTIES

Example Method¹ I.V.² Melt Viscosity Tm³ ΔH Tc⁴ ΔHc (poise) m

T('C) 100 sec^"' lOOOsec^"1 (°C) (J/g) CC) (J/g)

1 Xes 2.9 330 4268 920 327 1.7 299 -2.3

2 33.3% 4.9 330 2126 727 321 5.4 280 -4.5 Xes

3 33.3% 3.1 330 1066 352 319 4.9 278 -5.3 Xes

4 43.5% _5 Xes

5 Xes 4.9 325 1672 641 318 3.1 277 -3.8

¹ "Sto" means "Stoichiometric" acetic anhydride; a 2.5% excess was used. "Xes" means excess acetic anhydride. Unless otherwise stated, 23% excess was used.

² Inherent viscosity.

³ Measured by DSC at a heating rate of 20°C/min.

⁴ Measured by DSC on cooling from the melt (Negative means heat is released) .

⁵ Polymer solidified during synthesis. No properties were measured. Table 2. fcont'dl PHYSICAL PROPERTIES

Example Method I.V. Melt Viscosity (poise) Tm ΔH Tc ΔHc m

TOO 100 sec"¹ lOOOsec^"1 CC) (J/g) CC) (J/g)

6 Xes 5.5 335 1163 469 327 4.8 284 -5

7 Xes 4.2 340 4844 1179 335 1.4 292 -2.3

8(a) Sto. 2.4 315 3843 705 318 5 286 -6.3

8(b) Xes 2.8 320 414 273 312 6 270 -5.4

9 Xes 4.1 320 2327 833 313 4.4 271 -5.1

10(a) Sto. 3.7 320 532 301 314 4.4 271 -4.2

10(b) Xes 3.0 320 470 287 311 5.8 269 -6.1

11(a) Xes 4.4 320 5855 1440 314 4.6 275 -4.5

11(b) Sto. 3.2 325 788 344 324 5.2 286 -5.4

12 Xes 4.3 360 730 307 319 2.8 277 -2.9

13 Xes 5.8 360 3512 1113 323 2.6 279 -2.4

14 Xes 3.7 360 883 405 329 3.8 287 -2

15 Xes 4.5 330 924 388 325 3.2 281 -4.7

16 Xes _6

⁶ Polymer solidified during synthesis. No properties were measured. Table 2. fcont'dl PHYSICAL PROPERTIES

Example Method I.V. MeltViscosity(poise) Tm ΔH Tc ΔHc m

T("C) 100sec^"1 lOOOsec"¹ CC) (J/g) CC) (J/g)

17 Xes 4.6 330 5149 1291 327 2.7 284 -3.2

18 Xes 4.8 320 2576 919 313 3.8 270 -3.3

19 Xes 5.3 325 2298 795 318 3.6 273 -3.7

20 Xes 4.8 340 3765 1138 321 2.2 279 -2.7

21 Sto. 4.0 275 2524 775 277 3.4 235 -4.3

22 Xes 5.4 300 2355 793 293 3.8 250 -3.3

C-1 Sto. 4.9 350 4582 1217 328 4 281 -4.1

C-2 Sto. 1.9 330 1030 346 326 4.6 -4.5 & 296

333

C-3 Sto. 0.8 ^■290 1516 461 265 5.3 212 -4.9

&

283

C-4 Sto. 2.2 280 967 390 269 0.9 215 -1.9

C-5 Sto. 3.6 310 2309 708 304 3.6 256 -3.1

C-6(a) Xes 2.7 315 253 192 310 6.2 269 -6.1

C-6(b) Sto. 2.0 316 4047 715 316 7.7 285 -6.2

C-7 Sto. 5.0 330 1060 355 326 1.4 291 -2.8

Table 2. fcont'd) PHYSICAL PROPERTIES

Example Method I.V. Melt Viscosity (poise) Tm ΔH Tc ΔHc m

TCQ 100 sec^"1 lOOOsec'¹ CQ (J/g) CQ (J/g)

C-8 Sto. 6.4 360 1457 445 363 3.3 304 -2.2

C-9 Sto. 7.0 300 5859 1208 303 0.8 262 -3.2

C-10 Sto. 4.7 275 1699 553 272 3 246 -3.2

Table 3. MECHANICAL PROPERTIES OF 30 WT% GLASS-FILLED POLYMERS

Example HDT Tensile Properties Flexural Properties Notched Tm-HDT

@ 264 Modulus Strength Elong. Modulus Strength Izod CQ psi

CC) (Mpsi) (Kpsi) (%) (Mpsi) (Kpsi) (ft-lb/in.)

1 294 1.9 17.3 1.3 1.8 28.3 2.5 33

2 297 2.4 27 2.2 2.1 34.8 2.3 24

3 297 n.m. n.m. n.m. 1.9 30.9 2.0 22

4 n. . n.m. n.m. n.m. n.m. n.m. n.m. n.m.

5 279 2 22 2 1.7 3^*1.4 2.9 39

6 296 2.3 27.1 2.4 2 35 2.1 31

7 281 1.8 15 1.3 1.8 29 3.5 54

8(a) 276 1.9 18.8 1.5 1.7 26.1 1.5 42

8(b) 280 2.1 18.6 1.2 1.8 29.2 2 32

9 281 2.2 19.3 1.3 2 32.5 2.6 32

10(a) 275 2.1 18.4 1.3 1.9 30.1 1.7 39

10(b) 278 2.2 23 1.7 2 31.4 1.9 33

11(a) 278 2.3 20.9 1.4 2.1 32.4 3 36

1 Kb) 278 2.1 17.8 1.3 1.8 28.1 1.5 46

12 286 2.7 28.7 1.8 2.3 38 2.6 33

13 282 n.m. n.m. n.m. 2.4 40 6.1 41

14 288 2.7 28.5 1.7 2.6 37 2.4 41

15 295 2.3 25.4 2.2 2 33 2.3 30

16 n.m. n.m. n.m. n.m. n.m. n.m. n.m. n.m.

17 ^' 290 2.4 26.6 2 2.1 33.3 2.5 37

18 279 2.7 27.4 1.9 2.2 34.4 5.1 34

19 278 2.9 30.5 2.1 2.2 35.2 4.2 40

20 283 2.7 29.7 2 2.3 33.4 4 38

21 232 2.3 23.9 1.8 1.7 31.7 1.9 45 Table 3. fcont'dl MECHANICAL PROPERTIES OF 30 WT% GLASS-FILLED POLYMERS

Example HDT Tensile Properties Flexural Properties Notched Tm-HDT

@ 264 Modulus Strength Elong. Modulus Strength Izod CQ psi

CO (Mpsi) (Kpsi) (%) (Mpsi) (Kpsi) (ft-lb/in.)

22 257 2.5 27.9 2.2 2.1 33.9 3.4 36

C-1 281 2.3 20.4 1.4 2.4 29.5 1.6 47

C-2 271 2.2 14.6 0.8 1.9 23.9 1.5 55&62

C-3 137 1.9 16 1.5 1.7 24.4 0.8 128&146

C-4 193 2.2 24.4 1.7 2 32 0.2 76

C-5 234 2.2 22.4 1.6 1.9 29.3 2 70

C-6(a) 268 2 15.4 1 1.6 24.5 1.4 42

C-6(b) 256 1.4 7.4 0.6 1.3 18.6 1.3 60

C-7 269 1.8 19 2 1.6 23.3 2.1 57

C-8 269 2.1 20.6 2 1.6 23.8 2.8 94

C-9 242 1.8 18 2.1 1.7 25.3 2.3 61

C-10 221 1.8 18.3 1.7 1.8 26.2 1.6 51

Claims

ClaimsWe claim:

1. A thermotropic liquid crystalline poly(esteramide) consisting essentially of monomer repeat units I, II, III, IV, V and optional VI, wherein:

rv ^is -°^{→ _o~}

and VI

wherein X is selected from the group consisting of NR', C=0, O, and mixtures thereof;

wherein R and R' are alike or different and are selected from the group consisting of H, alkyl groups having 1" to 4 carbon atoms, fluoroalkyl groups having 1 to 4 carbon atoms, phenyl, and mixtures thereof;

wherein some of the hydrogen atoms on the aromatic rings of said monomer repeat units I, II, III, IV, V and VI optionally may be replaced with substituents selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, fluoroalkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, Cl, Br, F, I, aromatic groups having up to 7 carbon atoms, and mixtures thereof;

wherein said liquid crystalline poly(esteramide) on a mole basis consists essentially of about 5% to about 80% of monomer repeat unit I, about 5% to about 35% of monomer repeat unit II, about 3% to about 20% of monomer repeat unit III, about 5% to about 35% of monomer repeat unit IV, about 2% to about 30% of monomer repeat unit V, and 0 to about 10% of monomer repeat unit VI.

2. The thermotropic liquid crystalline poly(esteramide) recited in Claim 1 , wherein said monomer repeat unit V is

r©^→

3. The thermotropic liquid crystalline poly(esteramide) recited in Claim 2, wherein said aromatic rings of said monomer repeat units I, II, III, IV, V and VI are unsubstituted.

4. The thermotropic liquid crystalline poly(esteramide) recited in Claim 3, consisting essentially of monomer repeat units I, II, III, IV and V.

5. The thermotropic liquid crystalline poly(esteramide) recited in Claim 3, on a mole basis consisting essentially of about 20% to about 60% of monomer repeat unit I, about 10% to about 30% of monomer repeat unit II, about 5% to about 15% of monomer repeat unit III, about 10% to about 30% of monomer repeat unit IV, about 5% to about 20% of monomer repeat unit V, and about 0 to about 10% of monomer repeat unit VI.

6. The thermotropic liquid crystalline poly(esteramide) recited in Claim 5, consisting essentially of monomer repeat units I, II, III, IV and V. 25

7. The thermotropic liquid crystalline poly(esteramide) recited in Claim 3, on a mole basis consisting essentially of about 30% to about 50% of monomer repeat unit I, about 15% to about 25% of monomer repeat unit II, about 5% to about 15% of monomer repeat unit III, about 20% to about 30% of monomer repeat unit IV, and about 5% to about 10% of monomer repeat unit V.

8. The thermotropic liquid crystalline poly(esteramide) recited in Claim 3, on a mole basis consisting essentially of about 40% of monomer repeat unit I, about 20% of monomer repeat unit II, about 10% of monomer repeat unit III, about 25% of monomer repeat unit IV, and about 5% of monomer repeat unit V.

9. A composition suitable for injection molding comprising the liquid crystalline poly(esteramide) of Claim 1 and up to about 70% by weight of one or more additives selected from the group consisting of reinforcing fillers, reinforcing fibers, oxidation stabilizers, heat stabilizers, light stabilizers, lubricants, mold release agents, dyes, pigments and plasticizers.

10. A composition suitable for injection molding comprising the liquid crystalline poly(esteramide) of Claim 1 and up to about 70% by weight of one or more additives selected from the group consisting of glass fiber, calcium silicate, silica, clays, talc, mica, polytetrafiuoroethylene, graphite, alumina, sodium aluminum carbonate, barium ferrite, woUastonite, carbon fiber, polymeric fiber, aluminum silicate fiber, titanium fiber, rock wool fiber, steel fiber, tungsten fiber, and woUastonite fiber.

11. A composition suitable for injection molding comprising the liquid crystalline poly(esteramide) of Claim 6 and up to about 70% by weight of one or more additives selected from the group consisting of reinforcing fillers, reinforcing fibers, oxidation stabilizers, heat stabilizers, light stabilizers, lubricants, mold release agents, dyes, pigments and plasticizers.

12. A composition suitable for injection molding comprising the liquid crystalline poly(esteramide) of Claim 6 and up to about 70% by weight of one or more additives selected from the group consisting of glass fiber, calcium silicate, silica, clays, talc, mica, polytetrafluoroethylene, graphite, alumina, sodium aluminum carbonate, barium ferrite, woUastonite, carbon fiber, polymeric fiber, aluminum silicate fiber, titanium fiber, rock wool fiber, steel fiber, tungsten fiber, and woUastonite fiber.

13. A shaped article comprising the polymer of Claim 1.

14. A shaped article comprising the polymer of Claim 5.

15. A shaped article comprising the polymer of Claim 6.

16. A fiber comprising the polymer of Claim 1.

17. A fiber comprising the polymer of Claim 6.

18. An extruded sheet or film comprising the polymer of claim 1.

19. An extruded sheet or film comprising the polymer of claim 6.