1. A polymer composition comprising a functional aromatic compound, wherein the functional aromatic compound comprises an aromatic diol, an aromatic dicarboxylic acid, or a combination thereof, the polymer composition further comprising a plurality of mineral fibers embedded in a thermotropic liquid crystalline polymer matrix, wherein the thermotropic liquid crystalline polymer matrix comprises monomeric repeat units derived from an aromatic diol, an aromatic dicarboxylic acid, an aromatic hydroxycarboxylic acid, or a combination thereof, wherein the mineral fibers have a median width of 1 to 35 micrometers and comprise 5 to 60 weight percent of the polymer composition, wherein the mineral fibers have an aspect ratio of 2 to 15.

2. The polymer composition of claim 1, wherein the liquid crystalline polymer matrix comprises 25 to 95 wt% of the composition.

3. The polymer composition according to claim 1 or claim 2, wherein the polymer has a total amount of repeating units derived from naphthenic hydroxycarboxylic acids and/or naphthenic dicarboxylic acids of greater than 10 mole%.

4. The polymer composition of claim 1 or claim 2, wherein the polymer comprises repeat units derived from 4-hydroxybenzoic acid, terephthalic acid, hydroquinone, 4' -biphenol, 6-hydroxy-2-naphthoic acid, 2, 6-naphthalenedicarboxylic acid, or combinations thereof.

5. The polymer composition according to claim 1 or claim 2, wherein at least 60 volume% of the mineral fibers have a diameter of 1 to 35 microns.

6. The polymer composition according to claim 1 or claim 2, wherein the mineral fibers have an aspect ratio of 4 to 15.

7. The polymer composition of claim 1 or claim 2, wherein the mineral fibers have a median width of 3 to 15 micrometers.

8. The polymer composition according to claim 1 or claim 2, wherein the mineral fibers comprise fibers derived from silicates.

9. The polymer composition according to claim 8, wherein the silicate is an inosilicate.

10. The polymer composition of claim 9, wherein the inosilicate comprises wollastonite.

11. The polymer composition of claim 1 or claim 2, wherein the functional aromatic compound comprises an aromatic diol.

12. The polymer composition of claim 11, wherein the aromatic diol is 4,4' -biphenol.

13. The polymer composition of claim 1 or claim 2, wherein the functional aromatic compound comprises an aromatic carboxylic acid.

14. The polymer composition of claim 13, wherein the aromatic carboxylic acid is 2, 6-naphthalene dicarboxylic acid.

15. The polymer composition of claim 1 or claim 2, wherein functional aromatic compound comprises 0.001 to 5 wt.% of the polymer composition.

16. The polymer composition of claim 1 or claim 2, further comprising an electrically conductive filler, a glass filler, a clay mineral, or a combination thereof.

17. The polymer composition according to claim 1 or claim 2, characterized in that the composition has a standard ISO test No.11443 of 0.1 to 80 Pa-s at 1000 seconds^-1And a melt viscosity measured at a temperature 15 ℃ above the melting temperature of the composition.

18. The polymer composition according to claim 1 or claim 2, wherein the composition further comprises at least one non-aromatic hydrate-functional compound.

19. The polymer composition of claim 18, wherein the hydrate comprises aluminum trihydrate.

20. The polymer composition of claim 18, wherein the hydrate comprises from 0.02 to 2 weight percent of the polymer composition.

21. The polymer composition of claim 16, wherein the electrically conductive filler comprises a carbon filler.

22. An electronic connector comprising a molded part comprising the polymer composition of any of the preceding claims.

Background

Compact camera modules ("CCMs") are commonly used for mobile phones, notebook computers, digital cameras, digital video cameras, and the like that include a plastic lens barrel mounted on a base. Because conventional plastic lenses cannot withstand reflow soldering, camera modules are typically not surface mounted. However, attempts have been made to use liquid crystal polymers having high heat resistance for molded parts of compact camera modules such as lens barrels or bases on which the lens barrels are mounted. In order to improve the mechanical properties of such polymers, it is known to add plate-like substances (e.g. talc) and milled glass. Although strength and modulus of elasticity can be improved in this manner, problems are still encountered when attempting to use such materials for compact camera modules due to their small dimensional tolerances. For example, mechanical properties are often poor or non-uniform, which results in poor filling and lack of dimensional stability in molded parts. In addition, increasing the amount of ground glass to improve mechanical properties can result in an overly rough surface, which can lead to errors in camera performance and sometimes cause undesirable particulate generation.

There is also a need for a polymer composition that can be easily used for molded parts of compact camera modules and that also achieves good mechanical properties.

Disclosure of Invention

In accordance with one embodiment of the present invention, a polymer composition comprising a functional aromatic compound and a plurality of mineral fibers embedded in a thermotropic liquid crystalline polymer matrix is disclosed. The mineral fibers have a median width of from about 1 to about 35 microns and comprise from about 5% to about 60% by weight of the polymer composition.

Other features and aspects of the present invention are set forth in more detail below.

Drawings

A full and enabling disclosure of the present invention, including the best mode thereof to one skilled in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which:

FIG. 1 is an exploded perspective view of one embodiment of a fine pitch electrical connector that may be formed in accordance with the present invention;

fig. 2 is a front view of an opposing wall of the fine pitch electrical connector of fig. 1;

FIG. 3 is a schematic view of one embodiment of an extruder screw that can be used to form the polymer composition of the present invention;

FIGS. 4-5 are respective front and rear perspective views of an electronic assembly that may use an antenna structure formed in accordance with one embodiment of the present invention; and

fig. 6-7 are perspective and front views of a compact camera module ("CCM") that may be formed according to an embodiment of the present invention.

Detailed Description

"alkyl" refers to a monovalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and in some embodiments, 1 to 6 carbon atoms. "C_x-yAlkyl "refers to an alkyl group having x to y carbon atoms. The term includes by way of example straight or branched chain hydrocarbon radicals such as methyl (CH)₃) Ethyl (CH)₃CH₂) N-propyl (CH)₃CH₂CH₂) (CH) isopropyl group₃)₂CH) and n-butyl (CH)₃CH₂CH2CH₂) And isobutyl ((CH)₃)₂CHCH₂) Sec-butyl ((CH)₃)(CH₃CH₂) CH), tert-butyl ((CH)₃)₃C) N-pentyl group (CH)₃CH₂CH₂CH₂CH₂) And neopentyl ((CH)₃)₃CCH₂)。

"alkoxy" means the group-O-alkyl. Alkoxy groups include, by way of example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy and n-pentoxy.

"alkenyl" means having 2 to 10 carbon atoms and in some embodiments 2 to 6 carbon atoms or 2 to 4 carbon atoms and having at least 1 site of vinyl unsaturation (>C＝C<) A straight or branched hydrocarbon group of (1). For example, (C)_x-C_y) Alkenyl refers to alkenyl groups having x to y carbon atoms and is intended to include, for example, ethenyl, propenyl, 1, 3-butadienyl, and the like.

"aryl" refers to an aromatic group of 3 to 14 carbon atoms and no ring heteroatoms and having a single ring (e.g., phenyl) or multiple condensed (fused) rings (e.g., naphthyl or anthracenyl). For polycyclic ring systems, including fused, bridged, and spiro ring systems having aromatic and non-aromatic rings that do not contain ring heteroatoms, the term "aryl" applies when the point of attachment is at an aromatic carbon atom (e.g., 5,6,7, 8-tetrahydronaphthalen-2-yl is aryl, since its point of attachment is at the 2-position of the aromatic phenyl ring).

"aryloxy" refers to the group-O-aryl, which includes by way of example phenoxy and naphthoxy.

"carboxy (" Carboxyl "or" carboxy ")" means-COOH or a salt thereof.

"Carboxyester" or "carboxy ester" means the group-C (O) O-alkyl, C (O) O-alkenyl, C (O) O-aryl, C (O) O-cycloalkyl, -C (O) O-heteroaryl, -C (O) O-heterocyclyl.

"cycloalkyl" means 3 to 14 carbon atoms and no ring heteroatoms and has a saturated or partially saturated cyclic group of monocyclic or polycyclic rings including fused, bridged and spiro ring systems. For polycyclic systems having aromatic and non-aromatic rings that do not contain ring heteroatoms, the term "cycloalkyl" applies when the point of attachment is at a non-aromatic carbon atom (e.g., 5,6,7, 8-tetrahydronaphthalen-5-yl). The term "cycloalkyl" includes cycloalkenyl groups such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, and cyclohexenyl. The term "cycloalkenyl" is sometimes used to refer to partially saturated cycloalkyl rings having at least one site of > C ═ C < ring unsaturation.

"Cycloalkoxy" refers to-O cycloalkyl.

"halo" or "halogen" refers to fluoro, chloro, bromo, and iodo.

"haloalkyl" refers to an alkyl group substituted with 1 to 5, or in some embodiments, 1 to 3 halo groups.

"heteroaryl" refers to aryl groups of 1 to 14 carbon atoms and 1 to 6 heteroatoms selected from oxygen, nitrogen and sulfur and includes monocyclic (e.g., imidazolyl) and polycyclic systems (e.g., benzimidazol-2-yl and benzimidazol-6-yl). For polycyclic ring systems, including fused, bridged, and spiro ring systems having aromatic and non-aromatic rings, the term "heteroaryl" applies where at least one ring heteroatom is present and the point of attachment is at an atom of the aromatic ring (e.g., 1,2,3, 4-tetrahydroquinolin-6-yl and 5,6,7, 8-tetrahydroquinolin-3-yl). In some embodiments, one or more nitrogen and/or sulfur ring atoms of the heteroaryl group are optionally oxidized to provide an N oxide (N → O), sulfinyl, or sulfonyl moiety. Examples of heteroaryl groups include, but are not limited to, pyridyl, furyl, thienyl, thiazolyl, isothiazolyl, triazolyl, imidazolyl, imidazolinyl, isoxazolyl, pyrrolyl, pyrazolyl, pyridazinyl, pyrimidinyl, purinyl, naphthyridinyl, naphthylpyridyl, benzofuryl, tetrahydrobenzofuryl, isobenzofuryl, benzothiazolyl, benzisothiazolyl, benzotriazolyl, indolyl, isoindolyl, indolizinyl, indazolyl, indolinyl, benzoxazolyl, quinolyl, isoquinolyl, quinolizinyl, quinazolinyl, quinoxalinyl, tetrahydroquinolyl, isoquinolyl, quinazolinone, benzimidazolyl, benzisoxazolyl, benzothienyl, benzopyrazinyl, pteridinyl, carbazolyl, carbolinyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, imidazolyl, isoxazolyl, pyrimidinyl, oxazolyl, benzoxazolyl, and the like, Phenoxazinyl, phenothiazinyl and phthalimidyl.

"heteroaryloxy" means-O-heteroaryl.

"heterocyclic" or "heterocycle" or "heterocycloalkyl" or "heterocyclyl" refers to a saturated or partially saturated cyclic group having from 1 to 14 carbon atoms and from 1 to 6 heteroatoms selected from nitrogen, sulfur or oxygen, and includes monocyclic rings and polycyclic ring systems including fused, bridged and spiro ring systems. For polycyclic ring systems having aromatic and/or non-aromatic rings, the terms "heterocyclic", "heterocycle", "heterocycloalkyl", or "heterocyclyl" apply when at least one ring heteroatom is present and the point of attachment is at an atom of the non-aromatic ring (e.g., decahydroquinolin-6-yl). In some embodiments, one or more of the nitrogen and/or sulfur atoms of the heterocyclic group is optionally oxidized to provide an N-oxide, sulfinyl, or sulfonyl moiety. Examples of heterocyclyl groups include, but are not limited to, azetidinyl, tetrahydropyranyl, piperidinyl, N-methylpiperidin-3-yl, piperazinyl, N-methylpyrrolidin-3-yl, 3-pyrrolidinyl, 2-pyrrolidin-1-yl, morpholinyl, thiomorpholinyl, imidazolidinyl, and pyrrolidinyl.

"heterocyclyloxy" refers to the group-O-heterocyclyl.

"acyl" refers to the groups H-C (O) -, alkyl-C (O) -, alkenyl-C (O) -, cycloalkyl-C (O) -, aryl-C (O) -, heteroaryl-C (O) -, and heterocyclyl-C (O) -. Acyl includes the "acetyl" group CH₃C(O)-。

"acyloxy" refers to the groups alkyl-C (O) O-, alkenyl-C (O) O-, aryl-C (O) O-, cycloalkyl-C (O) O-, heteroaryl-C (O) O-, and heterocyclyl-C (O) O-. Acyloxy groups including the "acetoxy" group CH₃C(O)O-。

"acylamino" refers to the group-NHC (O) alkyl, -NHC (O) alkenyl, -NHC (O) cycloalkyl, -NHC (O) aryl, -NHC (O) heteroaryl, and-NHC (O) heterocycle. Acylamino groups include "acetylamino" -NHC (O) CH₃。

It is to be understood that the above definitions include unsubstituted groups as well as groups substituted with one or more other functional groups known in the art. For example, an aryl, heteroaryl, cycloalkyl or heterocyclyl group may be substituted with 1 to 8, in some embodiments 1 to 5, in some embodiments 1 to 3 and in some embodiments 1 to 2 substituents selected from the group consisting of: alkyl, alkenyl, alkynyl, alkoxy, acyl, acylamino, acyloxy, amino, quaternary amino, amide, imino, amidino, aminocarbonylamino, amidinocarbonylamino, aminothiocarbonyl, aminocarbonylamino, aminothiocarbonylamino, aminocarbonyloxy, aminosulfonyl, aminosulfonyloxy, aminosulfonylamino, aryl, aryloxy, arylthio, azido, carboxyl ester, (carboxyl ester) amino, (carboxyl ester) oxy, cyano, cycloalkyl, cycloalkoxy, cycloalkylthio, guanidino, halogen, haloalkyl, haloalkoxy, hydroxyl, hydroxyamino, alkoxyamino, hydrazino, heteroaryl, heteroaryloxy, heteroarylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, nitro, oxo, thione, phosphate, phosphonate, phosphinate, phosphonamidate, amino, carboxyl ester, amino (carboxyl ester) amino, cyano, cycloalkyl, cycloalkoxy, cycloalkyloxy, guanidino, halogen, haloalkyl, haloalkoxy, hydroxyl, amino, nitro, amino, phosphoramidates, cyclic phosphorodiamidates, phosphoramidates, sulfates, sulfonates, sulfonyls, substituted sulfonyloxy groups, thioacyl groups, thiocyanates, mercapto groups, alkylthio groups, and the like, as well as combinations of the foregoing substituents.

It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.

The present invention relates generally to polymer compositions comprising a functional aromatic compound and a plurality of mineral fibers (also referred to as "whiskers") distributed within a liquid crystalline polymer matrix. In particular, the inventors have found that such compositions can achieve low melt viscosities without sacrificing the mechanical properties of the composition. Without wishing to be bound by theory, it is believed that the aromatic-functional aromatic compound may react with the polymer chain to shorten its length and thus reduce melt viscosity. As a result of the present invention, the melt viscosity of the polymer composition is generally low enough that it can easily flow into the cavities of a mold having small dimensions. For example, in a particular embodiment, the polymer composition may have a melt viscosity of from about 0.5Pa · s to about 100Pa · s, in some embodiments from about 1Pa · s to about 80Pa · s, and in some embodiments, from about 5Pa · s to about 50Pa · s. The melt viscosity can be measured according to ISO test No.11443 at 1000 seconds^-1And a temperature 15 c above the melting temperature of the composition (e.g., 350 c).

In general, it is believed that polymer compositions having such low viscosities also do not have sufficiently good thermal and mechanical stability or sufficiently smooth surfaces that enable them to be used in certain types of applications. Contrary to conventional thinking, however, it has been found that the polymer compositions of the present invention have excellent thermal and mechanical properties. This is due in part to the use of certain characteristics, sizes and relative concentrations of mineral fibers. Examples of such mineral fibers include, for example, those derived from: silicates such as nesosilicate, sorosilicate, inosilicates (examples)Such as calcium chain silicates, e.g. wollastonite; calcium magnesium chain silicates such as tremolite; calcium magnesium iron chain silicates such as actinolite; magnesium iron chain silicates such as dellite, etc.), layered silicates (e.g., aluminum layered silicates such as palygorskite), network silicates, etc.; sulfates such as calcium sulfate (e.g., dehydrated or anhydrous gypsum); mineral wool (e.g., rock wool or slag wool), and the like. Particularly suitable are inosilicates such as wollastonite fibers, which may be available under the trade name Nyco Minerals(e.g. in4W or8) And (4) obtaining.

The mineral fibers may have a median width (e.g., diameter) of from about 1 to about 35 microns, in some embodiments from about 2 to about 20 microns, in some embodiments from about 3 to about 15 microns, in some embodiments from about 7 to about 12 microns. The mineral fibers may also have a narrow size distribution. That is, at least about 60% by volume of the fibers, in some embodiments at least about 70% by volume of the fibers, and in some embodiments at least about 80% by volume of the fibers can have a size within the above-described ranges. Without wishing to be bound by theory, it is believed that mineral fibers having the above dimensional characteristics can move more easily through the molding apparatus, which enhances distribution within the polymer matrix and minimizes the generation of surface defects. In addition to having the above dimensional characteristics, the mineral fibers may also have a relatively high aspect ratio (average length divided by median width) to help further improve the mechanical properties and surface quality of the resulting polymer composition. For example, the mineral fibers may have an aspect ratio of from about 1 to about 50, in some embodiments from about 2 to about 20, and in some embodiments, from about 4 to about 15. The volume average length of such mineral fibers may range, for example, from about 1 to about 200 microns, in some embodiments from about 2 to about 150 microns, in some embodiments from about 5 to about 100 microns, and in some embodiments, from about 10 to about 50 microns.

The relative amount of such mineral fibers can be selectively controlled to help achieve desired mechanical properties without negatively affecting other properties of the composition such as its smoothness when formed into a molded part. For example, mineral fibers typically constitute from about 5% to about 60%, in some embodiments from about 10% to about 50%, and in some embodiments, from about 20% to about 40% by weight of the polymer composition. Similarly, the functional aromatic compound typically comprises from about 0.001 wt.% to about 5 wt.%, in some embodiments from about 0.01 wt.% to about 1 wt.%, and in some embodiments, from about 0.05 wt.% to about 0.5 wt.% of the polymer composition. While the concentration of the liquid crystalline polymers may generally vary based on the presence of other optional components, they are typically present in an amount of from about 25% to about 95% by weight, in some embodiments from about 30% to about 80% by weight, and in some embodiments, from about 40% to about 70% by weight.

Various embodiments of the present invention will now be described in more detail.

I. Liquid crystalline polymers

Thermotropic liquid crystalline polymers typically have a high degree of crystallinity that allows them to effectively fill the small spaces of the mold. Suitable thermotropic liquid crystalline polymers can include aromatic polyesters, aromatic poly (ester amides), aromatic poly (ester carbonates), aromatic polyamides, and the like, and can likewise contain repeating units formed from one or more aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic aminocarboxylic acids, aromatic amines, aromatic diamines, and the like, as well as combinations thereof.

Liquid crystal polymers are generally classified as "thermotropic" in the sense that they can have a rod-like structure and exhibit crystalline behavior in their molten state (e.g., thermotropic nematic state). Such polymers may be formed from one or more types of repeating units known in the art. The liquid crystalline polymer may, for example, typically comprise one or more aromatic ester repeat units in an amount of from about 60 mole% to about 99.9 mole%, in some embodiments from about 70 mole% to about 99.5 mole%, and in some embodiments, from about 80 mole% to about 99 mole% of the polymer. The aromatic ester repeat unit may be generally represented by the following formula (V):

wherein ring B is a substituted or unsubstituted 6-membered aryl (e.g., 1, 4-phenylene or 1, 3-phenylene), a substituted or unsubstituted 6-membered aryl (e.g., 2, 6-naphthalene) fused to a substituted or unsubstituted 5 or 6-membered aryl, or a substituted or unsubstituted 6-membered aryl (e.g., 4, 4-biphenylene) linked to a substituted or unsubstituted 5 or 6-membered aryl; and

Y₁and Y₂Independently O, C (O), NH, C (O) HN or NHC (O).

Typically, Y₁And Y₂At least one of (a) is C (O). Examples of such aromatic ester repeating units may include, for example, aromatic dicarboxylic acid repeating units (Y in formula V)₁And Y₂Is C (O), an aromatic hydroxycarboxylic acid repeating unit (Y in the formula V)₁Is O and Y₂C (O)) and various combinations thereof.

For example, aromatic dicarboxylic acid repeating units derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, diphenyl ether-4, 4 '-dicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4' -dicarboxybiphenyl, bis (4-carboxyphenyl) ether, bis (4-carboxyphenyl) butane, bis (4-carboxyphenyl) ethane, bis (3-carboxyphenyl) ether, bis (3-carboxyphenyl) ethane, and the like, as well as alkyl, alkoxy, aryl, and halogen substituents thereof, and combinations thereof, may be used. Particularly suitable aromatic dicarboxylic acids may include, for example, terephthalic acid ("TA") and isophthalic acid ("IA") and 2, 6-naphthalene dicarboxylic acid ("NDA"). When used, the repeat units derived from aromatic dicarboxylic acids (e.g., IA, TA, and/or NDA) typically comprise from about 5 mol% to about 60 mol%, in some embodiments from about 10 mol% to about 55 mol%, and in some embodiments, from about 15 mol% to about 50% of the polymer.

Aromatic hydroxycarboxylic acid repeating units derived from aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 4-hydroxy-4 '-bibenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-5-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, 4' -hydroxyphenyl-4-benzoic acid, 3 '-hydroxyphenyl-4-benzoic acid, 4' -hydroxyphenyl-3-benzoic acid, and the like, as well as alkyl, alkoxy, aryl, and halogen substituents thereof, and combinations thereof, may also be used. Particularly suitable aromatic hydroxycarboxylic acids are 4-hydroxybenzoic acid ("HBA") and 6-hydroxy-2-naphthoic acid ("HNA"). When used, the repeat units derived from hydroxycarboxylic acids (e.g., HBA and/or HNA) typically constitute from about 10 mole% to about 85 mole%, in some embodiments from about 20 mole% to about 80 mole%, and in some embodiments, from about 25 mole% to about 75 mole% of the polymer.

Other repeat units may also be used in the polymer. For example, in certain embodiments, repeating units derived from aromatic diols such as hydroquinone, resorcinol, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 4' -dihydroxybiphenyl (or 4,4' -biphenol), 3' -dihydroxybiphenyl, 3,4' -dihydroxybiphenyl, 4' -dihydroxybiphenyl ether, bis (4-hydroxyphenyl) ethane, as well as alkyl, alkoxy, aryl, and halogen substituents thereof, and combinations thereof, may be used. Particularly suitable aromatic diols may include, for example, hydroquinone ("HQ") and 4,4' -biphenol ("BP"). When used, the repeat units derived from aromatic diols (e.g., HQ and/or BP) typically comprise from about 1 mole% to about 30 mole%, in some embodiments from about 2 mole% to about 25 mole%, and in some embodiments, from about 5 mole% to about 20% of the polymer. Repeating units such as those derived from aromatic amides (e.g., acetaminophen ("APAP")) and/or aromatic amines (e.g., 4-aminophenol ("AP"), 3-aminophenol, 1, 4-phenylenediamine, 1, 3-phenylenediamine, etc.) may also be used. When used, the repeating units derived from an aromatic amide (e.g., APAP) and/or an aromatic amine (e.g., AP) typically comprise from about 0.1 mole% to about 20 mole%, in some embodiments from about 0.5 mole% to about 15 mole%, and in some embodiments, from about 1 mole% to about 10% of the polymer. It is also understood that various other monomeric repeat units may be incorporated into the polymer. For example, in certain embodiments, the polymer may comprise one or more repeat units derived from a non-aromatic monomer such as an aliphatic or cycloaliphatic hydroxycarboxylic acid, dicarboxylic acid, diol, amide, amine, and the like. Of course, in other embodiments, the polymer may be "wholly aromatic" in that it lacks repeat units derived from non-aromatic (e.g., aliphatic or cycloaliphatic) monomers.

Although not required, the liquid crystalline polymer can be a "cycloalkane-rich" polymer in the sense of containing relatively high levels of repeating units derived from cycloalkane hydroxycarboxylic acids and cycloalkane dicarboxylic acids such as naphthalene-2, 6-dicarboxylic acid ("NDA"), 6-hydroxy-2-naphthoic acid ("HNA"), or combinations thereof. That is, the total amount of repeating units derived from naphthenic hydroxycarboxylic and/or dicarboxylic acids (e.g., NDA, HNA, or a combination of HNA and NDA) is typically greater than about 10 mole%, in some embodiments greater than about 15 mole%, and in some embodiments from 18 mole% to about 70 mole% of the polymer. In a particular embodiment, for example, "naphthenic-rich" aromatic polyesters can be formed that comprise aromatic polyesters derived from naphthenic acids (e.g., NDA and/or HNA); 4-hydroxybenzoic acid ("HBA"), terephthalic acid ("TA") and/or isophthalic acid ("IA"), and various other optional moieties. The monomeric units derived from 4-hydroxybenzoic acid ("HBA") may comprise from about 30 mole% to about 95 mole%, in some embodiments from about 35 mole% to about 90 mole%, and in some embodiments, from about 40 mole% to about 80 mole% of the polymer, while the monomeric units derived from terephthalic acid ("TA") and/or isophthalic acid ("IA") may each comprise from about 1 mole% to about 30 mole%, in some embodiments, from about 2 mole% to about 25 mole%, and in some embodiments, from about 3 mole% to about 20 mole% of the polymer. Other possible monomer repeat units include aromatic diols such as 4,4' -biphenol ("BP"), hydroquinone ("HQ"), and the like, and aromatic amides such as acetaminophen ("APAP"). When used, in certain embodiments, for example, BP, HQ, and/or APAP may comprise from about 1 mole% to about 40 mole%, in some embodiments from about 10 mole% to about 35 mole%, and in some embodiments, from about 20 mole% to about 30 mole%.

Regardless of the particular components and nature of the polymer, the liquid crystal composition may be prepared by first introducing one or more aromatic monomers (e.g., aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, etc.) and/or other repeating units (e.g., aromatic diols, aromatic amides, aromatic amines, etc.) used to form the ester repeating units into a reaction vessel to initiate the polycondensation reaction. The specific conditions and procedures used in such reactions are well known and can be described in more detail in U.S. patent nos. 4,161,470; U.S. patent No. 5,616,680 to linstid.iii et al; U.S. patent No. 6,114,492 to linstid.iii et al; U.S. Pat. No. 6,514,611 to Shepherd et al and WO 2004/058851 to Waggoner. The vessel used for the reaction is not particularly limited, but it is typically desirable to use a vessel generally used for the reaction of a highly viscous fluid. Examples of such a reaction vessel may include a stirring tank type apparatus having a stirrer having a variable-shaped stirring blade such as an anchor type, a multistage type, a helical ribbon type, a helical shaft type, etc., or a modified shape thereof. Other examples of such a reaction vessel may include mixing devices commonly used for resin kneading such as a kneader, a roll kneader, a banbury mixer, and the like.

The reaction may be carried out by acetylation of monomers known in the art, if desired. This can be accomplished by adding an acetylating agent (e.g., acetic anhydride) to the monomer. Acetylation is typically initiated at a temperature of about 90 ℃. Reflux may be employed during the initial stages of acetylation to maintain the vapor phase temperature below the point at which distillation of acetic acid by-product and anhydride begins. The temperature during acetylation is typically in the range of 90 ℃ to 150 ℃, in some embodiments from about 110 ℃ to about 150 ℃. If reflux is used, the vapor phase temperature typically exceeds the boiling point of acetic acid, but remains low enough to retain residual acetic anhydride. For example, acetic anhydride is evaporated at a temperature of about 140 ℃. It is therefore particularly desirable to provide a reactor having a vapor phase that is refluxed at a temperature of about 110 ℃ to about 130 ℃. To ensure substantially complete reaction, an excess of acetic anhydride may be used. The amount of excess anhydride will vary depending on the particular acetylation conditions used (including the presence or absence of reflux). It is not uncommon to use an excess of about 1 to about 10 mole percent acetic anhydride, based on the total moles of reactant hydroxyl groups present.

The acetylation may occur in a separate reaction vessel, or may occur in situ in the polymerization reaction vessel. When a separate reaction vessel is used, one or more monomers may be introduced into the acetylation reactor and subsequently transferred to the polymerization reactor. Likewise, it is also possible to introduce one or more monomers directly into the reaction vessel without prior acetylation.

In addition to the monomers and optional acetylating agent, other components may be included in the reaction mixture to help promote polymerization. For example, a catalyst such as a metal salt catalyst (e.g., magnesium acetate, tin (I) acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, etc.) and an organic compound catalyst (e.g., N-methylimidazole) may be optionally used. Such catalysts are typically used in amounts of about 50 to about 500ppm based on the total weight of the repeating unit precursor. When a separate reactor is used, it is typically desirable to apply the catalyst to the acetylation reactor rather than the polymerization reactor, although this is by no means a requirement.

The reaction mixture is typically heated to an elevated temperature in the polymerization reaction vessel to initiate melt polycondensation of the reactants. For example, polycondensation may occur at a temperature in the range of from about 250 ℃ to about 400 ℃, in some embodiments from about 280 ℃ to about 395 ℃, and in some embodiments, from about 300 ℃ to about 380 ℃. For example, one suitable technique for forming the liquid crystalline polymer may include feeding precursor monomers and acetic anhydride into a reactor, heating the mixture to a temperature of about 90 ℃ to about 150 ℃ to acetylate the hydroxyl groups of the monomers (e.g., to form acetoxy groups), and then raising the temperature to about 250 ℃ to about 400 ℃ to perform melt polycondensation. Volatile by-products of the reaction (e.g., acetic acid) can also be removed as the final polymerization temperature is approached, so that the desired molecular weight can be easily obtained. During the polymerization, the reaction mixture is usually stirred to ensure good heat and mass transfer and thus good material homogeneity. The rate of rotation of the stirrer may vary during the reaction, but typically ranges from about 10 to about 100 revolutions per minute ("rpm") and in some embodiments from about 20 to about 80 rpm. In order to build molecular weight in the melt, the polymerization reaction can also be carried out under vacuum, the application of which helps to remove the volatiles formed during the final stages of polycondensation. The vacuum may be created by applying a suction pressure, for example, in the range of about 5 to about 30 pounds per square inch ("psi") and in some embodiments, about 10 to about 20 psi.

After melt polymerization, the molten polymer may be discharged from the reactor, typically through an extrusion orifice equipped with a die of the desired configuration, cooled and collected. Typically, the melt is discharged through a perforated die to form a collected strand in a water bath, pelletized and dried. In some embodiments, the melt polymerized polymer may also be subjected to a subsequent solid state polymerization process to further increase its molecular weight. The solid state polymerization may be carried out in the presence of a gas (e.g., air, inert gas, etc.). Suitable inert gases may include, for example, nitrogen, helium, argon, neon, krypton, xenon, and the like, as well as combinations thereof. The solid state polymerization reaction vessel can be of virtually any design that allows for the desired residence time of the polymer at the desired solid state polymerization temperature. Examples of such vessels may be those having a fixed bed, a stationary bed, a moving bed, a fluidized bed, and the like. The temperature at which the solid state polymerization is carried out may vary, but is typically in the range of from about 250 ℃ to about 350 ℃. Of course, the polymerization time will vary based on the temperature and the target molecular weight. However, in most cases, the solid state polymerization time will be in the range of from about 2 to about 12 hours and in some embodiments from about 4 to about 10 hours.

Functional aromatic compounds

As indicated above, the polymer composition of the present invention further comprises a functional aromatic compound. Such compounds typically contain one or more carboxyl and/or hydroxyl functional groups that are capable of reacting with the polymer chain to shorten its length, as described above. In some cases, the compound may be capable of bonding shorter chains of the polymer together even after the melt viscosity of the composition has been reduced after the shorter chains of the polymer have been cut to help maintain the mechanical properties of the polymer. The functional compound typically has the following general structure provided in formula (I) or a metal salt thereof:

wherein

Ring B is a 6-membered aromatic ring, wherein 1 to 3 ring carbon atoms are optionally replaced by nitrogen or oxygen, wherein each nitrogen is optionally oxidized, and wherein ring B may be optionally fused or connected to a 5-or 6-membered aryl, heteroaryl, cycloalkyl or heterocyclyl group;

R₄is OH or COOH;

R₅is acyl, acyloxy (e.g., acetoxy), acylamino (e.g., acetamido), alkoxy, alkenyl, alkyl, amino, aryl, aryloxy, carboxyl ester, cycloalkyl, cycloalkyloxy, hydroxyl, halo, haloalkyl, heteroaryl, heteroaryloxy, heterocyclyl, or heterocyclyloxy;

m is from 0 to 4, in some embodiments from 0 to 2, and in some embodiments from 0 to 1; and

n is 1 to 3, and in some embodiments 1 to 2. When the compound is in the form of a metal salt, suitable metal counterions can include transition metal counterions (e.g., copper, iron, etc.), alkali metal counterions (e.g., potassium, sodium, etc.), alkaline earth metal counterions (e.g., calcium, magnesium, etc.), and/or main group metal counterions (e.g., aluminum).

In one embodiment, for example in formula (I) where B is phenyl, the resulting phenolic compound has the following general formula (II) or a metal salt thereof:

wherein

R₄Is OH or COOH;

R₆is acyl, acyloxy, acylamino, alkoxy, alkenyl, alkyl, amino, carboxyl ester, hydroxyl, halogen or halogenated alkyl; and

q is from 0 to 4, in some embodiments from 0 to 2, and in some embodiments from 0 to 1. Specific examples of such phenol compounds include, for example, benzoic acid (q is 0); 4-hydroxybenzoic acid (R)₄Is COOH, R₆Is OH and q is 1); phthalic acid (R)₄Is COOH, R₆Is COOH and q is 1); isophthalic acid (R)₄Is COOH, R₆Is COOH and q is 1); terephthalic acid (R)₄Is COOH, R₆Is COOH and q is 1); 2-Methylphthalic acid (R)₄Is COOH, R₆Is COOH and CH₃And q is 2); phenol (R)₄Is OH and q is 0); sodium phenolate (R)₄Is OH and q is 0); hydroquinone (R)₄Is OH, R₆Is OH and q is 1); resorcinol (R)₄Is OH, R₆Is OH and q is 1); 4-hydroxybenzoic acid (R)₄Is OH, R₆C (O) OH and q is 1), and the like, and combinations thereof.

In another embodiment, in formula (I) above, B is phenyl and R is₅Is phenyl such that the diphenol compound has the following general formula (III), or a metal salt thereof:

wherein

R₄Is COOH or OH;

R₆is acyl, acyloxy, acylamino, alkoxy, alkenyl, alkyl, amino, aryl, aryloxy, carboxyl ester, cycloalkyl, cycloalkoxy, hydroxyl, halo, haloalkyl, heteroaryl, heteroaryloxy, heterocyclyl or heterocycloxy; and

q is from 0 to 4, in some embodiments from 0 to 2, and in some embodiments from 0 to 1. Such diphenolsSpecific examples of the compound include, for example, 4-hydroxy-4' -bibenzoic acid (R)₄Is COOH, R₆Is OH and q is 1); 4' -hydroxyphenyl-4-benzoic acid (R)₄Is COOH, R₆Is OH and q is 1); 3' -hydroxyphenyl-4-benzoic acid (R)₄Is COOH, R₆Is OH and q is 1); 4' -hydroxyphenyl-3-benzoic acid (R)₄Is COOH, R₆Is OH and q is 1); 4,4' -Diphenyl Carboxylic acid (R)₄Is COOH, R₆Is COOH and q is 1); (R)₄Is OH, R₆Is OH and q is 1); 3,3' -Biphenyldiphenol (R)₄Is OH, R₆Is OH and q is 1); 3,4' -Biphenyldiphenol (R)₄Is OH, R₆Is OH and q is 1); 4-Phenylphenol (R)₄Is OH and q is 0); bis (4-hydroxyphenyl) ethane (R)₄Is OH, R₆Is C₂(OH)₂Phenol and q is 1); tris (4-hydroxyphenyl) ethane (R)₄Is OH, R₆Is C (CH)₃) Bisphenol and q is 1); 4-hydroxy-4' -biphenylcarboxylic acid (R)₄Is OH, R₆Is COOH and q is 1); 4' -hydroxyphenyl-4-benzoic acid (R)₄Is OH, R₆Is COOH and q is 1); 3' -hydroxyphenyl-4-benzoic acid (R)₄Is OH, R₆Is COOH and q is 1); 4' -hydroxyphenyl-3-benzoic acid (R)₄Is OH, R₆COOH and q is 1), and the like, and combinations thereof.

In still another embodiment, in the above formula (I), B is naphthyl, so that the resulting cycloalkane compound has the following general formula (IV):

wherein the content of the first and second substances,

R₄is OH or COOH;

R₆is acyl, acyloxy, acylamino, alkoxy, alkenyl, alkyl, amino, aryl, aryloxy, carboxyl ester, cycloalkyl, cycloalkoxy, hydroxyl, halo, haloalkyl, heteroaryl, heteroaryloxy, heterocyclyl or heterocycloxy; and

q is from 0 to 4, in some embodiments from 0 to 2,and in some embodiments from 0 to 1. Specific examples of such cycloalkane compounds include, for example, 1-naphthoic acid (R)₄Is COOH and q is 0); 2-naphthoic acid (R)₄Is COOH and q is 0); 2-hydroxy-6-naphthoic acid (R)₄Is COOH, R₆Is OH and q is 1); 2-hydroxy-5-naphthoic acid (R)₄Is COOH, R₆Is OH and q is 1); 3-hydroxy-2-naphthoic acid (R)₄Is COOH, R₆Is OH and q is 1); 2-hydroxy-3-naphthoic acid (R)₄Is COOH, R₆Is OH and q is 1); 2, 6-naphthalenedicarboxylic acid (R)₄Is COOH, R₆Is COOH and q is 1); 2, 3-naphthalenedicarboxylic acid (R)₄Is COOH, R₆Is COOH and q is 1); 2-hydroxy-naphthalene (R)₄Is OH and q is 0); 2-hydroxy-6-naphthoic acid (R)₄Is OH, R₆Is COOH and q is 1); 2-hydroxy-5-naphthoic acid (R)₄Is OH, R₆Is COOH and q is 1); 3-hydroxy-2-naphthoic acid (R)₄Is OH, R₆Is COOH and q is 1); 2-hydroxy-3-naphthoic acid (R)₄Is OH, R₆Is COOH and q is 1); 2, 6-dihydroxynaphthalene (R)₄Is OH, R₆Is OH and q is 1); 2, 7-dihydroxynaphthalene (R)₄Is OH, R₆Is OH and q is 1); 1, 6-dihydroxynaphthalene (R)₄Is OH, R₆OH and q is 1), and the like, and combinations thereof.

In certain embodiments of the present invention, for example, the polymer composition may comprise aromatic diols such as hydroquinone, resorcinol, 4' -biphenol, and the like, as well as combinations thereof. When used, such aromatic diols may comprise from about 0.01 wt.% to about 1 wt.%, and in some embodiments, from about 0.05 wt.% to about 0.4 wt.% of the polymer composition. Aromatic carboxylic acids may also be used in certain embodiments, either alone or in combination with the aromatic diols. The aromatic carboxylic acid may comprise from about 0.001 wt.% to about 0.5 wt.%, and in some embodiments, from about 0.005 wt.% to about 0.1 wt.% of the polymer composition. In a particular embodiment, an aromatic diol (in the above formula, R) is used in the present invention₄And R₆Is OH) (e.g. 4,4' -biphenol) with an aromatic dicarboxylic acid (in the above formula, R₄And R₆Being COOH) (e.g. 2, 6-naphthalenedicarboxylic acid) to assist inHelping to achieve the desired flow properties.

Optional Components

A. Non-aromatic functional compounds

Non-aromatic functional compounds other than those indicated above may also be used in the present invention. Such compounds may be used for various purposes, such as to further assist in reducing melt viscosity. One such non-aromatic functional compound is water. Water may be added if desired in the form of water produced under the process conditions. For example, the water may be added as a hydrate that effectively "loses" water under process conditions (e.g., elevated temperature). Such hydrates include aluminum trihydrate, copper sulfate pentahydrate, barium chloride dihydrate, calcium sulfate dehydrate, and the like, as well as combinations thereof. When used, the hydrate may comprise from about 0.02% to about 2%, and in some embodiments, from about 0.05% to about 1%, by weight of the polymer composition. In a particular embodiment, a mixture of an aromatic diol, a hydrate, and an aromatic dicarboxylic acid is used in the composition. In such embodiments, the weight ratio of hydrate to aromatic diol is typically from about 0.5 to about 8, in some embodiments from about 0.8 to about 5, and in some embodiments, from about 1 to about 5.

B. Conductive filler

If desired, electrically conductive fillers may be used in the polymer composition to help reduce the tendency for static electricity to develop during the molding operation. In fact, the inventors have found that the presence of a controlled size and amount of said mineral fibres, as indicated above, can enhance the ability of the conductive filler to be dispersed in said liquid crystalline polymer matrix, thereby allowing the use of relatively low concentrations of said conductive filler to achieve the desired electrostatic properties. However, because it is used in a relatively low concentration, the impact on thermal and mechanical properties can be minimized. In this aspect, when used, the electrically conductive filler typically comprises from about 0.1% to about 25%, in some embodiments from about 0.3% to about 10%, in some embodiments from about 0.4% to about 3%, and in some embodiments, from about 0.5% to about 1.5% by weight of the polymer composition.

Any of a variety of conductive fillers can generally be used in the polymer composition to help improve its electrostatic properties. Examples of suitable conductive fillers include, for example, metal particles (e.g., aluminum flakes), metal fibers, carbon particles (e.g., graphite, expanded graphite, graphene (graphene), carbon black, graphitized carbon black, and the like), carbon nanotubes, carbon fibers, and the like. Carbon fibers and carbon particles (e.g., graphite) are particularly suitable. When used, suitable carbon fibers may include pitch-based carbons (e.g., pitch), polyacrylonitrile-based carbons, metal-coated carbons, and the like. Desirably, the carbon fibers are of high purity, so they have a relatively high carbon content, such as a carbon content of about 85% by weight or greater, in some embodiments about 90% by weight or greater and in some embodiments about 93% by weight or greater. For example, the carbon content may be at least about 94 wt.%, such as at least about 95 wt.%, such as at least about 96 wt.%, such as at least about 97 wt.%, such as even at least about 98 wt.%. The carbon purity is typically less than 100 wt%, such as less than about 99 wt%. The carbon fibers typically have a density of about 0.5 to about 3.0g/cm³In some embodiments from about 1.0 to about 2.5g/cm³And in some embodiments from about 1.5 to about 2.0g/cm³。

In one embodiment, the carbon fibers are incorporated into the matrix with minimal fiber breakage. Even when fibers having an initial length of about 3mm are used, the volume average length of the fibers after molding can typically be from about 0.1mm to about 1 mm. The average length and distribution of the carbon fibers can also be selectively controlled in the final polymer composition to achieve better connection and electrical pathways in the liquid crystalline polymer matrix. The fibers may have an average diameter of from about 0.5 to about 30 microns, in some embodiments from about 1 to about 20 microns, and in some embodiments, from about 3 to about 15 microns.

To improve dispersion within the polymer matrix, the carbon fibers may be at least partially coated with a sizing agent that increases the compatibility of the carbon fibers with the liquid crystal polymer. The sizing agent may be stable so that it does not thermally degrade at the temperature at which the liquid crystal polymer is molded. In one embodiment, the sizing agent may include a polymer such as an aromatic polymer. For example, the aromatic polymer may have a thermal decomposition temperature greater than about 300 ℃, such as greater than about 350 ℃, such as greater than about 400 ℃. As used herein, the thermal decomposition temperature of a material is the temperature at which the material loses 5% of its mass during thermogravimetric analysis as determined according to ASTM test E1131 (or ISO test 11358). The sizing agent may also have a relatively high glass transition temperature. For example, the glass transition temperature of the sizing agent may be greater than about 300 ℃, such as greater than about 350 ℃, such as greater than about 400 ℃. Specific examples of sizing agents include polyimide polymers, aromatic polyester polymers (including wholly aromatic polyester polymers), and high temperature epoxy polymers. In one embodiment, the sizing agent may include a liquid crystal polymer. The sizing agent may be present on the fibers in an amount of at least about 0.1 wt.%, such as in an amount of at least 0.2 wt.%, such as in an amount of at least about 0.1 wt.%. The sizing agent is typically present in an amount of less than about 5 wt.%, such as in an amount of less than about 3 wt.%.

Another suitable conductive filler is an ionic liquid. One benefit of such materials is that in addition to being electrically conductive, the ionic liquid can exit in liquid form during melt processing, which allows it to be more uniformly blended within the liquid crystalline polymer matrix. This improves the electrical connection and thereby enhances the ability of the composition to rapidly dissipate electrostatic charges from its surface.

The ionic liquid is typically a salt having a sufficiently low melting temperature so that it can be in liquid form when melt processed with the liquid crystalline polymer. For example, the ionic liquid may have a melting temperature of about 400 ℃ or less, in some embodiments about 350 ℃ or less, in some embodiments from about 1 ℃ to about 100 ℃, and in some embodiments, from about 5 ℃ to about 50 ℃. The salt comprises a cationic species and a counter ion. The cationic species comprises as a "cationic center" a compound having at least one heteroatom (e.g., nitrogen or phosphorus). Examples of such heteroatom compounds include, for example, quaternary onium having the structure:

wherein R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Independently selected from hydrogen; substituted or unsubstituted C₁-C₁₀Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, etc.); substituted or unsubstituted C₃-C₁₄Cycloalkyl groups (e.g., adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, cyclohexenyl, and the like); substituted or unsubstituted C₁-C₁₀Alkenyl groups (e.g., ethenyl, propenyl, 2-methylpropenyl, pentenyl, etc.); substituted or unsubstituted C₂-C₁₀Alkynyl groups (e.g., ethynyl, propynyl, etc.); substituted or unsubstituted C₁-C₁₀Alkoxy (e.g., methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, etc.); substituted or unsubstituted acyloxy (e.g., methacryloxy, methacryloxyethyl, etc.); substituted or unsubstituted aryl (e.g., phenyl); substituted or unsubstituted heteroaryl (e.g., pyridyl, furyl, thienyl, thiazolyl, isothiazolyl, triazolyl, imidazolyl, isothiazolylOxazolyl, pyrrolyl, pyrazolyl, pyridazinyl, pyrimidinyl, quinolinyl, and the like); and the like. In a particular embodiment, for example, the cationic species can be of structure N⁺R¹R²R³R⁴Wherein R is¹、R²And/or R³Independently is C₁-C₆Alkyl (e.g., methyl, ethyl, butyl, etc.) and R⁴Is hydrogen or C₁-C₄Alkyl (e.g., methyl or ethyl). For example, the cationic component can be tributylmethylammonium, wherein R is¹、R²And R³Is butyl, and R⁴Is methyl.

Suitable counter ions for cationic species may include, for example, halogens (e.g., chloride, bromide, iodide, etc.); sulfate or sulfonate groups (e.g., methyl sulfate, ethyl sulfate, butyl sulfate, hexyl sulfate, octyl sulfate, hydrogen sulfate, methane sulfonate, dodecyl benzene sulfonate, dodecyl sulfate, trifluoromethane sulfonate, heptadecafluorooctane sulfonate, sodium lauryl ethoxy sulfate, etc.); a sulfosuccinate group; amides (e.g., dicyandiamide); imides (e.g., bis (pentafluoroethyl-sulfonyl) imide, bis (trifluoromethylsulfonyl) imide, bis (trifluoromethyl) imide, and the like); borates (e.g., tetrafluoroborate, tetracyanoborate, bis [ oxalato ] borate, bis [ salicylato ] borate, etc.); phosphate or phosphinate (e.g., hexafluorophosphate, diethylphosphate, bis (pentafluoroethyl) phosphinate, tris (pentafluoroethyl) -trifluorophosphate, tris (nonafluorobutyl) trifluorophosphate, etc.); antimonate (e.g., hexafluoroantimonate); aluminates (e.g., tetrachloroaluminates); fatty acid carboxylates (e.g., oleate, isostearate, pentadecafluorooctanoate, etc.); cyanate radical; acetate, and the like, as well as combinations of any of the foregoing. To help improve compatibility with the liquid crystalline polymer, it may be desirable to select counter ions that are generally hydrophobic in nature, such as imides, fatty acid carboxylates, and the like. Particularly suitable hydrophobic counterions can include, for example, bis (pentafluoroethylsulfonyl) imide, bis (trifluoromethylsulfonyl) imide and bis (trifluoromethyl) imide.

In certain embodiments, a synergistic effect may be achieved by using the ionic liquid in combination with a carbon filler (e.g., graphite, carbon fiber, etc.). Without wishing to be bound by theory, the present invention believes that the ionic liquid can flow easily during melt processing to help provide better connection and electrical pathways between the carbon filler and the liquid crystalline polymer matrix, thereby further reducing surface resistance.

C.Glass filler

Glass fillers, which are not generally electrically conductive, may also be used in the polymer composition to help improve strength. For example, the glass filler may comprise from about 2% to about 40%, in some embodiments from about 5% to about 35%, and in some embodiments, from about 6% to about 30% by weight of the polymer composition. Glass fibers are particularly suitable for use in the present invention, such as those formed from E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass, and the like, and mixtures thereof. The median width of the glass fibers may be relatively small, such as from about 1 to about 35 microns, in some embodiments from about 2 to about 20 microns, and in some embodiments, from about 3 to about 10 microns. When used, it is believed that the small diameter of such glass fibers may make their length more susceptible to reduction during melt blending, which may further improve surface appearance and mechanical properties. In molded parts, for example, the volume average length of the glass fibers may be relatively small, such as from about 10 to about 500 micrometers, in some embodiments from about 100 to about 400 micrometers, in some embodiments from about 150 to about 350 micrometers, and in some embodiments, from about 200 to about 325 micrometers. The glass fibers may also have a relatively high aspect ratio (average length divided by nominal diameter), such as from about 1 to about 100, in some embodiments from about 10 to about 60, and in some embodiments, from about 30 to about 50.

D.Particulate filler

Particulate fillers, which are generally non-conductive, may also be used in the polymer composition to help achieve desired properties and/or color. When used, such particulate fillers typically constitute from about 5% to about 40%, in some embodiments, from about 10% to about 35%, and in some embodiments, from about 10% to about 30% by weight of the polymer composition. Particulate clay minerals may be particularly suitable for use in the present invention. Such clay mineralExamples include talc (Mg)₃Si₄O₁₀(OH)₂) Halloysite (Al)₂Si₂O₅(OH)₄) Kaolin (Al)₂Si₂O₅(OH)₄) Illite ((K, H)₃O)(Al,Mg,Fe)₂(Si,Al)₄O₁₀[(OH)₂,(H₂O)]) Montmorillonite (Na, Ca)_0.33(Al,Mg)₂Si₄O₁₀(OH)₂·nH₂O), vermiculite ((MgFe, Al)₃(Al,Si)₄O₁₀(OH)₂·4H₂O), palygorskite ((Mg, Al)₂Si₄O₁₀(OH)·4(H₂O)), pyrophyllite (Al)₂Si₄O₁₀(OH)₂) And the like, as well as combinations thereof. Other particulate fillers may also be used instead of or in addition to clay minerals. For example, other suitable particulate silicate fillers such as mica, diatomaceous earth, and the like may also be employed. For example, mica may be a particularly suitable mineral for use in the present invention. As used herein, the term "mica" refers to the generic inclusion of any of these materials: such as muscovite (KAl)₂(AlSi₃)O₁₀(OH)₂) Biotite (K (Mg, Fe)₃(AlSi₃)O₁₀(OH)₂) Phlogopite (KMg)₃(AlSi₃)O₁₀(OH)₂) Lepidolite (K (Li, Al)_2-3(AlSi₃)O₁₀(OH)₂) Glauconite (K, Na) (Al, Mg, Fe)₂(Si,Al)₄O₁₀(OH)₂) And the like, as well as combinations thereof.

E.Other additives

Other additives that may be included in the composition may include, for example, antimicrobials, pigments, antioxidants, stabilizers, surfactants, waxes, solid solvents, flame retardants, anti-drip additives, and other materials added to enhance properties and processability. Lubricants that are able to withstand the processing conditions of the liquid crystalline polymer without significant decomposition may also be used in the polymer composition. Examples of such lubricants include fatty acid esters, salts thereof, esters, fatty acid amides, organic phosphates, and hydrocarbon waxes of the type frequently used as lubricants in the processing of engineering plastic materials, including mixtures thereof. Suitable fatty acids typically have a backbone carbon chain of about 12 to about 60 carbon atoms, such as myristic acid, palmitic acid, stearic acid, arachidic acid, montanic acid, stearic acid (octadecynic acid), parinaric acid (parinaric acid), and the like. Suitable esters include fatty acid esters, fatty alcohol esters, wax esters, glycerol esters, glycol esters, and complex esters. Fatty acid amides include fatty primary amides, fatty secondary amides, methylene and ethylene bis-amides, and alkanolamides such as palmitic acid amide, stearic acid amide, oleic acid amide, N' -ethylene bis-stearamide, and the like. Also suitable are: metal salts of fatty acids such as calcium stearate, zinc stearate, magnesium stearate, and the like; hydrocarbon waxes, including paraffin waxes, polyolefin and oxidized polyolefin waxes and microcrystalline waxes. Particularly suitable lubricants are acids, salts, or amides of stearic acid, such as pentaerythritol tetrastearate, calcium stearate, or N, N' -ethylene bisstearamide. When used, the one or more lubricants typically comprise from about 0.05 wt.% to about 1.5 wt.%, and in some embodiments, from about 0.1 wt.% to about 0.5 wt.% of the polymer composition (by weight).

III.Shaping of

The liquid crystalline polymer, mineral fibers, functional compound, and other optional additives may be melt processed or blended together at a temperature in the range of about 250 ℃ to about 450 ℃, in some embodiments, in the range of about 280 ℃ to about 400 ℃, and in some embodiments, in the range of about 300 ℃ to about 380 ℃ to form the polymer composition. For example, the components (e.g., liquid crystal polymer, mineral fiber, functional compound, etc.) may be provided, individually or in combination, to an extruder that includes at least one screw rotatably mounted and received within a barrel (e.g., a cylindrical barrel) and that may define a feed section and a melt section located downstream of the feed section along the length of the screw.

The extruder may be a single screw or twin screw extruder. Referring to fig. 3, for example, one embodiment of a single screw extruder 80 is shown, comprising a housing or barrel 114 and a screw 120, which may be rotatably driven on one end by a suitable drive 124 (typically including a motor and gear box). If desired, a twin screw extruder containing two separate screws may be used. The configuration of the screw is not particularly critical to the present invention and it may contain any number and/or orientation of flights and passages as is known in the art. As shown in fig. 3, for example, the screw 120 contains flights that form a generally helical channel extending radially around the core of the screw 120. The hopper 40 is positioned adjacent to a drive 124 for supplying liquid crystal polymer and/or other materials (e.g., mineral fibers and/or functional compounds) to the feed section 132 through an opening in the barrel 114. Opposite the drive 124 is an output 144 of the extruder 80, where the extruded plastic is an output for further processing.

A feed section 132 and a melt section 134 are defined along the length of the screw 120. The feed section 132 is an input to the barrel 114 where liquid crystal polymer, mineral fibers, and/or functional compounds are added. Melt zone 134 is a phase change zone in which the liquid crystalline polymer changes from a solid to a liquid. Although these sections are not described as precisely defined when manufacturing the extruder, one of ordinary skill in the art can reliably identify the feed section 132 and the melt section 134 in which the phase change from solid to liquid occurs. Although not required, the extruder 80 can also have a mixing section 136 positioned adjacent the output end of the barrel 114 and downstream of the melting section 134. If desired, one or more distributive and/or dispersive mixing elements may be used within the mixing and/or melting section of the extruder. Suitable distributive mixers for single screw extruders may include, for example, Saxon, Dulmage, Cavity Transfer mixers, and the like. Likewise, suitable dispersive mixers may include Blister rings, Leroy/Maddock, CRD mixers, and the like. Mixing can be further improved by using pins in the barrel that fold or reorient the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers, and Vortex intervening Pin mixers, as is well known in the art.

Mineral fibers may also be added to the hopper 40 or at a location downstream thereof. In one embodiment, the mineral fibers may be added at a location downstream of the point of supplying the liquid crystalline polymer. In this manner, the extent to which the length of the microfibers are reduced can be minimized, which helps maintain the desired aspect ratio. The ratio of the length ("L") to the diameter ("D") of the screws can be selected, if desired, to achieve an optimal balance between flux and retention of the aspect ratio of the mineral fibers. The L/D value may range, for example, from about 15 to about 50, in some embodiments from about 20 to about 45, and in some embodiments, from about 25 to about 40. The length of the screw may range, for example, from about 0.1 to about 5 meters, in some embodiments from about 0.4 to about 4 meters, and in some embodiments, from about 0.5 to about 2 meters. Likewise, the diameter of the screw may be from about 5 to about 150 millimeters, in some embodiments from about 10 to about 120 millimeters, and in some embodiments, from about 20 to about 80 millimeters. It is also possible to control the L/D ratio of the screw after the point of feeding the mineral fibres within a certain range. For example, the screw has a blend length ("L") defined from the point where the fibers are supplied to the extruder to the end of the screw_B") the blend length is shorter than the total length of the screw. L of the screw after the point of feeding the mineral fibres_BThe ratio/D, for example, may be in the range of from about 4 to about 20, in some embodiments from about 5 to about 15, and in some embodiments, from about 6 to about 10.

In addition to length and diameter, other aspects of the extruder may be controlled. For example, the speed of the screw may be selected to achieve a desired residence time, shear rate, melt processing temperature, and the like. For example, the screw rate may range from about 50 to about 800 revolutions per minute ("rpm"), in some embodiments from about 70 to about 150rpm, and in some embodiments, from about 80 to about 120 rpm. The apparent shear rate may also be about 100 seconds during melt blending^-1To about 10,000 seconds^-1In some embodiments, about 500 seconds^-1To about 5000 seconds^-1And in some embodiments about 800 seconds^-1To about 1200 seconds^-1In the middle range. The appearance is cutThe cut rate is equal to 4Q/pi R³Wherein Q is the volumetric flow rate of the polymer melt ('m')³S ") and R is the radius (" m ") of a capillary (e.g., an extruder die) through which the molten polymer flows.

Regardless of the particular manner of shaping, the present inventors have discovered that the resulting polymer composition can have excellent thermal properties. For example, as noted above, the melt viscosity of the polymer composition may be sufficiently low that it can easily flow into the cavity of a mold having small dimensions. However, the composition may still exhibit a relatively high melting temperature. For example, the melting temperature of the polymer may be from about 250 ℃ to about 400 ℃, in some embodiments from about 280 ℃ to about 395 ℃, and in some embodiments, from about 300 ℃ to about 380 ℃.

IV.Molded part

Once formed, the polymer composition can be molded into shaped parts for a variety of different applications. For example, the shaped part may be molded using a one-component injection molding process, wherein dried and preheated plastic pellets are injected into a mold. Regardless of the molding technique used, it has been found that the polymer compositions of the present invention having a unique combination of high flow and good mechanical properties are particularly well suited for electronic components having small dimensional tolerances. For example, such components typically contain at least one dimension (e.g., thickness, width, height, etc.) of a microscale, such as about 500 microns or less, in some embodiments, from about 50 to about 450 microns, and in some embodiments, from about 100 to about 400 microns.

One such component is a fine pitch electrical connector. More specifically, such electrical connectors are often used to removably mount a central processing unit ("CPU") to a printed circuit board. The connector may contain insertion channels configured to receive contact pins. The channels are defined by opposing walls, which may be formed of a thermoplastic resin. To help achieve the desired electrical performance, the pitch of these pins is typically small to accommodate the large number of contact pins required in a given space. This in turn requires that the spacing of the pin insertion channels and the width of the opposing walls separating those channels also be small. For example, the walls may have a width of about 500 microns or less, in some embodiments from about 50 to about 450 microns, and in some embodiments, from about 100 to about 400 microns. In the past, it has often been difficult to adequately fill such thin width molds with thermoplastic resins. However, due to its unique properties, the polymer composition of the present invention is particularly well suited for forming the walls of fine pitch connectors.

A particularly suitable fine pitch electrical connector is shown in fig. 1. An electrical connector 200 is shown having a board side C2 mountable to a surface of a circuit board P. The connector 200 may further include a wiring material side C1 configured to connect the discrete wires 3 to the circuit board P by coupling to a board-side connector C2. The board side portion C2 may include a first housing 10 having a fitting groove 10a in which the wiring material side connector C1 is fitted, and a configuration which is thin and long in the width direction of the housing 10. The wiring material side portion C1 may also include the second case 20 that is thin and long in the width direction of the case 20. In the second housing 20, a plurality of terminal receiving cavities 22 may be provided in parallel in the width direction so as to create a two-layer array including upper and lower terminal receiving cavities 22. Terminals 5 mounted to the distal ends of the discrete wires 3 may be received within respective terminal receiving cavities 22. If necessary, a locking portion 28 (engaging portion) corresponding to a connecting member (not shown) on the board-side connector C2 may also be provided on the housing 20.

As discussed above, the inner wall of the first housing 10 and/or the second housing 20 may have a relatively small width dimension and may be formed from the polymer composition of the present invention. For example, the wall is shown in more detail in fig. 2. As shown, an insertion channel or space 225 is defined between the opposing walls 224, which insertion channel or space 225 can accommodate the contact pins. The wall 224 has a width "w" within the above range. As shown, the wall 224 may be formed from a polymer composition containing mineral fibers (e.g., element 400). In addition to or in place of the wall, it is also understood that any other portion of the housing may also be formed from the polymer composition of the present invention. For example, the connector may also include a shield surrounding the housing. Some or all of the shields may be formed from the polymer compositions of the present invention. For example, the housing and the shield can each be a one-piece structure integrally molded from the polymer composition. Also, the shield may be a two-piece structure including a first shell and a second shell, each of which may be formed from the polymer composition of the present invention.

Of course, the polymer composition may also be used for a wide variety of other components. For example, the polymer composition can be molded into a flat substrate for electronic components. The substrate may be thin, for example, having a thickness of about 500 microns or less, in some embodiments, from about 50 to about 450 microns, and in some embodiments, from about 100 to about 400 microns. In one embodiment, for example, one or more conductive elements may be applied to a planar substrate using various known techniques (e.g., laser direct structuring, electroplating, etc.). The conductive element may be used for a variety of different purposes. In one embodiment, for example, the conductive elements form an integrated circuit, such as those used in SIM cards. In another embodiment, the conductive elements form various different types of antennas, such as antennas having resonating elements formed from patch antenna structures, inverted-F antenna structures, closed and open slot antenna structures, loop antenna structures, monopole, dipole, planar inverted-F antenna structures, hybrids of these designs, and the like. The resulting antenna structure may be incorporated into the housing of a relatively compact portable electronic component (such as described above), wherein the available internal space is relatively small.

One particularly suitable electronic assembly that includes the antenna structure shown in fig. 4-5 is a handheld device 410 having cellular telephone capabilities. As shown in fig. 4, the device 410 may have a housing 412, the housing 412 being formed of plastic, metal, other suitable dielectric material, other suitable conductive material, or a combination of such materials. A display 414, such as a touch screen display, may be provided on the front surface of the device 410. The device 410 may also have a speaker port 440 and other input-output ports. One or more buttons 438 and other user input devices may be used to gather user input. As shown in fig. 5, the antenna structure 426 may also be provided on the rear surface 442 of the device 410, but it should be understood that the antenna structure may generally be disposed at any desired location on the device. As indicated above, the antenna structure 426 may contain a planar substrate formed from the polymer composition of the present invention. The antenna structure may be electrically connected to other components within the electronic device using any of a variety of known techniques. For example, the housing 412 or a component of the housing 412 may serve as a conductive ground plane for the antenna structure 426.

The flat substrates formed from the polymer compositions of the present invention may also be used in other applications. For example, in one embodiment, a flat substrate may be used to form a base for a compact camera module ("CCM") commonly used in wireless communication devices, such as cellular telephones. Referring to fig. 6-7, for example, one embodiment of a compact camera module 500 is shown in more detail. As shown, the compact camera module 500 contains a lens assembly 504 that is superimposed on a base 506. The base 506 in turn overlies an optional main plate 508. Due to its relatively thin nature, the base 506 and/or the motherboard 508 are particularly suitable for being formed from the polymer compositions of the present invention as described above. The optic assembly 504 can have any of a variety of configurations known in the art, and can include a fixed focus lens and/or an auto focus lens. In one embodiment, for example, the optic assembly 504 is in the form of a hollow cylinder that houses a lens 604, the lens 604 being in communication with an image sensor 602 disposed on the motherboard 508 and controlled by the circuitry 601. The barrel may have any of a variety of shapes, such as rectangular, cylindrical, etc. In certain embodiments, the barrel may also be formed from the polymer composition of the present invention and have a wall thickness within the ranges described above. It should be understood that other components of the camera module may also be formed from the polymer composition of the present invention. For example, as shown, a polymeric film 510 (e.g., polyester film) and/or an insulative cover 502 can cover the lens assembly 504. In some embodiments, the film 510 and/or the cover 502 can also be formed from the polymer compositions of the present invention.

Other possible electronic components for which the polymer composition may be used include, for example, cellular telephones, notebook computers, small portable computers (e.g., ultra-portable computers, netbook computers, and tablet computers), wrist-watch devices, pendant devices, earpiece and earpiece devices, media players with wireless communication capabilities, handheld computers (also sometimes referred to as personal digital assistants), remote controls, Global Positioning System (GPS) devices, handheld gaming devices, battery covers, speakers, camera modules, integrated circuits (e.g., SIM cards), housings for electronic devices, electrical controls, circuit breakers, switches, power electronics (printer components), and the like.

Regardless of the particular application in which it is used, the molded part can have excellent mechanical and thermal properties. The part may, for example, have a thickness of greater than about 3kJ/m as measured at 23 ℃ according to ISO test number 179-1 (technically equivalent to ASTM D256, method B)²Greater than about 4kJ/m²In some embodiments from about 5 to about 40kJ/m²And in some embodiments from about 6 to about 30kJ/m²The impact strength of the gap of the simply supported beam. The tensile and flexural mechanical properties of the parts are also good. For example, the component may have a tensile strength of from about 20 to about 500MPa, in some embodiments from about 50 to about 400MPa, and in some embodiments, from about 100 to about 350 MPa; a tensile strain at break of about 0.5% or greater, in some embodiments from about 0.6% to about 10%, and in some embodiments, from about 0.8% to about 3.5%; and/or a tensile modulus of from about 5,000MPa to about 20,000MPa, in some embodiments from about 8,000MPa to about 20,000MPa, and in some embodiments, from about 10,000MPa to about 15,000 MPa. Tensile properties can be determined according to ISO test No. 527 (technically equivalent to ASTM D638) at 23 ℃. The component may also have a flexural strength of from about 20 to about 500MPa, in some embodiments from about 50 to about 400MPa, and in some embodiments, from about 100 to about 350 MPa; a flex fracture strain of about 0.5% or greater, in some embodiments from about 0.6% to about 10%, and in some embodiments, from about 0.8% to about 3.5%; and/or from about 5,000MPa to about 20,000MPa, in someFlexural modulus in embodiments from about 8,000MPa to about 20,000MPa, and in some embodiments from about 10,000MPa to about 15,000 MPa. Tensile properties can be determined according to ISO test number 178 (technically equivalent to ASTM D790) at 23 ℃. The molded part can also have a load Deflection Temperature (DTUL) of about 200 ℃ or more, and in some embodiments, about 200 ℃ to about 280 ℃, measured at a rated load of 1.8MPa according to ASTM D648-07 (technically equivalent to ISO test No. 75-2).

Furthermore, the molded parts may also have excellent antistatic behavior, especially when conductive fillers are included in the polymer composition. Such antistatic behavior may be characterized by a relatively low surface and/or volume resistivity, determined according to IEC 60093. For example, the molded part may exhibit about 1 × 10¹⁵Ohm or less, and in some embodiments, about 1X 10¹⁴Ohm or less, and in some embodiments, about 1X 10¹⁰Ohm to about 9 x 10¹³Ohmic, and in some embodiments, about 1 x 10¹¹To about 1X 10¹³Ohmic surface resistivity. Likewise, the molded part may also exhibit about 1 × 10¹⁵Ohm-meters or less, and in some embodiments, about 1X 10¹⁰Ohm-meter to about 9 x 10¹⁴Ohm-meter, and in some embodiments, about 1 x 10¹¹To about 5X 10¹⁴Ohm-meter volume resistivity. Of course, such antistatic behavior is by no means required. For example, in some embodiments, the molded part can exhibit a relatively high surface resistivity, such as about 1 x 10¹⁵Ohmic or greater, and in some embodiments about 1X 10¹⁶Ohmic or greater, and in some embodiments about 1X 10¹⁷Ohm to about 9 x 10³⁰Ohmic, and in some embodiments about 1 × 10¹⁸To about 1X 10²⁶Ohm.

The compositions may have improved flame retardant properties even in the absence of conventional flame retardants. The flame retardancy of the compositions can be determined, for example, according to the method known under the name "Tests for flame properties of Plastic Materials, UL 94" by Underwriter's Laboratory Bulletin 94. Several ratings may be applied based on the extinguishing time (total flame time) and the anti-drip capability as described in more detail below. According to this procedure, for example, molded parts formed from the compositions of the present invention can achieve a V0 rating, meaning that the part has a total flame time of about 50 seconds or less, as measured at a given part thickness (e.g., 0.25mm or 0.8 mm). To achieve a V0 rating, the part may also have a total number of 0 drips of burning particles that ignite cotton. For example, molded parts formed from the compositions of the present invention may exhibit a total flame time of about 50 seconds or less, in some embodiments, about 45 seconds or less, and in some embodiments, from about 1 to about 40 seconds, when exposed to an open flame. Further, the total number of drips of combustion particulates produced during the UL94 test may be 3 or less, in some embodiments 2 or less, and in some embodiments, 1 or less (e.g., 0). Such tests can be carried out after conditioning for 48 hours at 23 ℃ and 50% relative humidity.

The molded part may also have a relatively high degree of heat resistance. For example, the molded part may have a "bubble free temperature" of about 240 ℃ or greater, in some embodiments about 250 ℃ or greater, in some embodiments from about 260 ℃ to about 320 ℃, and in some embodiments, from about 270 ℃ to about 300 ℃. As explained in more detail below, the "bubble free temperature" is the highest temperature at which the molded part does not exhibit bubbles when placed in a heated silicone oil bath. Such bubbles are typically formed when the vapor pressure of the trapped moisture exceeds the strength of the part, thereby causing delamination and surface defects.

The invention may be better understood with reference to the following examples.

Test method

Melt viscosity: can be tested according to ISO test number 11443 at 1000s^-1(iii) and melting temperature (e.g., 350 ℃) the melt viscosity (Pa · s) was determined using a Dynisco LCR7001 capillary rheometer at a temperature above 15 ℃. The rheometer orifice (die) had a diameter of 1mm, a length of 20mm, an L/D ratio of 20.1, and an entrance angle of 180 °. CartridgeThe diameter of the body was 9.55mm +0.005mm and the rod length was 233.4 mm.

Melting temperature: the melting temperature ("Tm") is determined by differential scanning calorimetry ("DSC") as known in the art. The melting temperature is the Differential Scanning Calorimetry (DSC) peak melt temperature as determined by ISO test No. 11357. Under the DSC program, the sample was heated and cooled at 20 ℃/min using DSC measurements performed on a TA Q2000 instrument as described in ISO standard 10350.

Load deformation temperature ("DTUL"): the load deflection temperature was determined according to determination ISO test No. 75-2 (technically equivalent to ASTM D648-07). More specifically, test strip samples 80mm in length, 10mm in thickness and 4mm in width were subjected to a three-point bending test along the edge with a nominal load (maximum external fiber stress) of 1.8 mpa. The sample was placed in a silicone oil bath where the temperature was increased at 2 deg.C/min until it deformed 0.25mm (0.32 mm for ISO test number 75-2).

Tensile modulus, tensile stress and tensile elongation: tensile properties were tested according to ISO test No. 527 (technically equivalent to ASTM D638). Modulus and strength measurements were made on the same test strip samples 80mm in length, 10mm in thickness and 4mm in width. The test temperature was 23 ℃ and the test speed was 1 or 5 mm/min.

Flexural modulus, flexural stress and flexural strain: flexural properties were tested according to ISO test No. 178 (technically equivalent to ASTM D790). The test was performed on a 64mm support span. The test was performed on the center portion of an uncut ISO 3167 multipurpose stick. The test temperature was 23 ℃ and the test speed was 2 mm/min.

Impact strength of the notched simply supported beam: notched simple beam properties were tested according to ISO test number ISO 179-1 (technically equivalent to ASTM D256, method B). The test was conducted using a type a notch (0.25mm base radius) and type 1 specimen dimensions (length 80mm, width 10mm, and thickness 4 mm). Samples were cut from the center of the multi-purpose bar using a single tooth grinder. The test temperature was 23 ℃.

Seam Strength seam strength can be determined as is well known in the art by first forming an injection molded wire mesh grid array ("LGA") connector (dimensions: 49 mm. times.39 mm. times.1 mm) from a sample of the polymer composition. Once formed, the LGA connector may be placed on a sample holder. The center of the connector can be subjected to tension by moving the rod at a speed of 5.08 mm/min. The peak stress can be recorded as an estimate of the joint strength.

Bubble-free temperature: to test the blister resistance, 127 × 12.7 × 0.8mm test strips were molded at 5 ℃ to 10 ℃ above the melting temperature of the polymer resin (as determined by DSC). Ten (10) strips were immersed in silicone oil for 3 minutes at a given temperature, then removed, cooled to ambient conditions, and then examined for bubbles that may have formed (i.e., surface modifications). The silicone oil test temperature started at 250 ℃ and increased in 10 ℃ increments until air bubbles were observed on one or more test strips. The "bubble free temperature" of the test material is defined as the highest temperature at which all ten (10) of the tested bars show no bubbles. A higher bubble-free temperature indicates a higher degree of heat resistance.

UL 94: the specimen was supported in a vertical state and a flame was applied to the bottom of the specimen. The flame was applied for ten (10) seconds and then removed until the flame extinguished, at which point the flame was again applied for another ten (10) seconds and then removed. Two (2) groups of samples were tested, five (5) per group. The sample size was 125mm long, 13mm wide and 0.8mm thick. The two groups were adjusted before and after aging. For the unaged test, each thickness was tested after conditioning at 23 ℃ and 50% relative humidity for 48 hours. For the aged test, five (5) samples of each thickness were tested after conditioning at 70 ℃ for 7 days.

Example 1

Samples 1-5 were made from various percentages of liquid crystalline polymer, wollastonite4W or 8), anhydrous calcium sulfate, lubricant (Glycolube)^TMP), conductive filler and black masterbatch, as shown in table 1 below. The above-mentionedThe black masterbatch comprises 80 wt% liquid crystalline polymer and 20 wt% carbon black. In samples 1-5, the conductive filler includes carbon fibers. In sample 6, the conductive filler further includes graphite. Finally in sample 7, the conductive filler was an ionic liquid, i.e., tri-n-butyl methylammonium bis (trifluoromethanesulfonyl) -imide (FC-4400 from 3M). The liquid crystalline polymer in each sample was formed from HBA, HNA, TA, BP and APAP as described in U.S. patent No. 5,508,374 to Lee et al. A comparative sample (comparative sample 1) was also formed without wollastonite. Compounding was carried out using an 18-mm single screw extruder. Parts were injection molded from the samples into plaques (60 mm. times.60 mm).

TABLE 1

Some molded parts were also tested for thermal and mechanical properties. The results are shown in table 2 below.

TABLE 2

	Sample No. 6	Sample 7
			1000s-1And a melt viscosity (Pa. s) at 350 DEG C	48.6	51.6
400s-1And a melt viscosity (Pa. s) at 350 DEG C	78.5	78.6
			Tm(℃)	330.4	329.7
DTUL at 1.8MPa (. degree.C.)	212.4	215.7
			Tensile stress at break (MPa)	117.63	81.8
Tensile modulus (MPa)	9,249	8,842
			Tensile strain at break (%)	2.5	1.5
Flexural stress at Break (MPa)	114	105
			Flexural modulus (MPa)	8,518	9,344
Flexural strain at break (%)	2.6	1.9
			Simply supported beam gap (KJ/m)2)	6.1	1.7

Example 2

Samples 8-9 were made from various percentages of liquid crystalline polymer, wollastoniteLubricant (Glycolube)^TMP), mica, hydrated alumina ("ATH"), 4' -biphenol ("BP"), and 2, 6-naphthalenedicarboxylic acid ("NDA") as shown in table 3 below. The liquid crystal polymer in each sample was formed from 4-hydroxybenzoic acid ("HBA"), 2, 6-hydroxynaphthoic acid ("HNA"), terephthalic acid ("TA"), and hydroquinone ("HQ"), as described in U.S. patent No. 5,969,083 to Long et al. NDA is used in the polymer in an amount of 20 mol%. Comparative samples (comparative samples 2 and 3) were also formed without wollastonite. Compounding was carried out using an 18-mm single screw extruder. Parts were injection molded from the samples into plaques (60 mm. times.60 mm).

TABLE 3

Some molded parts were also tested for thermal and mechanical properties. The results are shown in table 4 below.

TABLE 4

Example 3

Sample 10 was prepared from liquid crystalline polymer, wollastonite: (4W), lubricant (Glycolube)^TMP), talc, alumina hydrate ("ATH"), 4' -biphenol ("BP"), 2, 6-naphthalene dicarboxylic acid ("NDA"), and black masterbatch, as shown in table 5 below. Each one ofThe liquid crystalline polymer in each sample was formed from 4-hydroxybenzoic acid ("HBA"), 2, 6-hydroxynaphthoic acid ("HNA"), terephthalic acid, and 4,4' -biphenol ("BP"). HNA was used in the polymer in an amount of 20 mol%. Compounding was carried out using an 18-mm single screw extruder. Parts were injection molded from the samples into plaques (60 mm. times.60 mm).

TABLE 5

The molded parts were also tested for thermal and mechanical properties. The results are shown in table 6 below.

TABLE 6

	Sample 8
		1000s-1And a melt viscosity (Pa. s) at 350 DEG C	20.0
400s-1And a melt viscosity (Pa. s) at 350 DEG C	34.3
		Tm(℃)	343.79
[email protected](℃)	274
		Simply supported beam gap (KJ/m)2)	2
Tensile stress at break (MPa)	11
		Tensile modulus (MPa)	97
Tensile strain at break (%)	8,254
		Flexural stress at Break (MPa)	2.02
Flexural modulus (MPa)	127
		Flexural strain at break (%)	9,005
Joint strength (lbf)	2.35

These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention. Additionally, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.