EP0275295A4

EP0275295A4 - Blends containing liquid crystalline polyesters.

Info

Publication number: EP0275295A4
Application number: EP19870905075
Authority: EP
Inventors: Marcus Matzner; Donald Mark Papuga
Original assignee: BP Corp North America Inc
Current assignee: BP Corp North America Inc
Priority date: 1986-07-21
Filing date: 1987-07-15
Publication date: 1990-02-21
Also published as: JPH01501066A; WO1988000605A1; EP0275295A1

Abstract

Improved blends wherein one constituent is a poly(aryl ether ketone), a poly(aryl ether), or a poly(phenylene oxide), and wherein the second constituent is a liquid crystalline polyester. The blends display improved mechanical properties, good high temperature stability and solvent resistance, and good melt-fabricability.

Description

BLENDS CONTAINING LIQUID CRYSTALLINE POLYESTERS

FIELD OF THE INVENTION

This invention is directed to improved blends wherein one constituent is a poly(aryl ether ketone), a poly (aryl ether), or a poly(phenylene oxide), and wherein the second constituent is a liquid crystalline polyester. A new process for the preparation of the subject blends is described. The blends display improved mechanical properties, good high temperature stability and solvent resistance, and good melt-fabricability.

BACKGROUND OF THE INVENTION

Poly(aryl ether ketone)s are a known class of engineering polymers. Several poly(aryl ether ketone)s are highly crystalline with melting points above 300ºC. Two of these crystalline poly(aryl ketone)s are commercially available and are of the following structure:

Over the years, there has been developed a substantial body of patent and other literature directed to the formation and properties of poly(aryl ethers) (hereinafter called "PAE"). Some of the earliest work such as by Bonner, U.S. 3,065,205, involves the electrophilic aromatic substitution (viz. Friedel-Crafts catalyzed) reaction of aromatic diacylhalides with unsubstituted aromatic compounds such as diphenyl ether. The evolution of this class to a much broader range of PAEs was achieved by Johnson et al., Journal of Polymer Science, A-1, vol. 5, 1967, pp. 2415-2427, Johnson et al., U.S. Patent Nos. 4,108,837, and 4,175,175. Johnson et al. show that a very broad range of PAEs can be formed by the nucleophilic aromatic substitution (condensation) reaction of an activated aromatic dihalide and an aromatic diol. By this method, Johnson et al. created a host of new PAEs including a broad class of poly(aryl ether ketones), hereinafter called "PAEK's".

In recent years, there has developed a growing interest in PAEK's as evidenced by Dahl, U.S. Patent No. 3,953,400; Dahl et al., U.S. Patent No. 3,956,240; Dahl, U.S. Patent No. 4,247,682; Rose et al., U.S. Patent No. 4,320,224; Maresca, U.S. Patent No. 4,339,568; Attwood et al., Polymer, 1981, vol 22, August, pp. 1096-1103; Blundell et al., Polymer, 1983, vol. 24, August, pp. 953-958, Attwood et al., Polymer Preprints, 20, No. 1, April 1979, pp. 191-194; and Rueda et al., Polymer Communications, 1983, vol. 24, September, pp. 258-260. In early to mid-1970, Raychem Corp. commercially introduced a PAEK called STILAN^™, a polymer whose acronym is PEK, each ether and keto group being separated by 1,4-phenylene units. In

1978, Imperial Chemical Industries PLC (ICI) commercialized a PAEK under the trademark Victrex

PEEK. As PAEK is the acronym of poly(aryl ether ketone), PEEK is the acronym of poly(ether ether ketone) in which the phenylene units in the structure are assumed.

Thus, PAEK's are well known; they can be synthesized from a variety of starting materials; and they can be made with different melting temperatures and molecular weights. The PAEK's are crystalline, and as shown by the Dahl and Dahl et al. patents, supra, at sufficiently high molecular weights they can be tough, i.e., they exhibit high values (>50 ft-1bs/in²) in the tensile impact test (ASTM D-1822). They have potential for a wide variety of uses, but because of the significant cost to manufacture them, they are expensive polymers.

Their favorable properties class them in the upper bracket of engineering polymers.

PAEK's may be produced by the

Friedel-Crafts catalyzed reaction of aromatic diacylhalides with unsubstituted aromatic compounds such as diphenyl ether as described in, for example,

U.S. Patent No. 3,065,205. These processes are generally inexpensive processes; however, the polymers produced by these processes have been stated by Dahl et al., supra, to be brittle and thermally unstable. The Dahl patents, supra. allegedly depict more expensive processes for making superior PAEK's by Friedel-Crafts catalysis. In contrast, PAEK's such as PEEK made by nucleophilic aromatic substitution reactions are produced from expensive starting fluoro monomers, and thus would be classed as expensive polymers.

These poly(aryl ether ketone)s exhibit an excellent combination of properties; i.e., thermal and hydrolytic stability, high strength and toughness, wear and abrasion resistance and solvent resistance. Thus, articles molded from poly(aryl ether ketones) have utility where high performance is required. However, in some applications where articles having a complex shape are sought fabrication difficulties arise due to the high melt viscosity of the poly(aryl ether ketones).

Poly(aryl ethers) have been known for about two decades; they are tough linear polymers that possess a number of attractive features such as excellent high temperature resistance, good electrical properties, and very good hydrolytic stability. Two poly(aryl ethers) are commercially available. A poly(aryl ether sulfone) is available from Imperial Chemical Industries Limited. It has the formula (3) and is produced by the

(3) polycondensation of 4-(4'-chlorophenylsulfonyl)- phenol, as described in British Patent Specif ication No . 1 , 153 , 035. The polymer contains no aliphatic moieties and has a heat deflection temperature of approximately 210°C. Another commercial poly(aryl ether) is available from Union Carbide Corporation under the trademark UDEL . It corresponds to formula (4) and has a heat deflection temperature of about 180°C.

n (4)

Illustrative poly(phenylene oxide) resin descriptions are found, for example, in U.S. Patent Nos. 3,306,874; 3,306,875; 4,140,675 and 4,234,706. A typical poly(phenylene oxide) is shown:

Various combinations of poly(phenylene oxide) resins and vinyl aromatic resins are known such as described, for example, in U.S. Pat. Nos. 3,308,435; 4,166,055; 4,166,812; and 4,164,493. Some of the above blends are offered commercially by the General Electric Co. The solvent and chemical resistance of the poly(aryl ethers) and of the poly(phenylene oxides) are only marginal, however.

The liquid crystalline aromatic polyesters which may be used herein are well known from the art. These liquid crystalline polyesters are described in, for example, U.S. Patents 3,804,805; 3,637,595; 4,130,545; 4,161,470; 4,230,817 and 4,265,802. The materials are characterized in that they exhibit optical anisotropy in the melt phase. Liquid crystalline polyesters are ordered, high strength materials, having very good high temperature properties; they are characterized by a relatively low melt viscosity and are particularly suitable for high strength fibers and filaments. Due to their high crystallinity their solvent and chemical resistance are excellent. Their main drawback as molding materials resides in the anisotropy of properties displayed by molded parts. Liquid crystalline polyesters were reviewed several times, see, for example, W.J. Jackson, Jr. Journal of Applied Polymer Science, Applied Polymer Symposium 41, 25-33 (1985).

THE INVENTION

The present invention is directed to improved blends wherein one component is a poly(aryl ether ketone), a poly(aryl ether), or a poly(phenylene oxide), and wherein the second component is a liquid crystalline polyester. More particularly, the invention is directed to a new process whereby the subject blends are prepared. The process consists in preparing the liquid crystalline polyester in the presence of a preformed poly(aryl ether ketone), poly(aryl ether), or poly(phenylene oxide). The method leads to blends having a better and more intimate degree of mixing than those obtained by mixing the two preformed polymers. As a result, products with improved mechanical properties and good melt-fabricability are obtained. These properties are superior to those of the materials made as described for example in U.S. Pat. Nos. 4,460,736 and 4,438,236.

The polymeric mixtures of the instant invention display, moreover, a significantly decreased degree of anisotropy of the molded parts. Their solvent, chemical and stress-crack resistance are very good, as are also their high temperature properties.

The poly(aryl ether ketones) useful in the present invention may be characterized by one or more of the following formulae:

& o wherein Ar is independently a divalent aromatic radical selected from phenylene, biphenylene, or

naphthalene, X is independently O, , SO₂, or a direct bond and a is an integer of from 1 to 4, b, c, d and e are 0 to 1 and preferably d is 0 when b is 1.

Preferred poly(aryl ether ketones)s include those having repeating units of the formula:

and copolymers thereof.

The process for preparing the poly(aryl ether ketones) comprises reacting a mixture (substantially equimolar amounts when maximum molecular weight is sought) of at least one bisphenol and at least one dihalobenzenoid compound or a halophenol. The bisphenols may be depicted as follows:

wherein X' is independently O, , SO₂, or a direct bond and Ar is independently a divalent radical selected from phenylene, biphenylene or naphthalene, most preferably 1,4-phenylene.

The dihalobenzenoid compound may be depicted as follows:

wherein Y is halogen, preferably fluorine, chlorine, or nitro; the Y's may be the same or different and are ortho or para to the X or X'; Ar, X, and X' are as defined above with the proviso that X or X' ortho or para to the Y's are electron withdrawing groups,

i.e., or SO_2. In the preferred embodiment, each aromatic radical is para substituted and most preferably, 1,4-phenylene. The halophenols may be depicted as follows:

jΛ wherein Y, X, and Ar are as defined above with the proviso that the X ortho or para to Y is an electron

withdrawing group, i.e., or SO₂.

Preferred bisphenols in such a process include: hydroquinone,

4,4'-dihydroxybenzophenone,

4,4'-dihydroxybiphenyl,

4,4'-dihydroxydiphenyl ether,

4,4'-dihydroxydiphenyl sulfone, and

4,4'-bis(4-hydroxyphenylsulfonyl)biphenyl.

Preferred dihalobenzenoid and halophenol compounds include:

4,4'-diGhlorodiphenyl sulfone,

4,4'-difluorodiphenyl sulfone,

4-(4'-chlorobenzoyl)phenol,

4-(4'-fluorobenzoyl)phenol,

4,4'-difluorobenzophenone,

4,4'-dichlorobenzophenone,

4-chloro-4'-fluorobenzophenone,

1,4-bis(4-fluorobenzoyl)benzene, and 1,3-bis(4-fluorobenzoyl)benzene.

The reaction is carried out by heating a mixture of one or more bisphenols and one or more dihalobenzenoid compounds or halophenols at a temperature of from about 100 to about 400°C. The reactions are conducted in the presence of an alkali metal carbonate or bicarbonate. Preferably a mixture of alkali metal carbonates or bicarbonates is used. When a mixture of alkali metal carbonates or bicarbonates is used, the mixture comprises sodium carbonate or bicarbonate with a second alkali metal carbonate or bicarbonate wherein the alkali metal of the second carbonate or bicarbonate has a higher atomic number than that of sodium. The amount of the second alkali metal carbonate or bicarbonate is such that there is from 0.01 to about 0.25 gram atoms of the second alkali metal per gram atom of sodium. Of course, it is possible to use the preformed alkali metal salts of diphenols.

The higher alkali metal carbonates or bicarbonates are thus selected from the group consisting of potassium, rubidium and cesium carbonates and bicarbonates. Preferred combinations are sodium carbonate or bicarbonate with potassium carbonate or cesium carbonate.

The alkali metal carbonates or bicarbonates should be anhydrous although, if hydrated salts are employed, where the polymerization temperature is relatively low, e.g. 100 to 250°C, the water should be removed, e.g. by heating under reduced pressure, prior to reaching the polymerization temperature.

Where high polymerization temperatures (>250°C) are used, it is not necessary to dehydrate the carbonate or bicarbonate first as any water is driven off rapidly before it can adversely affect the course of the polymerization reaction.

Optionally, an entraining organic medium can be used to remove water from the reaction such as toluene, xylene, chlorobenzene, and the like. The total amount of alkali metal carbonate or bicarbonate employed should be such that there is at least 1 atom of alkali metal for each phenol group. Hence, when using a diphenol there should be at least 1 mole of carbonate, or 2 moles of bicarbonate, per mole of the aromatic diol. Likewise where a halophenol is employed there should be at least 0.5 mole of carbonate, or 1 mole of bicarbonate, per mole of the halophenol.

An excess of carbonate or bicarbonate may be employed. Hence there may be 1 to 1.2 atoms of alkali metal per phenol group. While the use of an excess of carbonate or bicarbonate may give rise to faster reactions, there is the attendant risk of cleavage of the resulting polymer, particularly when using high temperatures and/or the more active carbonates.

As stated above the amount of the second (higher) alkali metal carbonate or bicarbonate employed is such that there are 0.001 to about 0.2 grams atoms of the alkali metal of higher atomic number per gram atom of sodium.

Thus when using a mixture of carbonates, e.g. sodium carbonate and cesium carbonate, there should be 0.1 to about 20 moles of cesium carbonate per 100 moles of sodium carbonate. Likewise when using a mixture of a bicarbonate and a carbonate, e.g. sodium bicarbonate and potassium carbonate, there should be 0.05 to 10 moles of potassium carbonate per 100 moles of sodium bicarbonate.

A mixed carbonate, for example sodium and potassium carbonate, may be employed as the second alkali metal carbonate. In this case, where one of the alkali metal atoms of the mixed carbonate is sodium, the amount of sodium in the mixed carbonate should be added to that in the sodium carbonate when determining the amount of mixed carbonate to be employed.

Preferably, from 0.001 to 0.2 gram atoms of the alkali metal of the second alkali metal carbonate or bicarbonate per gram atom of sodium is used.

Where a bisphenol and a dihalobenzenoid compound are employed, they should be used in substantially equimolar amounts. An excess of one over the other leads to the production of lower molecular weight products. However a slight excess, up to 5 mole %, of the dihalide or of the diphenol may be employed if desired. The reaction is carried out in the presence of an inert solvent or partially in the absence of a solvent. Preferably, the solvent is an aliphatic or aromatic sulphoxide or sulphone of the following formula

R - S(O)_x- R'

where x is 1 or 2 and R and R' are alkyl or aryl groups and may be the same or different. R and R' may together form a divalent radical. Preferred solvents include dimethyl sulphoxide, dimethyl sulphone, sulpholane (1,1 dioxothiolan), or aromatic sulphones of the formula: where R₂ is a direct link, an oxygen atom or two hydrogen atoms (one attached to each benzene ring) and R₃ and R'₃, which may be the same or different, are hydrogen atoms and alkyl or phenyl groups. Examples of such aromatic sulphones include diphenylsulphone, dibenzothiophen dioxide, phenoxathiin dioxide and 4-phenylsulphonyl biphenyl. Diphenylsulphone is the preferred solvent. Other solvents that may be used include benzophenone, N,N-dimethyl acetamide, N,N-dimethyl formamide and N-methyl-2-pyrrolidone.

The polymerization temperature is in the range of from about 100° to about 400°C and will depend on the nature of the reactants and the solvent, if any, employed. The preferred temperature is above 270°C. The reactions are generally performed under atmospheric pressure. However, higher or lower pressures may be used.

For the production of some polymers, it may be desirable to commence polymerization at one temperature, e.g. between 200° and 250°C and to increase the temperature as polymerization ensues. This is particularly necessary when making polymers having only a low solubility in the solvent. Thus, it is desirable to increase the temperature progressively to maintain the polymer in solution as its molecular weight increases. To minimize cleavage reactions it is preferred that the maximum polymerization temperature be below 350°C.

The polymerization reaction may be terminated by mixing a suitable end capping reagent, e.g. a mono or polyfunctional halide such as methyl chloride, difluorobenzophenone, monofluoro benzophenone, 4,4'-dichlorodiphenylsulphone with the reaction mixture at the polymerization temperature, heating for a period of up to one hour at the polymerization temperature and then discontinuing the polymerization.

This invention is also directed to an improved process for making the poly(aryl ether ketones). Specifically, this process is directed to preparing the poly(aryl ether ketone) polymer by the reaction of a mixture of at least one bisphenol and at least one dihalobenzenoid compound and/or by the reaction of a halophenol. The reactions are carried out by heating the above reactants at a temperature of from about 100 to about 400°C. The reaction is conducted in the presence of added sodium carbonate and/or bicarbonate, and potassium, rubidium or cesium fluorides or chlorides. The sodium carbonate or bicarbonate and the chloride and fluoride salts should be anhydrous although, if hydrated salts are employed, where the reaction temperature is relatively low, e.g. 100 to 250°C, the water should be removed, e.g. by heating under reduced pressure, prior to reaching the reaction temperature.

Where high reaction temperatures (>250ºC) are used, it is not necessary to dehydrate the carbonate or bicarbonate first as any water is driven off rapidly before it can adversely affect the course of the reaction. Optionally, an entraining organic medium can be used to remove water from the reaction such as toluene, xylene, chlorobenzene, and the like.

The total amount of sodium carbonate and/or bicarbonate and potassium, rubidium or cesium fluoride or chloride employed should be such that there is at least 1 atom of total alkali metal for each phenol group, regardless of the anion (carbonate, bicarbonate or halide). Likewise where a halophenol is employed there should be at least one mole of total alkali metal per mole of halophenol.

Preferably, from about 1 to about 1.2 atoms of sodium for each phenol group is used. In another preferred embodiment from 0.001 to about 0.5 atoms of alkali metal (derived from alkali metal halide) is used for each phenol group.

The sodium carbonate and/or bicarbonate and potassium fluoride are used such that the ratio of potassium to sodium therein is from about 0.001 to about 0.5, preferably from about 0.01 to about 0.25, and most preferably from about 0.02 to about 0.20.

An excess of total alkali metal may be employed. Hence there may be about 1 to about 1.7 atoms of alkali metal per phenol group. While the use of a large excess of alkali metal may give rise to faster reactions, there is the attendant risk of cleavage of the resulting polymer, particularly when using high temperatures and/or the more active alkali metal salts. Of course it is well known to those skilled in the art that cesium is a more active metal and potassium is a less active metal so that less cesium and more potassium are used. Further, it has been observed that the chloride salts are less active than the fluoride salts so that more chloride and less fluoride is used.

Where a bisphenol and dihalobenzenoid compound are employed, they should be used in substantially equimolar amounts when maximum molecular weight is sought. However an excess of bisphenol or dihalide may be employed if desired. An excess of one monomer over the other leads to the production of low molecular weight products which can be desirable when the process is directed to making lower molecular weight PAEK.

The reaction may be carried out in the presence of an inert solvent, or partially in the absence of a solvent.

Preferably a solvent is employed and is an aliphatic or aromatic sulphoxide or sulphone of the formula

where x is 1 or 2 and R and R' are alkyl or aryl groups and may be the same or different. R and R' may together form a divalent radical. Preferred solvents include dimethyl sulphoxide, dimethyl sulphone, sulpholane (1,1 dioxothiolan), or aromatic sulphones of the formula. where R₂ is a direct link, an oxygen atom or two hydrogen atoms (one attached to each benzene ring) and R₃ and R'₃, which may be the same or different, are hydrogen atoms or phenyl groups. Examples of such aromatic sulphones include diphenylsulphone, ditolyl sulphone, tolylphenyl sulphone, dibenzothiophen dioxide, phenoxathiin dioxide and 4-phenylsulphonyl biphenyl. Diphenylsulphone is the preferred solvent. Other solvents that may be used include N,N-dimethyl formamide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N-cyclohexyl pyrrolidone. In another embodiment the reaction is started in a relatively low boiling. polar aprotic solvent such as dimethyl formamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and the like. Heating at reflux results in the formation of low molecular weight product with attendant precipitation. The solvent may be removed and the low molecular weight product may be advanced if desired by solid state polymerization, i.e. by heating to a temperature in the range of from about 200 to about 400°C; preferably, an inert atmosphere is maintained during this latter step.

The reaction temperature is in the range of from about 100° to about 400°C and will depend on the nature of the reactants and the solvent, if any, employed. The preferred temperature is above 250°C. The reactions are preferably carried out at ambient pressure. However, higher or lower pressure can also be used. The reaction is generally carried out in an inert atmosphere.

For the production of some poly(aryl ether ketone)s, it may be desirable to commence reaction at one temperature, e.g. between 200° and 250°C and to increase the temperature as reaction ensues. This is particularly necessary when making high molecular weight polymers having only a low solubility in the solvent. Thus, there it is desirable to increase the temperature progressively to maintain the polymer in solution as its molecular weight increases.

To minimize cleavage reactions it is preferred that the maximum polymerization temperature be below about 350°C.

The polymerization reaction may be terminated by mixing a suitable end capping reagent,e.g. a mono or polyfunctional halide such as methyl chloride, difluorobenzophenone, monofluorobenzophenone, 4,4'-dichlorodiphenyl sulphone with the reaction mixture at the polymerization temperature, heating for a period of up to one hour at the polymerization temperature and then discontinuing the polymerization.

Also, the poly(aryl ketone) polymers such as those containing repeating units of the formula:

may be produced by Friedel-Crafts reactions utilizing hydrogen fluoride-boron trifluoride catalysts as described, for example, in U.S. Patent 3,953,400.

Additionally, poly(aryl ketone) polymers of the following formula:

may be prepared by Friedel-Crafts reactions using a boron trifluoride-hydrogen fluoride catalyst as described in, for example, U.S. Patents 3,441,538; 3,442,857 and 3,516,966.

Moreover, the poly(aryl ketones) may be prepared by Friedel-Crafts processes as described in, for example, U.S. Patents Nos. 3,065,205; 3,419,462; 3,441,538; 3,442,857; 3,516,966; and 3,666,612. In these patents a PAEK is produced by Friedel-Crafts polymerization techniques using Friedel-Crafts catalysts such as aluminum trichloride, zinc chloride, ferric bromide, antimony pentachloride, titanium tetrachloride, etc. and a solvent.

The polyketones may also be prepared according to the process as described in, for example, U.S. Defensive Publication T 103,703 and U.S. Patent 4,396,755. In such processes, reactants such as (a) an aromatic monocarboxylic acid, (b) a mixture of at least one aromatic dicarboxylic acid, and an aromatic hydrocarbon, and (c) combinations of ( a) and (b) are reacted in the presence of a fluoroalkane sulphonic acid, particularly trifluoromethane sulphonic acid.

Additionally, poly(aryl ether ketone) polymers of the following formulas:

may also be prepared according to the process as described in, for example, U.S. Patent 4 398 020. In such a process,

(a) a mixture of

(i) at least one aromatic diacyl halide of the formula:

YOC-Ar₁-COY where -Ar₁- is a divalent aromatic radical, Y is halogen and COY is an aromatically bound acyl halide group, which diacyl halide is polymerizable with at least one aromatic compound of (a)(ii), and

(ii) at least one aromatic compound of the formula:

H-Ar₂-H wherein -Ar₂- is a divalent aromatic radical and H is an aromatically bound hydrogen atom, which compound is polymerizable with at least one diacyl halide of (a)(i), or

(b) at least one aromatic monoacyl halide of the formula:

H-Ar₃-COW where -Ar₃- is a divalent aromatic radical and H is an aromatically bound hydrogen atom, W is halogen, and COW is an aromatically bound acyl halide group, which monoacyl halide is self-polymerizable, or

(c) a combination of (a) and (b) is reacted in the presence of a fluoroalkane sulphonic acid.

Specifically, the polymers may be prepared by reacting any of the well-known aromatic coreactants such as diphenyl sulfide, dibenzofuran, thianthrene, phenoxathiin, dibenzodioxine, phenodioxin, diphenylene, 4,4'-diphenoxybiphenyl, xanthone, 2,2'-diphenoxybiphenyl, 1,4-diphenoxybenzene, 1,3-diphenoxybenzene, 1-phenoxynapthalene, 1,2-diphenoxynapthalene, dipherioxybenzophenone, diphenoxy dibenzoyl benzene, diphenyl ether, 1,5-diphenoxynapthalene, and the like. Among these, diphenyl ether, diphenyl, diphenyl methane, 1,4-diphenoxy benzene, and 4,4'-diphenoxy diphenyl ether are preferred.

Similarly, the following compounds are diacyl halides which may be used as reactants: terephthaloyl chloride, isophthaloyl chloride, thio-bis(4,4'-benzoyl chloride), benzophenone-4,4'-di(carbonyl chloride), oxy-bis(3,3'-benzoyl chloride), dipheny1-3,3-'-di(carbonyl chloride), carbonyl-bis(3,3'-benzoyl chloride), sulfonyl-bis(4,4'-benzoyl chloride), sulfonyl-bis(3,3'-benzoyl chloride), sulfonyl-bis(3,4'-benzoyl chloride), thio-bis(3,4'-benzoyl chloride), diphenyl-3,4'-di(carbonyl chloride), oxy-bis[4,4'-(2-chlorobenzoyl chloride)], napthalene-1,6-di(carbonyl chloride), napthalene-1,5-di(carbonyl chloride), napthalene-2,6-di(carbonyl chloride), oxy-bis[7,7'-napthalene-2,2'-di(carbonyl chloride)], thio-bis[8,8'-napthalene-1,1-di(carbonyl chloride)],

[7,7'-binaphthyl-2,2-di(carbonyl chloride)], diphenyl-4,4'-di(carbonyl chloride), carbonyl-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)], sulfonyl-bis[6,6'-napthalene-

2,2'-di(carbonyl chloride)], dibenzofuran-2,7- di(carbonyl chloride) and the like.

Illustrative of suitable acyldihalides include carbonyl chloride (phosgene), carbonyl bromide, carbonyl fluoride and oxalyol chloride.

Preferably, diphenyl ether and/or diphenoxybenzene are reacted with terephthaloyl chloride and/or phosgene.

The preferred Friedel-Crafts catalysts are aluminum chloride, antimony pentachloride and ferric chloride. Other Friedel-Crafts catalysts, such as aluminum bromide, boron trifluoride, boron trifluoride/hydrogen fluoride, zinc chloride, antimony trichloride, ferric bromide, titanium tetrachloride, and stanic chloride, can also be used.

The reaction is generally carried out in the presence of a solvent. The preferred organic solvent is 1,2-dichloroethane. Other solvents such as symmetrical tetrachloroethane, o-dichlorobenzene, hydrogen fluoride or carbon disulfide may be employed.

The reaction may be carried out over a range of temperatures which are from about -40°C to about 160°C. In general, it is preferred to carry out the reaction at a temperature in the range of 0° to 30°C. In some cases it is advantageous to carry out the reaction at temperatures above 30°C or below 0°C. The reaction may be carried out at atmospheric pressure although higher or lower pressures may be used.

The term poly(aryl ether ketone) as used herein is meant to include homopolymers, copolymers, terpolymers, graft copolymers, and the like. The poly(aryl ether ketones) exhibit a reduced viscosity of from about 0.05 to about 5.0, and preferably, from about 0.1 to about 2.0 dl/g as measured in concentrated sulfuric acid (/g/100 ml.) at 25°C.

The poly(aryl ether), polymers suitable for the purposes of this invention are linear thermoplastic polyarylene polyethers containing recurring units of the formula:

-O-E-O-E'- wherein E is the residuum of a dihydric phenol, and E' is the residuum of a benzenoid compound having an inert electron withdrawing group in at least one of the positions ortho and para to the valence bonds; both of said residua are valently bonded to the ether oxygens through aromatic carbon atoms. Such aromatic polyethers are included within the class of polyarylene polyether resins described in, for example, U.S. Patents 3,264,536 and 4,175,175. It is preferred that the dihydric phenol be a weakly acidic dinuclear phenol such as, for example, the dihydroxyl diphenyl alkanes or the nuclear halogenated derivatives thereof, such as, for example, the 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)2-phenyl ethane, bis (4-hydroxyphenyl)methane, or their chlorinated derivatives containing one or two chlorines on each aromatic ring. Other materials also termed appropriately bisphenols are also highly valuable and preferred. These materials are the bisphenols of a symmetrical or unsymmetrical joining group, as,

for example, ether oxygen (-O-), carbonyl

sulfone or hydrocarbon residue in which the two phenolic nuclei are joined to the same or different carbon atoms of the residue.

Such dinuclear phenols can be characterized as having the structure:

wherein Ar₄ is an aromatic group and preferably is a phenylene group, R₄ and R'₄can be the same or different inert substituent groups such as alkyl groups having from 1 to 4 carbon atoms, aryl, halogen atoms, i.e., fluorine, chlorine, bromine or iodine, or alkoxyl radicals having from 1 to 4 carbon atoms, the d's are independently integers having a value of from 0 to 4, inclusive and R₅ is representative of a bond between aromatic carbon atoms as in dihydroxyl-diphenyl, or is a divalent radical, including for example, radicals such as -O-, -S-, -S-S- -SO-, -SO₂, and divalent hydrocarbon radicals such as alkylene, alkylidene, cycloalkylene, cycloalkylidene, or the halogen, alkyl, aryl or like substituted alkylene, alkylidene and cyloaliphatic radicals as well as aromatic radicals and radicals fused to both Ar₄ groups.

Examples of specific dihydric polynuclear phenols include among others: the bis-(hydroxyphenyl) alkanes such as

2,2-bis-(4-hydroxyphenyl)propane,

2,4'-dihydroxydiphenylmethane, bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane. bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane,

1,1-bis-(4-hydroxy-phenyl)ethane, 1,2-bis-(4-hydroxyphenyl)ethane,

1,1-bis-(4-hydroxy-2-chlorophenyl)ethane,

1,1-bis-(3-methyl-4-hydroxyphenyl)propane,

1,3-bis-(3-methyl-4-hydroxyphenyl)propane,

2,2-bis-(3-phenyl-4-hydroxyphenyl)propane,

2,2-bis-(3-isopropyl-4-hydroxyphenyl)propane,

2,2-bis-(2-isopropyl-4-hydroxyphenyl)propane,

2,2-bis-(4-hydroxy-naphthyl)propane,

2,2-bis-(4-hydroxyphenyl)pentane,

3,3-bis-(4-hydroxyphenyl)pentane,

2,2-bis-(4-hydroxyphenyl)heptane, bis-(4-hydroxyphenyl)phenylmethane,

2,2-bis-(4-hydroxyphenyl)-1-phenyl-propane,

2,2-bis-(4-hydroxyphenyl)1,1,1,3,3,3,-hexafluroro- propane and the like; di(hydroxyphenyl)sulfones such as bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, 5-chloro-2,4'-dihydroxydiphenyl sulfone, 5'-chloro-4,4'-dihydroxydiphenyl sulfone, and the like; di(hydroxyphenyl)ethers such as bis-(4-hydroxyphenyl)ether, the 4,3'-, 4,2'-2,2'-2,3'-,dihydroxyphenyl ethers, 4,4'-dihydroxyl-2,6-dimethyldiphenyl ether, bis-(4-hydroxy-3-isopropylphenyl)ether, bis-(4-hydroxy-3-chlorophenyl)ether, bis-(4-hydroxy-3-fluorophenyl)ether, bis-(4-hydroxy-3-bromophenyl)ether, bis-(4-hydroxynaphthyl)ether, bis-(4-hydroxy-3-chloronaphthyl)ether, and 4,4'-dihydroxyl-3,6-dimethoxydiphenyl ether.

As herein used the E term is defined as being the "residuum of the dihydric phenol" of course refers to the residue of the dihydric phenol after the removal of the two aromatic hydroxyl groups. Thus as is readily seen these polyarylene polyethers contain recurring groups of the residuum of the dihydric phenol and the residuum of the benzenoid compound bonded through aromatic ether oxygen atoms.

Any dihalobenzenoid or dinitrobenzenoid compound or mixtures thereof can be employed in this invention which compound or compounds has the two halogens or nitro-groups bonded to benzene rings having an electron withdrawing group in at least one of the positions ortho or para to the halogen or nitro group. The dihalobenzoid or dinitrobenzenoid compound can be either mononuclear, where the halogens or nitro groups are attached to the same benzenoid ring; or polynuclear where they are attached to different benzenoid rings, as long as there is an activating electron withdrawing group in the ortho or para position of that benzenoid nucleus. Fluorine and chlorine substituted benzenoid reactants are preferred; the fluorine compounds for fast reactivity and the chlorine compounds for their inexpensiveness. Fluorine substituted benzenoid compounds are most preferred, particularly when there is a trace of water present in the polymerization reaction system. However, this water content should be maintained below about 1% and preferably below 0.5% for best results.

An electron withdrawing group is employed as the activator group in these compounds. It should be, of course, inert under the reaction conditions, but otherwise its structure is not critical. Preferred are the strongly activating

groups such as the sulfone group bonding two halogen or nitro substituted benzenoid nuclei, as in 4,4'-dichlorodiphenyl sulfone and 4,4'-diflurodiphenyl sulfone, although such other strong withdrawing groups hereinafter mentioned can also be used with equal ease.

The more powerful of the electron withdrawing groups give the fastest reactions and hence are preferred. It is further preferred that the ring contain no electron supplying groups on the same benzenoid nucleus as the halogen or nitro group; however, the presence of other groups on the nucleus or in the residuum of the compound can be tolerated.

The activating groups can be basically either of two types:

(a) monovalent groups that activate one or more halogens or nitro-groups on the same ring such as another nitro or halo group, phenylsulfone, or alkylsulfone, cyano, trifluoromethyl, nitroso, and hetero nitrogen, as in pyridine.

(b) divalent groups which can activate displacement of halogens on two different rings,

such as the sulfone group the carbonyl group

the vinylene group the sulfoxide group

the azo group -N=N-; the saturated flurocarbon

groups -CF₂ -CF₂CF₂; organic phosphine

oxides where R₃ is a hydrocarbon group and the ethylidene group A-C A where A can be hydrogen or halogen.

- If desired, the polymers may be made with mixtures of two or more dihalobenzenoid or dinitrobenzenoid compounds. Thus, the E' residuum of the benzenoid compounds in the polymer structure may be the same or different.

It is seen also that as used herein, the E' term defined as being the "residuum of the benzenoid compound" refers to the aromatic or benzenoid residue of the compound after the removal of tne halogen atom or nitro group on the benzenoid nucleus.

The polyarylene polyether polymers of this invention are prepared by methods well known in the art as for instance the one-step reaction of a double alkali metal salt of a dihydric phenol with a dihalobenzenoid compound in the presence of specific liquid organic sulfoxide or sulfone solvents under substantially anhydrous conditions. Catalysts are not necessary for this reaction.

The polymers may also be prepared in a two-step process in which a dihydric phenol is first converted in situ in the primary reaction solvent to the alkali metal salt by the reaction with the alkali metal, the alkali metal hydride, alkali metal hydroxide, alkali metal alkoxide or the alkali metal alkyl compounds. Preferably, the alkali metal hydroxide is employed. After removing the water which is present or formed, in order to secure substantially anhydrous conditions, the dialkali metal salts of the dihydric phenol are admixed and reacted with the dihalobenzenoid or dinitrobenzenoid compound. Additionally, the polyethers may be prepared by the procedure described in, for example, U.S. Patent 4,176,222 in which at least one bisphenol and at least one dihalobenzenoid compound are heated at a temperature of from about 100° to about 400°C with a mixture of sodium carbonate or bicarbonate and a second alkali metal carbonate or bicarbonate having a higher atomic number than that of sodium.

Further, the polyethers may be prepared by the procedures described in Canadian Patent 847,963 wherein the bisphenol and dihalobenzenoid compound are heated in the presence of potassium carbonate using a high boiling solvent such as diphenylsulfone.

Halophenols or nitrophenols-wherein the halogen or nitro group is activated by an electron withdrawing group in the ortho- and/or para positions can also be used for the preparation of the poly(aryl ethers). The halophenols or nitrophenols can be used alone or in conjunction with a diphenol and a dihalo- or dinitrobenzenoid compound as defined above.

Preferred polyarylene polyethers of this invention are those prepared using the dihydric polynuclear phenols of the formulae (6)-(10) including the derivatives thereof which are substituted with inert substituent groups; f

(6) in which the R₆ groups represent independently hydrogen, lower alkyl, aryl and the halogen substituted groups thereof, which can be the same or different;

and substituted derivatives thereof.

It is also contemplated in this invention to use a mixture of two or more different dihydric phenols to accomplish the same ends as above. Thus when referred to above the -E- residuum in the polymer structure can actually be the same or different aromatic vresidua.

The preferred dichlorobenzenoid compounds are (11), (12), (13) and (14);. they may carry inert substituent groups.

(11) (12) O

( 14 )

The most preferred poly(aryl ether) polymers have the repeating units (3), (4), (15), and (16).

(3) (4)

(15)

(16)

The poly(aryl ethers) exhibit a reduced viscosity of from about 0.05 to about 5.0 and preferably, from about 0.3 to about 1.5 dl/g as measured in an appropriate solvent at 25°C and at a concentration of 0.2 g/100 ml. The poly(phenylene oxides) are resins of the general formula:

(17) wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer, and each Q is independently a monovalent substituent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals, and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.

The preferred poly(phenylene oxides) are those in which Q is an alkyl group having 1 to 4 carbon atoms, and in which n is at least 50. The most preferred polymer corresponds to formula (5) with n being at least 100 and higher.

Poly(phenylene ethers) such as described in, for example, U.S. Patent No. 4,011,200 and incorporating repeat units (18) and (19), are also useful in the present invention.

( 18 ) ( 19 )

The poly(phenylene oxide) resins and methods for their preparation are well known to the polymer art. These polymers may be made by a variety of catalytic and non-catalytic processes from the corresponding phenols or reactive derivatives thereof. By way of illustration, certain of the poly(phenylene oxides) and methods of preparation are disclosed in Hay, U.S. Pat. Nos. 3,306,874 and 3,306,875, and in Stamatoff, U.S. Pat. Nos. 3,257,357 and 3,257,358. In the Hay patents, the poly(phenylene oxides) are prepared by an oxidative coupling reaction comprising passing an oxygen-containing gas through a reaction solution of a phenol and a metal-amine complex catalyst. Other disclosures relating to processes of preparing poly(phenylene oxide) resins, including graft copolymers of poly(phenylene oxides) with styrene type compounds, are found in Fox, U.S. Pat. No. 3,356,761; Sumitomo, U.K. Pat. No. 1,291,609; Bussink et al., U.S. Pat. No. 3,337,499; Blanchard et al., U.S. Pat. No. 3,219,626; Laakso et al., U.S. Pat. No. 3,342,892; Borman, U.S. Pat. No. 3,344,166; Hori et al., U.S. Pat. No. 3,384,619, Faurote et al., U.S. Pat. No. 3,440,217; and disclosures relating to metal-based catalysts which do not include amines, are known from patents such as Wieden et al., U.S. Pat. No. 3,442,885 (copper-amidines); Nakashio et al., U.S. Pat. No. 3,573,257 (metal-alcoholate or -phenolate); Kobayashi et al., U.S. Pat. No. 3,455,880 (cobalt chelates); and the like. All of the above-mentioned disclosures are incorporated herein by reference.

The liquid crystalline polyarylates which may be used herein are well known in the art. These liquid crystalline polyarylates are described in, for example, U.S. Patents 3,804,805; 3,637,595; 4,130,545; 4,161,470; 4,230,817 and 4,265,802. Preferably, the liquid crystalline polyarylates are derived from one or more of the following: p-hydroxy-benzoic acid, m-hydroxy- benzoic acid, terephthalic acid, isophthalic acid, hydroquinone, phenyl hydroquinone, alkyl substituted hydroquinones, halo substituted hydroquinones, 4,4'-dihydroxydiphenyl ether, resorcinol, 4,4'-biphenol, 2,6-naphthalene diol, 2,6-naphthalene dicarboxylic acid, 6-hydroxy-2-naphthoic acid and 2,6-dihydroxy anthraquinone. Two commercially available liquid crystalline copolyesters are Ekonol, a homopolymer of p-hydroxybenzoic acid, and Ekkcel, a copolymer of p-hydroxybenzoic acid, terephthalic and isophthalic acids, and 4,4-'biphenol. Other liquid crystalline polyarylates of interest include the copolyester of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid in a 75/25 molar ratio.

The liquid crystalline polyesters which may be used as a component of the blends of the present invention are often referred to as "wholly aromatic polyesters". They comprise at least two recurring moieties which, when combined in the polyester, have been found to form an atypical anisotropic melt phase. The aromatic polyesters are considered to be "wholly" aromatic in the sense that each moiety present in the polyester contributes at least one aromatic ring to the polymer backbone. Recentpublications disclosing such polyesters include (a) Belgian Pat. Nos. 828,935 and 828,936, (b) Dutch Pat. No. 7505551, (c) West German Pat. Nos. 2,520,819; 2,520,820 and 2,722,120, (d) Japanese Pat. Nos. 43-223; 2132-116; 3017-692, and 3021-293,

(e) U.S. Pat. Nos. 3,991,013; 3,991,014; 4,057,597; 4,066,620; 4,075,262; 4,118,372; 4,156,070; 4,159,365; 4,169,933; 4,181,792 and 4,536,562; and

(f) U.K. Application No. 2,002,404.

The preferred polyesters are those derived from Ekonol and Ekkcel, those based on p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid mentioned above; and also the terephthalate copolyesters of hydroquinone and phenyl hydroquinone as described in U.S. Patent No. 4,159,365; the copolyester from terephthalic acid, 2,6-naphthalene dicarboxylic acid and phenyl hydroquinone, as described by W. J. Jackson, Jr., Macromolecules, 16 1027 (1983); the copolyester from terephthalic acid, methyl hydroquinone, and meta-hydroxybenzoic acid, see U.S. Patent No. 4,146,702. Other preferred liquid crystalline polyesters are derived from the materials described in U.S. Pat. Nos. 4,067,852; 4,083,829; 4,130,545; 4,161,470; 4,184,996; 4,238,599; 4,238,598; 4,230,817; 4,224,443; 4,219,461 and in 4,256,624. The above-described polyesters, in order to be useful in the present invention, must exhibit optical anisotropy in the melt phase. These polyesters readily form liquid crystals in the melt phase and accordingly exhibit a high tendency for the polymer chains to orient in the shear direction. Such anisotropic properties are manifested at a temperature at which the wholly aromatic polyester readily undergoes melt processing to form shaped articles. The anisotropic properties may be confirmed by conventional polarized light techniques whereby crossed-polarizers are utilized. More specifically, the anisotropic melt phase may conveniently be confirmed by the use of a Leitz polarizing microscope at a magnification of 40X with the sample on a Koffler hot stage and under a nitrogen atmosphere. The melt phases of the wholly aromatic polyesters which are suitable for use in the present invention are optically anisotropic, i.e., they transmit light when examined between crossed-polarizers. By contrast, the melt of a conventional polymer will not transmit appreciable light when placed between crossed-polarizers.

The most preferred liquid crystalline polyesters are derived from Ekonol and Ekkcel, and those incorporating units from (20) and (21).

The liquid crystalline polyesters of the instant invention should have molecular weights of at least 5,000 and preferably, of at least 10,000.

As mentioned before, the novel blends of the instant invention are prepared by synthesizing the liquid crystalline polyester in the presence of a preformed poly(aryl ether ketone), a poly(aryl ether), or a poly(phenylene oxide). Typical preparative methods known in the art can be used. They are outlined in Schemes (I) - (III).

Scheme I. heat

R₇COOAr₅OCOR₇ + HOOCAr₆COOH →Polyester+R₇COOH (I) 200-350ºC

(22) (23) vacuum or (24) (25) processing aid

The groups Ar₅ and Ar₆ are divalent aromatic radicals which are residues of diphenols and diacids that are suitable components for the liquid crystalline polyester. The method depicted above consists in first preparing an ester of the hydroxyl-containing reactants with a lower mono-carboxylic acid. R₇ preferably a C₁ to C₄ alkyl or a phenyl group. These esters are then reacted under acidolysis conditions with the acid containing reactants to yield the polyester and the lower monocarboxylic acid which can be recycled. The two steps, i.e., the preparation of the monocarboxylic acid esters of the phenolic reactants and their polymerization can be performed separately, or in a one-pot procedure. The acidolysis reaction can be performed in bulk or in the presence of from about 10 to about 60, more preferably, from about 25 to about 60, and most preferably, from about 30 to about 60 weight percent, based on the weight of the final blend produced, of a processing aid. The preferred processing aids are a diphenyl ether compound as described in U.S. Patent Nos. 4,294,956 and 4,296,232; a cycloaliphatic substituted aromatic or heteroaromatic compound, as described in U.S. Patent No. 4,294,957; and a halogenated and/or etherated substituted aromatic or heteroaromatic compound as described in U.S. Patent No. 4,374,239. Other useful processing aids are the diaryl sulfones, terphenyl, dibenzylbenzenes, and benzophenone. The polymerization reaction can also be conducted using a slurry process as described in U.S. Patent No. 4,083,829.

The lower monocarboxylic acid R₇COOH is most preferably acetic acid. The acidolysis reaction is preferably carried out within the temperature range of from about 200 to about 350°C. However, lower and higher temperatures may also be used. Also, if necessary, the molecular weights of the copolymers can be further advanced using solid state polymerization techniques such as described, for example, in U.S. Patent Nos. 3,684,766, 3,780,148, 4,075,173, and 4,314,051. The reaction can be carried out at atmospheric, or subatmospheric pressures; it can also be performed under pressures higher than atmosphpric. The acidolysis reaction generally does not require a catalyst. In some instances, however, the use of an appropriate catalyst may prove advantageous. Typical catalysts include dialkyl tin oxides (e.g., dibutyl tin oxide), diaryl tin oxides, titanium dioxide, antimony trioxide, alkoxy titanium silicates, titanium alkoxides, alkali and alkaline earth metal salts of carboxylic acids (e.g., zinc acetate), the gaseous acid catalysts, such as Lewis acids (e.g., BF₃), hydrogen halides (e.g., HCl), etc. The quantity of catalyst utilized typically is about 0.001 to 1 percent by weight based upon the total monomer weight, and most commonly about 0.01 to 0.2 percent by weight.

Scheme II

In this scheme the acid-containing monomers are first transformed into the corresponding diaryl esters. The latter are then submitted to an ester-exchange reaction as shown in the equation below. The two steps can be performed separately or in a one-pot procedure.

HOAr₅OH + Ar₇OCOAr₆COOAr₇ →Polyester + Ar₇OH (II) (26) (27) vacuum or (24) (28) processing aid

The groups Ar₅ and Ar₆ are divalent aromatic radicals as defined above; Ar₇ is a monovalent aromatic group, preferably phenyl or tolyl. The reaction can be performed in bulk or in the presence of from about 10 to about 60, more preferably from about 25 to about 60, and most preferably, from about 30 to about 60 weight percent, based on the weight of the final blend produced, of a processing aid. The preferred processing aids are a diphenyl ether compound, a cycloaliphatic substituted aromatic or heteroaromatic compound, or a halogenated and/or etherated substituted aromatic or heteroaromatic compound as described in, for example, U.S. Pat. No. 4,459,384. Other useful processing aids are for example, the diaryl sulfones, terphenyl, dibenzylbenzenes, and benzophenone.

Preferably, phenyl esters of the carboxylic acids are used. The ester-exchange reaction is generally carried out in the temperature range of about 200 to about 350°C. However, lower and higher temperatures can also be used. If necessary, the molecular weights of the block copolymers can be further advanced using solid state techniques, vide ultra. The reaction can be performed at atmospheric, reduced, or higher than atmospheric pressures. Catalysts such as, for example, alkali metal phenoxides, may be used to accelerate the polymerization.

Scheme III

In this scheme the acid function is first transformed into the corresponding acid chloride which is then condensed with the phenolic reactant to high polymer. The polymerization is illustrated in equation (III), wherein Ar₅ and Ar₆ are divalent aromatic radicals as defined above. The condensation depicted in the equation above can be performed in a variety of ways. Thus, it can be carried out via the interfacial technique, as described by P. W. Morgan in "Condensation Polymers by Interfacial and Solution Methods", Interscience, New York, 1965. The interfacial method, however , is rather of limited usefulness, due to the generally low solubility of the liquid crystalline polyesters. Hence, relatively low molecular weights are obtained via this route.

It is, thus, more advantageous to carry out the polycondensation in a high boiling solvent at elevated temperatures as described, for example, in U.S. Pat. Nos. 3,733,306 and 3,160,602. These temperatures are typically in the range of 100 to about 350°C. Typical solvents useful for this type of polymerization are, for example, the chlorinated aromatic hydrocarbons such as chlorobenzene, dichloro-, trichloro-, and tetrachlorobenzenes, chlorinated diphenyls or diphenyl ethers, chlorinated naphthalenes, as well as nonchlorinated aromatics such as terphenyl, benzophenone, dibenzylbenzenes, and the like. The reaction can be run with or without catalysts. Typical catalysts are metallic magnesium, as described in U.S. Pat. No. 3,733,306, tetravalent titanium esters, as described in German Patent Application 1,933,687, and the like.

Among the three types of processes, those following Schemes I and II are preferred. The process of Scheme I is most preferred. The weight ratio of the blend components, i.e., the ratio of the poly(aryl ether ketone) or of the poly(aryl ether), or of the poly(phenylene oxide) to the liquid crystalline polyester may be within the range of 90:10 to 10:90 by weight. It is preferably in the range of 20:80 to 80:20, and most preferably in the range of 25:75 to 75:25.

Obviously, ternary and quaternary blends are also feasible via the novel process of the instant invention. Thus, it is possible to prepare the liquid crystalline polyester in the presence of a mixture of two poly(aryl ethers), or in the presence of a mixture of a poly(aryl ether) and of a poly(aryl ether ketone), etc. The possible variations and permutations are obvious to those skilled in the art.

The blends of this invention may include mineral fillers such as carbonates including chalk, calcite and dolomite; silicates including mica, talc, wollastonite; silicon dioxide; glass spheres; glass powders; aluminum; clay; quartz; and the like. Also, reinforcing fibers such as fiberglass, carbon fibers, and the like may be used. The blends may also include additives such as titanium dioxide; thermal stabilizers, ultraviolet light stabilizers, plasticizers, and the like.

The blends of this invention may be fabricated into any desired shape, i.e., moldings, coatings, films, or fibers. They are particularly desirable for molding, for fiber, and for use as electrical insulation for electrical conductors. Also, the blends may be woven into monofilament threads which are then formed into industrial fabrics by methods well known in the art as exemplified by U.S. Patent 4,359,501. Further, the blends may be used to mold gears, bearings and the like.

EXAMPLES

The following examples serve to give specific illustrations of the practice of this invention but they are not intended in any way to limit the scope of this invention.

The following designations are used in the examples and they have the following meaning:

Poly(aryl ether ketone) I. A polymer having a repeat unit of the formula:

and a reduced viscosity (RV) greater than 1.0 dl/g as measured is concentrated sulfuric acid (lg/100 ml.) at 25°C.

Poly(aryl ether ketone) II. A polymer having a repeat unit of the formula: and a reduced viscosity (RV) greater than 1.0 dl/g as measured in concentrated sulfuric acid (lg/100 ml.) at 25°C.

Poly(aryl ether ketone) III. A polymer having a repeat unit of the formula: and a reduced viscosity (RV) greater than 1.0 dl/g as measured is concentrated sulfuric acid (lg/100 ml.) at 25°C.

Poly(aryl ether) I. A polymer having a repeat unit of the formula:

₃ and a reduced viscosity (RV) greater than 0.45 as measured in chloroform, (0.2 gms/100 ml.) at 25°C.

Poly(aryl ether) II. A polymer having a repeat unit of the formula:

and a reduced viscosity (RV) greater than 0.45 as measured in N-methylpyrrolidone (0.2 gms/100 ml.) at 25°C.

Poly(phenylene oxide). A polymer having the formula:

wherein the value of n is at least 100 Polymerization via the Diacetate Route

General Procedure The preformed poly(aryl ether ketone), poly(aryl ether), or poly(phenylene oxide) and the appropriate liquid crystal polyester forming reactants are placed into a reactor. About 40 wt. percent, based on the weight of the final blend to be produced, of an appropriate processing aid are also charged into the reactor. The system is purged with nitrogen for about 20 minutes and then the heat is turned on to raise the temperature of the reactor to about 270°C. Acetic acid starts to distill when the temperature of the mixture reaches about 255°C. Acetic acid distillation is followed by measuring its level in the receiver. After about 3.5 to 5 hrs. at 270-350°C the power draw on the agitator begins to increase which indicates a viscosity increase. The reaction is generally terminated after about 7 to 10 hours. If necessary, the polyester molecular weight can be increased further using solid-state polymerization techniques, vide ultra. The polymer blend can be isolated by either solvent evaporation using, for example, a twin-screw extruder; it can also be precipitated by coagulation in a non-solvent, e.g., alcohol, acetone, and the like. The reaction mixture may also be diluted with a good solvent, filtered either directly or after treatment with an absorbent such as charcoal, and the blend then isolated by the methods outlined above.

It is to be noted that the preparation of the blends via the ester-exchange route (Scheme II) follows a procedure very much similar to that outlined above for the acidolysis polymerization. Tables I and II list the blends that are prepared. They show excellent mechanical and thermal stability properties.

The polymer blends listed in Table I display outstanding chemical and solvent resistance.

The Polymer Blends listed in Table II display very good chemical and solvent resistance.

Claims

What is claimed is:

1. A process for the preparation of improved blends comprising a poly(aryl ether ketone), a poly(aryl ether), or a poly(phenylene oxide) and a liquid crystalline polyester which comprises preparing the liquid crystalline polyester in the presence of the preformed high molecular weight poly(aryl ether ketone), poly(aryl ether sulfone), or poly(phenylene oxide).

2. A process as defined in claim 1 wherein the liquid crystalline polyester is prepared by:

(a) forming esters of the hydroxyl-containing reactants with a lower monocarboxylic acid, and

(b) subjecting the esters so formed to acidolysis with the acid containing reactants. 3. A process as defined in claim 2 wherein the monocarboxylic acid is a C₁ to C₅ alkanoic acid or benzoic acid.

4. A process as defined in claim 2 wherein the acid is acetic acid. 5. A process as defined in claim 2 wherein the acidolysis of step (b) is carried out in the presence of a catalyst.

6. A process as defined in claim 5 wherein the catalyst is selected from dialkyl tin oxides, diaryl tin oxides, titanium dioxide, antimony trioxide, alkoxy titanium silicates, titanium alkoxides, alkali and alkaline earth metal salts of carboxylic acids, Lewis acids, and hydrogen halides.

7. A process as defined in claim 1 wherein the liquid crystalline polyester is prepared by:

(a) forming the aryl esters of the carboxyl containing reactants, and

(b) subjecting the esters so formed to an ester exchange reaction with the hydroxyl-containing reactants. 8. A process as defined in claim 2 or 7 wherein step (b) is carried out using solid state polymerization.

9. A process as defined in claim 2 or 7 wherein step (b) is carried out at a temperature of from about 200°-350°C.

10. A process as defined in claim 7 wherein step (b) is carried out in the presence of a catalyst.

11. A process as defined in claim 10 wherein the catalyst is an alkali metal phenoxide..

12. A process as defined in claim 1 wherein the liquid crystalline polyester is prepared by: (a) forming the acid chloride derivatives from the acid containing reactants, and

(b) condensing the acid chloride derivative so formed with the hydroxyl-containing reactants.

13. A process as defined in claim 12 wherein step (b) is carried out by an interfacial technique.

14. A process as defined in claim 12 wherein step (b) is carried out in a high boiling solvent at elevated temperatures.

15. A process as defined in claim 14 wherein the high boiling solvent is selected from chlorinated aromatic hydrocarbons, chlorinated diphenyls or diphenyl ethers and chlorinated naphthalenes.

16. A process as defined in claim 14 wherein the high boiling solvent is selected from terphenyl, benzophenone or dibenzylbenzene.

17. A process as defined in claim 12 wherein step (b) is carried out in the presence of a catalyst selected from metallic magnesium or tetravalent titanium esters.