Described herein are novel block copolymers wherein one block is a poly(aryl ether) oligomer and the other block is a liquid crystalline polyester oligomer. Processes for the preparation of the subject copolymers are also described. The novel block copolymers display excellent mechanical properties, good high temperature stability and excellent solvent and chemical resistance.

FIELD OF THE INVENTION 
This invention is directed to novel block copolymers wherein one block is a 
poly(aryl ether)oligomer and the other block is a liquid crystalline 
polyester oligomer. Processes for the preparation of the subject 
copolymers are also described. The novel block copolymers display 
excellent mechanical properties, good high temperature stability and 
excellent solvent and chemical resistance. 
BACKGROUND OF THE INVENTION 
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 repeating units of the following formula (1): 
##STR1## 
It is produced by the polycondensation of 
4-(4'-chlorophenylsulfonyl)phenol, as described in British Patent 
Specification No. 1,153,035. The polymer contains no aliphatic moieties 
and has a heat deflection temperature of approximately 210.degree. C. The 
other commercially available poly(aryl ether sulfone) is available from 
Union Carbide Corporation under the trademark UDEL.RTM.. It has a heat 
deflection temperature of about 180.degree. C. and repeating units of the 
following formula (2): 
##STR2## 
However, the solvent and chemical resistance of the poly(aryl ether 
sulfones) are only marginal. 
Liquid crystalline aromatic polyesters are well known in the art. These 
liquid crystalline polyesters are described in, for example, U.S. Pat. 
Nos. 3,804,805; 3,637,595; 4,130,545; 4,161,470; 4,230,817 and 4,265,802. 
The liquid crystalline polyesters 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 particularly suitable for high strength fibers and 
filaments. Their main drawback as molding materials resides in the 
anisotropy of properties displayed by molded parts. An excellent overview 
of liquid crystalline polyesters was published recently, see W. J. 
Jackson, Jr., Journal of Applied Polymer Science, Applied Polymer 
Symposium 41, 25-33 (1985). 
THE INVENTION 
The present invention is directed to novel block copolymers of poly(aryl 
ethers) and liquid crystalline polyesters. Processes for the preparation 
of the subject copolymers are also described. Due to the highly 
crystalline nature of the polyester blocks, the copolymeric materials of 
the instant invention are phase separated. The poly(aryl ether) rich 
products are thus an amorphous (or crystalline) poly(aryl ether)matrix 
that contains dispersed in it and chemically bound to it, the highly 
oriented crystalline domains of the liquid crystalline polyester. The 
materials are essentially molecular composites which show improved 
mechanical properties. An important mechanical property advantage is the 
fact that molded parts are significantly less anisotropic than those 
obtained from the unmodified liquid crystalline polyester. Unexpectedly, 
good solvent and chemical resistance are also observed with these 
composites, even though the liquid crystalline phase is not the continuous 
phase. On the other end of the compositional spectrum, i.e., for the 
polyester-rich block copolymers, the anisotropy of the molded parts is 
also decreased, though to a lesser extent. Again, the products display 
very good solvent and chemical resistance. 
Another advantage of the block copolymers of this invention is their 
relatively low melt viscosity which allows for easy fabricability. The 
polymers, as pointed out above, have very good mechanical properties and 
retain the favorable high temperature characteristics of the constituents. 
Finally, due to the chemical bond between the blocks the overall properties 
are superior to those displayed by the blends as described in U.S. Pat. 
No. 4,460,736. 
The block copolymers of the instant invention can be described by the 
formula (AB).sub.z where A and B are the poly(aryl ether) and the liquid 
crystalline polyester blocks, respectively; and where z is 1 or greater. 
The block copolymers may also have the structure (ABC).sub.n and 
(ABCD).sub.n, wherein A, B, and n are as defined above, and C and D are 
poly(aryl ether ketone) and liquid crystalline polyester blocks, different 
from the blocks A and B. 
The poly(aryl ether)oligomers suitable for the purposes of this invention 
are linear themoplastic polyarylene polyethers containing recurring units 
of the formula: 
EQU --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. Pat. Nos. 
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 
##STR3## 
sulfone 
##STR4## 
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 Ar is an aromatic group and preferably is a phenylene group, 
R.sub.1 and R'.sub.1 can 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 c's are independently integers having a 
value of from 0 to 4, inclusive and R.sub.2 is representative of a bond 
between aromatic carbon atoms as in dihydroxyl-diphenyl, or is a divalent 
radical, including for example, radicals such as 
##STR5## 
--O--, --S--, --S--S-- --SO--, --SO.sub.2, 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 Ar 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,-hexafluroropropane 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 groups 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 
##STR6## 
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 
##STR7## 
the carbonyl group 
##STR8## 
the vinylene group 
##STR9## 
the sulfoxide group 
##STR10## 
the azo group --N.dbd.N--; the saturated flurocarbon groups 
##STR11## 
--CF.sub.2 --CF.sub.2 CF.sub.2 ; organic phosphine oxides 
##STR12## 
where R.sub.3 is a hydrocarbon group and the ethylidene group 
##STR13## 
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 the halogen atom or nitro 
group on the benzenoid nucleus. 
The polyarylene polyether oligomers 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. Pat. No. 4,176,222 in which at least one bisphenol and 
at least one dihalobenzenoid are heated at a temperature of from about 
100.degree. to about 400.degree. 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 Pat. No. 847,963 wherein the bisphenol and dihalobenzenoid 
compound are heated in the presence of potassium carbonate using a high 
boiling solvent such as diphenylsulfone. 
Preferred polyarylene polyethers of this invention are those prepared using 
the dihydric polynuclear phenols of the formulae (3)-(7) including the 
derivatives thereof which are substituted with inert substituent groups; 
##STR14## 
in which the R.sub.4 groups represent independently hydrogen, lower alkyl, 
aryl, and the halogen substituted groups thereof, which can be the same or 
different; 
##STR15## 
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 residua. 
The preferred dichlorobenzenoid compounds are (8), (9), (10) and (11); they 
may carry inert substituent groups. 
##STR16## 
The most preferred poly(aryl ether)oligomers have the repeating units 
(12), (13), (14), and (15). 
##STR17## 
The poly(aryl ether) blocks have number average molecular weights of at 
least 1,000, preferably of at least 1,500, and most preferably of at least 
2,000. 
The liquid crystalline polyarylate oligomers which may be used herein are 
well known in the art. These liquid crystalline polyarylates are described 
in, for example, U.S. Pat. Nos. 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-hydroxy benzoic 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 polyester oligomers which may be used as a component 
of the block copolymers of the present invention are often referred to as 
oligomers of "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. Recent publications 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 and 4,181,792 and (f) U.K. Application No. 
2,002,404. 
The preferred polyester oligomers 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. Pat. 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-hyroxybenzoic acid, see U.S. Pat. No. 4,146,702. 
Other preferred liquid crystalline polyester oligomers 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 oligomers, 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 polyester blocks are derived from 
Ekonol and Ekkcel, and those incorporating units from (16) and (17). 
##STR18## 
The block copolymers of the present invention are prepared using 
hydroxyl-terminated poly(aryl ether)oligomers and the appropriate liquid 
crystal polyester monomers under typical polyester forming conditions. The 
methods are outlined in the schemes (I)-(III); the symbol HO(EOE'O).sub.n 
EOH represents a hydroxyl-terminated poly(aryl ether)oligomer wherein n is 
such that its number average molecular weight be at least 1,000, 
preferably at least 1,500, and most preferably at least 2,000. 
Scheme I 
##STR19## 
The groups Ar and Ar.sub.1 are divalent aromatic radicals which are 
residues of diphenols and diacids that are suitable components for the 
liquid crystalline polyester blocks. The method depicted above consists in 
first preparing an ester of the hydroxyl-containing reactants with a lower 
mono-carboxylic acid. These esters are then reacted under acidolysis 
conditions with the acid containing reactants to yield the block copolymer 
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 block copolymer produced, of a 
processing aid. The preferred processing aids are a diphenyl ether 
compound as described in U.S. Pat. Nos. 4,294,956 and 4,296,232; a 
cycloaliphatic substituted aromatic or heteroaromatic compound, as 
described in U.S. Pat. No. 4,294,957; and a halogenated and/or etherated 
substituted aromatic or heteroaromatic compound as described in U.S. Pat. 
No. 4,374,239. The polymerization reaction can also be conducted using a 
slurry process as described in U.S. Pat. No. 4,083,829. 
The lower monocarboxylic acid R.sub.5 COOH is preferably acetic acid. The 
acidolysis reaction is preferably carried out within the temperature range 
of about 200.degree. to 350.degree. C. However, lower and higher 
temperatures may also be used. Also, in some instances the molecular 
weight of the block copolymers may be advanced using solid state 
techniques of the type described in U.S. Pat. Nos. 4,075,173, 3,780,148, 
3,684,766 and 4,314,051. The reaction can be carried out at atmospheric or 
subatmospheric pressures; it can also be performed under pressures higher 
than atmospheric. 
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 oxide (e.g., dibutyl 
tin oxide), diaryl tin oxide, 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., BF.sub.3), 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. 
##STR20## 
The groups Ar and Ar.sub.1 are divalent aromatic radicals as defined above; 
Ar.sub.2 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 as the weight of the block 
copolymer 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. 
Preferably, phenyl esters of the carboxylic acids are used. The 
ester-exchange reaction is generally carried out in the temperature range 
of 200.degree.-350.degree. C. However, lower or higher temperatures can 
also be used. Also, in some instances the molecular weight of the block 
copolymer may be advanced using solid state techniques. 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). 
##STR21## 
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 is generally useful; however, in some instances, where 
the final block polymer has a limited solubility in the solvents generally 
employed in this type of condensation, only low molecular weight 
copolymers result. 
In such instances it is advantageous to carry out the polycondensation in a 
high boiling solvent as described, for example, in U.S. Pat. Nos. 
3,733,306 and 3,160,602. 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 No. 1,933,687, and the like. 
Among the three type of processes, those following Schemes I and II are 
preferred. The process of Scheme I is most preferred. 
The poly(aryl ether) oligomers (18) are prepared by using typical poly(aryl 
ether) preparative 
EQU HO(EOE'O).sub.n EOH (18) 
processes and an excess of diphenol component. The higher the excess of the 
diphenol the lower the molecular weight of the resulting 
dihydroxy-terminated oligomer (18). 
The number average molecular weight of the liquid crystalline polyester 
blocks in the block polymers of the instant invention should be at least 
1,000, preferably at least 1,500, and most preferably, at least 2,000. 
The weight ratios of the components, i.e. the ratio poly(aryl ether):liquid 
crystalline polyester may be within the range of 1:9 to 9:1. It is 
preferably in the range of 2:8 to 8:2, and most preferably in the range of 
25:75 to 75:25. 
The polymers of the instant invention have a reduced viscosity (RV) of at 
least 0.25 dl/g as measured in an appropriate solvent. Depending on the 
type of blocks and on the composition of the block polymer a variety of 
solvents may be used for the determination of the RV. These solvents are, 
for example, CH.sub.2 Cl.sub.2, CHCl.sub.3, phenol-tetrachloroethane 
mixtures, N-methylpyrrolidone, pentafluorophenol, and the like. 
The polymers 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 polymers may also 
include additives such as titanium dioxide; thermal stabilizers, 
ultraviolet light stabilizers, plasticizers, and the like. 
The polymers 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 polymers 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. Pat. No. 4,359,501. Further, the polymers 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. 
Preparation of Dihydroxy End-capped Poly(aryl ether) Oligomers 
General Procedure 
The desired amount of dihydric phenol is charged to a flask containing a 
solvent mixture of monochlorobenzene and dimethyl sulfoxide. The phenol is 
converted to the disodium salt in situ by adding the required amount of 
sodium hydroxide. The system is dehydrated by heating and removing the 
monochlorobenzene-water azeotrope. The desired amount of dihalo benzenoid 
compound is then added and reacted with the sodium salt of the phenol at 
about 140.degree. C. The polymer is recovered by filtering the solution, 
then precipitating, filtering, washing and drying. The molecular weight of 
the oligomer is controlled by the amounts of the monomers used, and to 
produce a hydroxy terminated oligomer, a molar excess of the bisphenol is 
employed. The material is treated with acid, such as oxalic, hydrochloric, 
or citric acids to convert the terminal --ONa groups to --OH groups. 
Using the procedure outline above the following oligomers are prepared: 
Oligomer A from excess of 2,2'-bis(4-hydroxyphenyl)propane ("bisphenol-A") 
and 4,4'-dichlorodiphenyl sulfone, molecular weight of 2,400. 
Oligomer B from reagents above, but having a molecular weight of 5,380. 
Oligomer C from the reagents above, having a molecular weight of 10,000. 
The procedure above is slightly modified in that 
(a) a higher boiling aprotic solvent (N-methylpyrrolidone or sulfolane) is 
used instead of the dimethylsulfoxide, and 
(b) the polycondensation is performed in the presence of the required 
amount of solid mixtures of Na.sub.2 CO.sub.3 /K.sub.2 CO.sub.3 at 
temperatures of up to 220.degree. C. 
In this manner oligomer D is prepared. It is made from an excess of 
4,4'-dihydroxydiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone and has a 
molecular weight of 6,000. Similarly, using an excess of 4,4'-biphenyl and 
4,4'-dichlorodiphenyl sulfone, oligomer E is prepared. It has a molecular 
weight of 6,000. 
Preparation of the Diacetates of the Hydroxyl-terminated Oligomers 
General Procedure 
Into a glass lined reactor are charged about 800 gms of the oligomer and 
2,000 grams of acetic anhydride. The mixture is heated to about 
135.degree. C. and held at this temperature for about 4 hours. Vacuum is 
then slowly applied to distill acetic acid and excess acetic anhydride. At 
maximum vacuum (.about.2 mm), the material temperature is allowed to rise 
to about 150.degree. C. and held until no further distillation is evident 
(approximately 30 to 50 minutes). Analysis of the crude product shows that 
the conversion of the oligomer to the diacetate is 99.9% complete. The 
material also contains some residual acetic anhydride (usually less than 
about 1,000 ppm based on the weight of the oligomer diacetate as measured 
by titration with morpholine as described in Siggia and Hana, 
"Quantitative Organic Analysis via Functional Groups", Fourth Edition, 
Wiley-Interscience, 1979, pages 231 to 235). 
The diacetates prepared by the procedure above can be used without any 
further purification for the preparation of the polyether-liquid 
crystalline polyester block copolymers. 
Polymerization via the Diacetate Route 
General Procedure 
The crude diacetate and the appropriate liquid crystal polyester forming 
reactants are placed into a reactor. About 40 wt. percent, based on the 
block copolymer 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.degree. C. Acetic acid starts to distill when the 
temperature of the mixture reaches about 255.degree. C. Acetic acid 
distillation is followed by measuring its level in the receiver. After 
about 3.5 to 5 hrs. at 270.degree. 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; the final temperature 
being in the range of about 270.degree. C. to about 350.degree. C. The 
polymer 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 then isolated by the 
methods outlined above. 
It is to be noted that the preparation of the block copolymers via the 
ester-exchange route follows a procedure very much similar to that 
outlined above for the acidolysis polymerization. 
Table I lists the polymers that are prepared. Their properties are also 
shown. 
TABLE I 
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Liquid crystal polyester 
Weight ratio of 
Properties 
reactant(s) blocks (Poly- Thermal 
Solvent and 
Oligomer 
(mole ratio) ether/Polyester) 
Mechanical 
Stability 
chemical resistance 
__________________________________________________________________________ 
##STR22## 1:1 Very good 
Very good 
Good 
##STR23## 
(75:25) 
B 
##STR24## 6:4 Very good 
Very good 
Good 
C 
##STR25## 8:2 Excellent 
Very good 
Moderate 
##STR26## 
##STR27## 
##STR28## 
(1:0.2:0.8:1.00) 
D 
##STR29## 3:7 Good Excellent 
Excellent 
##STR30## 
(75:25) 
E As above (under D) 1:1 Excellent 
Excellent 
Excellent 
F 
##STR31## 1:1 Excellent 
Excellent 
Excellent 
##STR32## 
##STR33## 
(0.5:1.00:0.5) 
__________________________________________________________________________ 
*In all of the examples a small additional amount of terephthalic acid 
equivalent to the amount of the particular oligomer is used.