Homopolyesters and copolyesters, of diacids and specific ketodiols, exhibiting melt-anisotropy and being melt-spinnable into oriented filaments that can be heat treated to high tenacity and modulus.

DESCRIPTION 
Technical Field 
This invention relates to fiber-forming, melt-spinnable polyesters that 
exhibit optical anisotropy in the melt. 
BACKGROUND 
Aromatic polyesters that form optically anisotropic melts and can be 
melt-spun into oriented filaments are disclosed in U.S. Pat. No. 
4,118,372. The filaments can be heat treated to high tenacity and modulus. 
The polyesters are prepared primarily from para-oriented dihydric aromatic 
compounds and para-oriented aromatic dicarboxylic acids. 
The use of selected aromatic monoand diketodiols and aromatic dicarboxylic 
acids in the preparation of polyesters that are optically anisotropic in 
the melt and can be melt-spun into oriented fibers is disclosed in U.S. 
Pat. Nos. 4,269,965; 4,245,082; and 4,226,970. 
It is an object of this invention to provide novel polyesters. Another 
object is to provide such polymers that form anisotropic melts and that 
can be melt-spun into filaments having a high as-spun modulus. A further 
object is to provide such filaments that can be heat treated to high 
tenacity and modulus. Other objects will become apparent hereinafter. 
DISCLOSURE OF INVENTION 
For further comprehension of the invention and of the objects and 
advantages thereof, reference may be made to the following description and 
to the appended claims in which the various novel features of the 
invention are more particularly set forth. 
The invention resides in homopolyesters consisting essentially of 
substantially equimolar amounts of the recurring units 
##STR1## 
wherein R.sup.1 is m-phenylene or p-phenylene; 
R.sup.2 is 
##STR2## 
each of R.sup.3, R.sup.4, R.sup.6 and R.sup.7 is independently selected 
from H, CH.sub.3 and Cl; 
R.sup.5 is m-phenylene, p-phenylene, ethylenedioxybis-p-phenylene or 
p,p'-biphenylene; and 
n is 0 or 1; 
provided; however: 
(aa) when n is 0, R.sup.2 is 
##STR3## 
R.sup.3 and R.sup.4 or R.sup.6 and R.sup.7 are both Cl and R.sup.5 is 
p-phenylene or ethylenedioxybis-p-phenylene, or R.sup.2 is 
##STR4## 
R.sup.3, R.sup.4, R.sup.6 and R.sup.7 are H and R.sup.5 is 
ethylenedioxybis-p-phenylene; and 
(bb) when n is 1, R.sup.1 is m-phenylene, R.sup.2 is 
##STR5## 
R.sup.5 is ethylenedioxybis-p-phenylene or p, p'-biphenylene, one of 
R.sup.3 and R.sup.4 is CH.sub.3 or Cl and the other is H, and one of 
R.sup.6 and R.sup.7 is CH.sub.3 or Cl and the other is H. 
The invention also resides in copolyesters consisting essentially of the 
recurring units 
##STR6## 
wherein each of X.sup.1 and Y.sup.1 is independently selected from 
m-phenylene and p-phenylene; 
##STR7## 
each of X.sup.3, X.sup.4, X.sup.6, X.sup.7, Y.sup.3, Y.sup.4, Y.sup.6 and 
Y.sup.7 is independently selected from H, CH.sub.3 and Cl; 
R.sup.5 is m-phenylene, p-phenylene, ethylenedioxybis-p-phenylene or 
p,p'-biphenylene; and 
n is 0 or 1, 
each of the recurring units (i) and (ii) comprising 40 to 60 mol % of their 
combined amounts which is substantially equimolar with the amount of (b), 
provided, however: 
(aa) when n is 0 and one of X.sup.2 and Y.sup.2 is attached at the 
p-phenylene positions and the other is attached at the m-phenylene 
positions, then X.sup.3, X.sup.4, X.sup.6, X.sup.7, Y.sup.3, Y.sup.4, 
Y.sup.6 and Y.sup.7 are H and R.sup.5 is p-phenylene or 
ethylenedioxybis-p-phenylene; 
(bb) when n is 0 and X.sup.2 and Y.sup.2 are both attached at the 
p-phenylene positions, 1 or 2 of X.sup.3, X.sup.4, X.sup.6 and X.sup.7 and 
1 or 2 of Y.sup.3, Y.sup.4, Y.sup.6 and Y.sup.7 are independently selected 
from CH.sub.3 and Cl, the remaining 2 or 3 of X.sup.3, X.sup.4, X.sup.6 
and X.sup.7 and the remaining 2 or 3 of Y.sup.3, Y.sup.4, Y.sup.6 and 
Y.sup.7 are H, and R.sup.5 is m-phenylene, p-phenylene or 
ethylenedioxybis-p-phenylene; 
(cc) when n is 0, X.sup.2 and Y.sup.2 are both attached at the p-phenylene 
positions, and either X.sup.3, X.sup.4, X.sup.6 and X.sup.7 are each 
independently selected from CH.sub.3 and Cl and Y.sup.3, Y.sup.4, Y.sup.6 
and Y.sup.7 are H or X.sup.3, X.sup.4, X.sup.6 and X.sup.7 are H and 
Y.sup.3, Y.sup.4, Y.sup.6 and Y.sup.7 are each independently selected from 
CH.sub.3 and Cl, then R.sup.5 is m-phenylene. 
(dd) when n is 0 and X.sup.2 and Y.sup.2 are both attached at the 
m-phenylene positions, 1 or 2 of X.sup.3, X.sup.4, X.sup.6, X.sup.7, 
Y.sup.3, Y.sup.4, Y.sup.6 and Y.sup.7 are independently selected from 
CH.sub.3 and Cl, the remaining 6 or 7 of X.sup.3, X.sup.4, X.sup.6, 
X.sup.7, Y.sup.3, Y.sup.4, Y.sup.6 and Y.sup.7 are H, and R.sup.5 is 
p-phenylene or ethylenedioxybis-p-phenylene; 
(ee) when n is 1, X.sup.2 is 
##STR8## 
and Y.sup.2 is 
##STR9## 
(ff) when n is 1 and X.sup.1 and Y.sup.1 are both m-phenylene, 6 of 
X.sup.3, X.sup.4, X.sup.6, X.sup.7, Y.sup.3, Y.sup.4, Y.sup.6 and Y.sup.7 
are independently selected from CH.sub.3 and Cl, the remaining 2 of 
X.sup.3, X.sup.4, X.sup.6, X.sup.7, Y.sup.3, Y.sup.4, Y.sup.6 and Y.sup.7 
are H, and R.sup.5 is p,p'-biphenylene; and 
(gg) when n is 1 and one of X.sup.1 and Y.sup.1 is m-phenylene and the 
other is p-phenylene, each of X.sup.3, X.sup.4, X.sup.6, X.sup.7, Y.sup.3, 
Y.sup.4, Y.sup.6 and Y.sup.7 is independently selected from CH.sub.3 and 
Cl, or one of each pair X.sup.3 and X.sup.4, X.sup.6 and X.sup.7, Y.sup.3 
and Y.sup.4 and Y.sup.6 and Y.sup.7 is independently selected from 
CH.sub.3 and Cl and the other of each pair is H, and R.sup.5 is 
p,p'-biphenylene. 
The invention also resides in shaped articles of the aforesaid polyesters, 
including molded and extruded articles, examples of the latter being films 
and filaments. 
As the terms are used herein, a homopolyester is the condensation polymer 
prepared from one diol and one dicarboxylic acid, and a copolyester is the 
condensation polymer prepared from a diol and a dicarboxylic acid and at 
least one additional diol and/or dicarboxylic acid. The term "polyester" 
includes both homopolyester and copolyester. 
As the term is used herein, "consisting essentially of" means that the 
polyester includes the recited essential recurring units. This definition 
is not intended to preclude the presence of minor amounts (less than 10 
mol %) of other recurring units of a nonessential type which do not 
deleteriously affect the properties, and particularly, the 
melt-anisotropic behavior, of the polyester. 
As indicated above, the invention herein also resides in high modulus 
filaments of the above polyesters, for example, a modulus of greater than 
200 g/denier (177 dN/tex), which filaments can be heat treated to high 
tenacity, for example, greater than 12 g/denier (10.7 dN/tex), and even 
higher modulus. 
The polyesters of this invention are prepared by means of conventional 
procedures using appropriate mono or diketodiols and appropriate 
dicarboxylic acids. The monoketodiol can be prepared by reacting, under 
anhydrous conditions, the appropriate R.sup.3 /R.sup.4 -, X.sup.3 /X.sup.4 
- or Y.sup.3 /Y.sup.4 -substituted phenol and the appropriate hydroxyacid 
(HO.sub.2 C-R.sup.2 -OH, HO.sub.2 C-X.sup.2 -OH or HO.sub.2 C-Y.sup.2 -OH) 
in hydrogen fluoride, in the presence of boron trifluoride, at a 
temperature in about the range 0.degree.-100.degree. C. The diketodiol can 
be similarly prepared by reacting the appropriate hydroxy acids of the 
formulas 
##STR10## 
and HO--R.sup.2 --CO.sub.2 H with the appropriate, aromatic hydrocarbon of 
the formula H-R.sup.1 -H, or by reacting the appropriate monophenols of 
the formulas 
##STR11## 
and H-R.sup.2 -OH with the appropriate dicarboxylic acid of the formula 
HO.sub.2 C-R.sup.1 -CO.sub.2 H, it being understood that, in all the 
aforesaid formulas, as is necessary to prepare the desired polyester, 
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be replaced with X.sup.1 or 
Y.sup.1, X.sup.2 or Y.sup.2, X.sup.3 or Y.sup.3 and X.sup.4 or Y.sup.4, 
respectively. The reaction can be conveniently carried out on an 
approximately molar scale, with the reactants being charged to a 1 L 
shaker tube (Hastalloy.RTM. C) which is then cooled and evacuated. Liquid 
HF is added, then BF.sub.3 in slight excess of such amount as to provide 
one mole for each mole of water produced and one mole for each mole of 
carbonyl functionality. The combined amounts of reactants, HF and BF.sub.3 
total about 700 g. The reaction time is generally about 4 to 18 hours. The 
product is discharged onto 2 L of ice (no water), then made up to 2.5 L 
with water and stirred vigorously. If the product is crystalline, it can 
be recovered by filtration; if it is not, sufficient methylene chloride is 
added to dissolve the product and, after pH adjustment to 7-8 with aqueous 
ammonia, the organic phase is separated from the aqueous phase and the 
product is recovered from the organic phase by evaporation. 
Diols prepared by the above procedure can be conveniently purified by 
conversion to esters, preferably acetate esters, by treatment with the 
appropriate carboxylic acid anhydride, for example, acetic anhydride. 
Acetylation of diols is accomplished with acetic anhydride, for example, 4 
moles of acetic anhydride/mole of diol, in sufficient acetic acid to 
ensure adequate fluidity for stirring, for example, 1 to 2 L of acetic 
acid/mole of diol. The reaction is conveniently run overnight at ambient 
temperature with acid catalysis, for example, 10 g of 
trifluoromethanesulfonic acid/mole of diol, or under reflux for 4 h with 
base catalysis, for example, 80 g of sodium acetate/mole of diol. The 
base-catalyzed acetylation usually produces purer product. When reaction 
is complete, the acid catalyst, if present, is neutralized with sodium 
acetate, and the reaction mixture is diluted to twice its volume with ice 
and water. Product is isolated by filtration, washed with water, dried, 
and further purified by crystallization from an appropriate solvent. 
As an example, 2,6-dichlorophenol (0.7 mole), m-hydroxybenzoic acid (0.7 
mole), BF.sub.3 (2.0 moles) and HF (400 g) were reacted in accordance with 
the above procedure for 4 h at 30.degree. C. The recovered diol product 
was acetylated as described above, and the 3,5-dichloro-4,3' 
diacetoxybenzophenone produced was recovered and recrystallized from 
ethyl acetate/cyclohexane; yield 37%; melting point 
115.degree.-116.degree. C. 
The polyesters of this invention are capable of forming optically 
anisotropic melts and exhibit molecular weights and melting points which 
permit melt-spinning into filaments at temperatures below 400.degree. C. 
Preferred polyesters of the invention have been melt-spun into filaments 
which have been heat-treated to increase strength properties. 
The polyesters of the invention can be prepared by standard melt 
polymerization techniques from one or more aromatic dicarboxylic acids of 
the formula HO.sub.2 C-R.sup.5 -CO.sub.2 H, wherein R.sup.5 is defined as 
above, and one or more appropriate mono- or diketodiols, as defined above, 
frequently in the diester for, for example, the diacetate. The diphenol 
and dicarboxylic acids are normally combined in substantially equimolar 
amounts and heated in a reaction vessel under nitrogen with stirring for 
about 4 to 24 hours. Temperatures employed for the polymerization 
(condensation) are above the melting points of the reactants and are 
generally in the range of 200.degree. to 350.degree. C. The reaction 
vessel is equipped with means to permit by-product removal while 
polymerization takes place. A vacuum is normally applied towards the end 
of the polymerization to facilitate removal or remaining by-products and 
to complete the polymerization. Polymerization conditions, such as 
temperature, duration of heating and pressure, can be varied, for example, 
in the light of the reactants employed and the degree of polymerization 
desired. 
The polyesters can be spun into filaments by conventional melt-spinning 
techniques. A melt of the polymer is extruded through a spinneret into a 
quenching atmosphere, for example, air or nitrogen maintained at room 
temperature, and wound up. Such general spinning conditions are given, for 
example, in U.S. Pat. No. 4,066,620. 
As the term is used herein in the description of the fiber, "as-spun" means 
that the fiber has not been drawn or heat treated after extrusion and 
normal windup. The as-spun fibers of this invention can be subjected to 
heat treatment in an oven to provide high strength fibers which are useful 
for a variety of industrial applications, such as plastic and rubber 
reinforcement. In the heat treating process, fiber samples, as skeins or 
on bobbins, preferably collapsible, Teflon.RTM.-coated, stainless-steel 
bobbins, are usually heated under various restraints in an oven that is 
continuously purged by flow of inert gas to remove by-products from the 
vicinity of the fiber. Temperatures approaching the fusion point, but 
sufficiently below to prevent interfilament fusion, are employed. 
Preferably, the maximum temperature is reached in a stepwise fashion. 
Inherent viscosity (.eta..sub.inh) is defined by the commonly used equation 
EQU .eta..sub.inh =[ln(.eta..sub.rel)/C] 
wherein .sub.rel is the relative viscosity and C is the concentration of 
polymer in the solvent (0.5 g/100 mL). The relative viscosity (.sub.rel) 
is determined by dividing the flow time, in a capillary viscometer, of the 
dilute solution by the flow time, in the same capillary viscometer, for 
the pure solvent. Flow times are determined at 30.degree. C., and the 
solvent is a mixture of, by weight, 7.5% trifluoroacetic acid, 17.5% 
methylene chloride, 12.5% dichlorotetrafluoroacetone hydrate, 12.5% 
perchloroethylene and 50% p-chlorophenol. 
Fiber tensile properties are reported herein in conventional units, with 
the corresponding SI units in parenthesis. 
Denier: g/9000 m (1.11 dtex) 
Tenacity: g/denier (0.89 dN/tex) 
Elongation: percent of unstretched length 
Modulus: g/denier (0.89 dN/tex) 
Measurements were made using established procedures, such as disclosed in 
U.S. Pat. No. 3,827,998, on fibers that had been conditioned for at least 
one hour. At least three breaks were averaged. The commonly used 
Thermooptical Test (TOT), as described, for example, is U.S. Pat. No. 
4,066,620, was used and involves heating a polymer sample between crossed 
(90.degree.) polarizers on the heating stage of a polarizing microscope. 
Polymers that pass this test (+) are considered to be optically 
anisotropic in the molten state. The orientation angle was determined 
according to established procedures, such as disclosed in U.S. Pat. No. 
3,671,542. 
The following examples are illustrative of the invention. All temperatures 
are in degrees Celsius unless otherwise indicated. Examples 1A, 1B and 3B 
include comparative experiments which are outside the invention and which 
demonstrate that the properties, and particularly melt-anisotropic 
behavior, of polyesters are not predictable from a consideration of the 
diester and diacid reactants used to prepare them. 
Tables 1 and 2 which follow summarize the homopolyesters and copolyesters 
prepared in the examples. All symbols have the same meanings as defined in 
the aforesaid formulas. 
TABLE 1 
______________________________________ 
A. Homopolyesters containing dioxy units (a) wherein 
n is one, R.sup.1 is m-phenylene and R.sup.4 and R.sup.7 
are H (Example 3A) 
Prep'n. R.sup.3 R.sup.6 R.sup.5 
______________________________________ 
O CH.sub.3 
CH.sub.3 p,p'-biphenylene 
P CH.sub.3 
CH.sub.3 ethylenedioxybis-p-phenylene 
Q Cl Cl ethylenedioxybis-p-phenylene 
R Cl Cl p,p'-biphenylene 
______________________________________ 
B. Homopolyesters containing dioxy units (a) where 
n is zero and R.sup.6 and R.sup.7 are H (Example 1A) 
Prep'n. R.sup.3 R.sup.4 R.sup.2 R.sup.5 
______________________________________ 
A Cl Cl p-bridged 
p-phenylene 
B Cl Cl p-bridged 
ethylenedioxybis- 
p-phenylene 
C H H m-bridged 
ethylenedioxybis- 
p-phenylene 
______________________________________ 
TABLE 2 
__________________________________________________________________________ 
A. Copolyesters containing dioxy units (a) (i) and 
(a) (ii) wherein n is one, Y.sup.1 is m-phenylene 
and R.sup.5 is p,p'-biphenylene (Example 3B) 
Prep'n. 
X.sup.3 
X.sup.4 
X.sup.6 
X.sup.7 
X.sup.1 Y.sup.3 
Y.sup.4 
Y.sup.6 
Y.sup.7 
__________________________________________________________________________ 
S CH.sub.3 
CH.sub.3 
CH.sub.3 
CH.sub.3 
p-phenylene 
CH.sub.3 
CH.sub.3 
CH.sub.3 
CH.sub.3 
T CH.sub.3 
CH.sub.3 
CH.sub.3 
CH.sub.3 
m-phenylene 
CH.sub.3 
H CH.sub.3 
H 
U CH.sub.3 
H CH.sub.3 
H p-phenylene 
CH.sub.3 
H CH.sub.3 
H 
V Cl Cl Cl Cl p-phenylene 
Cl Cl Cl Cl 
W Cl Cl Cl Cl m-phenylene 
Cl H Cl H 
__________________________________________________________________________ 
B. Copolyesters containing dioxy units (a) (i) and (a) (ii) 
wherein n is zero and X.sup.6 and X.sup.7 are H (Examples 1B and 2) 
Prep'n. 
X.sup.3 
X.sup.4 
X.sup.2 
Y.sup.3 
Y.sup.4 
Y.sup.6 
Y.sup.7 
Y.sup.2 
R.sup.5 
__________________________________________________________________________ 
-- H H p-bridged 
CH.sub. 3 
CH.sub.3 
CH.sub.3 
CH.sub.3 
p-bridged 
m-phenylene 
E H H p-bridged 
Cl Cl Cl Cl p-bridged 
m-phenylene 
F Cl 
Cl 
p-bridged 
CH.sub.3 
H H H p-bridged 
p-phenylene 
G Cl 
Cl 
p-bridged 
CH.sub.3 
H H H p-bridged 
ethylenedioxybis- 
p-phenylene 
H Cl 
Cl 
p-bridged 
CH.sub.3 
CH.sub.3 
H H p-bridged 
p-phenylene 
I Cl 
Cl 
p-bridged 
CH.sub.3 
CH.sub.3 
H H p-bridged 
ethylenedioxybis- 
p-phenylene 
J H H m-bridged 
CH.sub.3 
H H H m-bridged 
p-phenylene 
K H H m-bridged 
CH.sub.3 
H H H m-bridged 
ethylenedioxybis- 
p-phenylene 
L H H m-bridged 
CH.sub.3 
CH.sub.3 
H H m-bridged 
p-phenylene 
M H H p-bridged 
H H H H m-bridged 
p-phenylene 
N H H p-bridged 
H H H H m-bridged 
ethylenedioxybis- 
p-phenylene 
__________________________________________________________________________

EXAMPLE 1 
Homopolyesters and Copolyester of Monoketodiols and Dicarboxylic Acids 
A. Homopolyesters A-C shown in Table 1B and comparative homopolyesters S1 
and S2 were prepared using the following procedures. To a glass reactor 
equipped with a nitrogen inlet and sidearm were added the reactants shown 
in Table 3. The mixture was heated under a nitrogen atmosphere for about 8 
h at 283.degree., removed from the reactor and ground in a Wiley mill at 
liquid nitrogen temperature until the particles passed through a 20 mesh 
(U.S. Sieve Series) screen, and then reheated for 8 h at 283.degree.. The 
properties of the resulting polyesters are given in Table 4; 
homopolyesters A-C passed the TOT test (+); homopolyesters S1 and S2 
failed TOT (-) and are outside the invention since they do not meet the 
requirements of the homopolyester proviso (aa). 
Similarly, Preparation A was repeated except that isophthalic acid was used 
in place of terephthalic acid; Preparation A was repeated except that 
3-chloro-4,4'-diacetoxybenzophenone was used in place of 
3,5-dichloro-4-4'-diacetoxybenzophenone; and Preparation B was repeated 
except that 3,3',5,5'-tetrachloro-4,4'-diacetoxybenzophenone was used in 
place of 3,5-dichloro-4,4'-diacetoxybenzophenone. The three homopolyesters 
so produced failed the TOT test (-) and are outside the invention since 
they fail to meet the requirements of homopolyester proviso (aa). 
B. Copolyester E shown in Table 2B was prepared as described in Part A 
hereinabove except that the diester used was a 1:1 (molar) mixture of 
3,3',5,5'-tetrachloro-4,4'-diacetoxybenzophenone (1.090 g) and 
4,4'-diacetoxybenzophenone (0.745 g) and the diacid used was isophthalic 
acid (0.730 g). The resulting polymer passed the TOT test (+); the 
properties are given in Table 4. 
In place of 3,3',5,5'-tetrachloro-4,4'-diacetoxybenzophenone in preparation 
E of this Part B there may be employed 
3,3',5,5'-tetramethyl-4,4'-diacetoxybenzophenone. 
Similarly, Preparation E was repeated three times except that terephthalic 
acid, ethylenedioxybis-p-benzoic acid and 4,4'-bibenzoic acid, 
respectively, were used in place of isophthalic acid. The three 
copolyesters so produced failed the TOT test (-) and are outside the 
invention since they fail to meet the requirements of copolyester proviso 
(cc). 
TABLE 3 
______________________________________ 
Diester Diacid 
Struc- Struc- 
Prep'n. 
ture* wt(g) mmols ture* wt(g) mmols 
______________________________________ 
A 1 1.835 5.0 4 0.830 5.0 
B 1 1.468 4.0 5 1.208 4.0 
C 2 1.192 4.0 5 1.208 4.0 
S1 3 1.956 6.0 4 0.996 6.0 
S2 3 1.304 4.0 5 1.208 4.0 
______________________________________ 
*1 = 
2 = 3,4diacetoxybenzophenoneophenone 
3 = 
4 = terephthalic acidoxybenzophenone 
5 = ethylenedioxybisp-benzoic acid 
TABLE 4 
______________________________________ 
Inherent 
Prep'n. Viscosity PMT(.degree.C.)* 
FT(.degree.C.)* 
______________________________________ 
A 0.86 -- 350 
B 0.96 -- 260 
C 0.98 310 258 
E 0.83 -- 240 
S1 0.87 -- 250 
S2 0.90 -- 260 
______________________________________ 
*PMT = Polymer melt temperature; 
FT = flow temperature 
Homopolyester preparation A to C and S1 and S2 and copolyester preparation 
E were mechanically melt spun, using spinnerets having a single 0.23 mm 
diameter hole, at spinneret temperatures of 298.degree. to 355.degree., 
and the fibers were wound up at speeds of 400 to 1070 m/min; data are 
given in Table 5A. Tensile properties of single filaments of these fibers 
were measured at room temperature, as-spun, and after heat treatment on a 
bobbin, under restraint, in a nitrogen atmosphere at 205.degree. to 
300.degree. C. for periods of up to 24 h. Property data are given in Table 
5B; the data represent the average of five 2.54 cm breaks. In Table 6 are 
given the best single-break values obtained after heat-treatment of the 
same filaments of homopolyesters A-C and copolyester E. 
TABLE 5A 
______________________________________ 
Spinneret Wind-Up 
Temperature Speed 
Prep'n. (.degree.C.) (m/min) Denier 
______________________________________ 
A 355 920 4 
B 321 905 2.5 
C 324 1050 3 
E 328 1070 4 
S1 355 800 4 
S2 298 400 4 
______________________________________ 
TABLE 5B 
______________________________________ 
Orien- 
Fiber Tenacity Elong. Modulus 
tation 
Prep'n. 
Treatment* (g/d) (%) (g/d) Angle 
______________________________________ 
A 1 4.2 2.2 290 28 
2 17.8 2.3 620 
B 1 4.6 2.7 210 27 
2 18.9 3.1 400 
C 1 2.7 2.7 208 30 
17.1 4.3 315 
E 1 4.1 2.9 210 26 
2 18.1 2.2 500 
S1 1 2.5 6.1 175 31 
2 9.8 3.9 160 
S2 1 2.2 12.9 87 33 
2 5.6 6.1 87 
______________________________________ 
*1 = as spun; 
2 = after heat treatment 
TABLE 6 
______________________________________ 
Tenacity Elong. Modulus 
Prep'n. (g/d) (%) (g/d) 
______________________________________ 
A 18.4 2.3 610 
B 18.9 3.1 400 
C 17.9 4.1 320 
E 18.8 2.1 510 
______________________________________ 
Comparative preparations S1 and S2, which were not melt-anisotropic, 
resulted in relatively weak fibers, the modulus of which could not be 
improved by heat treatment. 
EXAMPLE 2 
Copolyesters of Monoketodiols and Dicarboxylic Acids 
Copolyesters F-N shown in Table 2B were prepared by the procedure described 
in Example 1B except that the reactants used were as shown in Table 7. In 
each preparation two diols in the form of diacetates were used in a molar 
ratio of 1:1. The resulting polymers had the properties given in Table 8; 
all passed the TOT test (+). 
TABLE 7 
__________________________________________________________________________ 
Diester (1) Diester (2) Diacid 
Struc- Struc- Struc- 
Prep'n. 
ture* 
wt(g) 
mmols 
ture* 
wt(g) 
mmols 
ture* 
wt(g) 
mmols 
__________________________________________________________________________ 
F 1 1.101 
3.0 6 0.936 
3.0 4 0.996 
6.0 
G 1 0.734 
2.0 6 0.624 
2.0 5 1.208 
4.0 
H 1 0.917 
2.5 3 0.815 
2.5 4 0.830 
5.0 
I 1 0.734 
2.0 3 0.652 
2.0 5 1.208 
4.0 
J 2 0.894 
3.0 7 0.936 
3.0 4 0.996 
6.0 
K 2 0.596 
2.0 7 0.624 
2.0 5 1.208 
4.0 
L 2 0.894 
3.0 8 0.978 
3.0 4 0.996 
6.0 
M 9 0.894 
3.0 2 0.894 
3.0 4 0.996 
6.0 
N 9 0.596 
2.0 2 0.596 
2.0 5 1.208 
4.0 
__________________________________________________________________________ 
*1 = 
2 = 3,4diacetoxybenzophenoneophenone 
3 = 
4 = terephthalic acidoxybenzophenone 
5 = ethylenedioxybisp-benzoic acid 
6 = 3methyl-4,4diacetoxybenzophenone 
7 = 3methyl-4,3diacetoxybenzophenone 
8 = 3,5dimethyl-4,3diacetoxybenzophenone 
9 = 4,4diacetoxybenzophenone 
TABLE 8 
______________________________________ 
Inherent 
Prep'n. Viscosity PMT(.degree.C.) 
FT(.degree.C.) 
______________________________________ 
F 0.56 -- 355 
G 0.61 280 265 
H 0.75 -- 360 
I 0.82 -- 320 
J 0.83 320 280 
K 0.92 310 250 
L 0.80 -- 338 
M 0.72 355 330 
N 0.82 320 270 
______________________________________ 
EXAMPLE 3 
Homopolyesters and Copolyesters of Diketodiols and Dicarboxylic Acids 
A. Homopolyesters O-R in Table 1A were prepared by the procedure described 
in Example 1A except that the reactants used were as shown in Table 9. The 
resulting polymers had the properties given in Table 10; all passed the 
TOT test (+). 
TABLE 9 
______________________________________ 
Diester Diacid 
Struc- Struc- 
Prep'n. 
ture* wt(g) mmols ture* wt(g) mmoles 
______________________________________ 
O 10 1.507 3.5 12 0.848 3.5 
P 10 1.507 3.5 5 0.998 3.3 
Q 11 1.410 3.0 12 0.726 3.0 
R 11 1.410 3.0 5 0.906 3.0 
______________________________________ 
*10 = 
11 = 
5 = ethylenedioxybisp-benzoic acidenzene 
12 = 4,4bibenzoic acid 
TABLE 10 
______________________________________ 
Inherent 
Prep'n. Viscosity PMT(.degree.C.) 
FT(.degree.C.) 
______________________________________ 
O 0.38 275 184 
P 0.41 300 201 
Q 0.40 295 200 
R 0.40 310 205 
______________________________________ 
B. Copolyesters S-W shown in Table 2A were prepared by the procedure 
described in Example 1B except that the reactants used were as shown in 
Table 11. In each preparation two diols in the form of diacetates were 
used in a molar ratio of 1:1. The resulting polymers had the properties 
given in Table 12; all passed the TOT test (+). 
Similarly, Preparation S was repeated two times except that terephthalic 
acid and ethylenedioxybis-p-benzoic acid, respectively, were used in place 
of 4,4'-bibenzoic acid; and Preparation S was repeated except that 
1,3-bis(3-methyl-4-acetoxy-benzoyl)benzene was used in place of 
1,3-bis(3,5-dimethyl-4-acetoxybenzoyl)benzene. The three copolyesters so 
produced failed the TOT test (-) and are outside the invention since they 
fail to meet the requirements of copolyester proviso (gg). 
TABLE 11 
__________________________________________________________________________ 
Diester (1) Diester (2) Diacid 
Struc- Struc- Struc- 
Prep'n. 
ture* 
wt(g) 
mmols 
ture* 
wt(g) 
mmols 
ture* 
wt(g) 
mmols 
__________________________________________________________________________ 
S 13 0.757 
1.65 
14 0.757 
1.65 
12 0.799 
3.3 
T 14 0.802 
1.75 
10 0.753 
1.75 
12 0.848 
3.5 
U 15 0.753 
1.75 
10 0.753 
1.75 
12 0.848 
3.5 
V 16 0.810 
1.5 17 0.810 
1.5 12 0.726 
3.0 
W 17 0.810 
1.5 11 0.675 
1.43 
12 0.726 
3.0 
__________________________________________________________________________ 
*13 = 
14 = 
15 = 
16 = 
17 = 
10 = 
11 = 
12 = 4,4bibenzoic acid 
TABLE 12 
______________________________________ 
Inherent 
Prep'n. Viscosity PMT(.degree.C.) 
FT(.degree.C.) 
______________________________________ 
S 0.27 -- 311 
T insoluble 300 181 
U insoluble -- 326 
V 0.29 -- 320 
W insoluble 320 200 
______________________________________ 
Best Mode for Carrying Out the Invention 
The best mode presently contemplated for carrying out the invention is 
reflected by the homopolyester and copolyester preparations of Example 1. 
Industrial Applicability 
The applicability of polyesters of high tenacity and modulus is well known 
in the textile industry. The polyesters of this invention are especially 
useful in this industry. 
Although the above description includes preferred embodiments of the 
invention, it is to be understood that there is no intent to limit the 
invention to the precise constructions herein disclosed and that the right 
is reserved to all changes and modifications coming within the scope of 
the invention as defined in the appended claims.