GB2030158A - Polyesters derived from 3,4'- dihydroxy-benzophenones or 3- hydroxy-4'-(4-hydroxyphenyl-) benzophenone and certain aromatic dicarboxylic acids and filaments thereof - Google Patents
Polyesters derived from 3,4'- dihydroxy-benzophenones or 3- hydroxy-4'-(4-hydroxyphenyl-) benzophenone and certain aromatic dicarboxylic acids and filaments thereof Download PDFInfo
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- GB2030158A GB2030158A GB7927468A GB7927468A GB2030158A GB 2030158 A GB2030158 A GB 2030158A GB 7927468 A GB7927468 A GB 7927468A GB 7927468 A GB7927468 A GB 7927468A GB 2030158 A GB2030158 A GB 2030158A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
- C07C49/83—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups polycyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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Abstract
The invention provides a fiber- forming (co)polyester consisting essentially of units having the structural formulas: <IMAGE> wherein R1 in at least 85 mol% of units I is <IMAGE> in which X is methyl or chloro and n is 0, 1 or 2, wherein R2 in at least 85 mol% of units II is selected from the group consisting of p-phenylene, 2,6-naphthylene and p,p'-biphenylene, and wherein R3 is m- or p-phenylene with units III constituting from 0 to 15 mol % of the total units I and III and with the proviso that when n is 1 or 2, R2 in at least 85 mol% of units II is 2,6- naphthylene or p,p'-biphenylene. Filaments are melt-spun from the (co)polyesters, which are optically anisotropic in the melt. As-spun filaments from the (co)polyesters can be heat treated while free from tension to increase their tenacity.
Description
SPECIFICATION
Polyesters derived from 3, 4'-dihydroxy-benzophenones or 3-hydroxy-4'-(4-hydroxyphenyl-)benzophenone and certain aromatic dicarboxylic acids and filaments thereof
This invention pertains to fiber-forming melt-spinnable aromatic polyesters and to high modulus filaments thereof.
A class of aromatic polyesters that form optically anisotropic melts from which oriented filaments can be melt-spun has been described in US 4,118,372 to Schaefgen et al. Other aromatic polyesters that have this property are disclosed in U. S. 4,066,620. The polyesters which are described in the aforementioned references are derived primarily from pa ra-oriented dihydric phenols and para-oriented aromatic dicarboxylic acids. Filaments that are melt-spun from such polyesters can be heat treated to high tenacity and modulus.
This invention provides different anisotropic-melt-forming polyesters which can be melt-spun into filaments of high as-spun modulus [e.g. greater than 200 g/denier (177dN/tex)]. The novel filaments can also be heat treated to increase theirtenacities, preferably to a level in excess of 10 g/denier (8.84dN/tex), while retaining moduli in excess of 200 g/denier (177 dN/tex).
According to the present invention, there is thus provided a fiber-forming (co) polyester consisting essentially of units having the structural formulas:
wherein R1 in at least 85 mol % of units I is
in which Xis methyl or chloro and n is 1 or 2, wherein R2 in at least 85 mol % of units II is selected from the group consisting of p-phenylene, 2,6-naphthylene and p, p'-biphenylene, and wherein Rg is m- or p-phenylene with units Ill constituting from 0 to 15 mol % of the total units land Ill and with the proviso that when n is 1 or 2, R2 is at least 85 mol % of units Ills 2,6-naphthylene or p, p'-biphenylene.
R1 in up to 15 mol % of the fO-R1-O units is preferably selected from the group consisting of m-phenylene, p-phenylene, chloro-p-phenylene, methyl-p-phenylene, p, p'-biphenylene, tetramethyl-p, p'-biphenylene, 2,6-naphthylene and 2,7-naphthylene; and R2 in up to 15 mol % of the
units is preferably m-phenylene.
Fiber-forming (co)polyesters according to the invention include the following: a) a fiber-forming (co)polyester consisting essentially of units having the structural formulas:
wherein R1 in at least 85 mol % of units lis
in which Xis methyl or chloro and n is 1 or 2 and wherein R2 in at least 85 mol % of the units Ills p-phenylene, 2,6-naphthylene or p,p'-biphenylene with the proviso that when n is 1 or 2, R2 in at least 85 mol % of the units Ills 2,6-naphthylene or p, p'-biphenylene.
b) a fiber-forming (co)polyester consisting essentially of units having the structural formulas:
wherein R1 is
in which Xis methyl or chloro and n is O, 1 or 2 and wherein R2 is p-phenylene, 2,6-naphthylene or p, p'-biphenylene with the proviso that when n is 1 or 2, R2 is 2,6-naphthylene or p, p'-biphenylene.
c) a fiber-forming (co)polyester consisting essentially of units having the structural formulas:
in which X is methyl or chloro and n is 0, 1 or 2, R2 is p-phenylene, 2,6-naphthylene or p,p'-biphenylene and
R3 is m- or p-phenylene with units Ill constituting up to 15 mol % of the total of units I and Ill.
According to a further feature of the present invention, there are provided filaments of (co)polyesters according to the invention as hereinbefore defined.
The (co)polyesters of the present invention consist essentially of -O-R1-O- units derived from dihydric phenols (with the option of up to 15 mol % of
units as hereinbefore defined) and
units derived from aromatic dicarboxylic acids in substantially equimoiar amounts. at least 85 mol % and preferably all of the -O-R1-O- units are
in which X is chloro or methyl and n is 1 or 2. Preferably n is 0, that is, the unit is unsubstituted.The remaining -O-R1-O- units, i.e., up to 15 mol %, are selected from the group consisting of
At least 85 mol % and preferably all of the
units are selected from the group consisting
and
The remaining
units, i.e., up to 15 mol %, are
when n is 1 or 2, R2 must be 2,6-naphthylene or p,p-'biphenylene in at least 85 mol % of the
units. Alternatively the (co) polyesters consist essentially of
in which X is methyl or chloro and n is 0, 1 or 2, (B) terephthaloyl, 2,6-naphthoyl or p,p'-bi-benzoyl and (C) m- or p-oxybenzoyl units in proportions as defined above.
The (co) polyesters of the invention are capable of forming optically anisotropic melts and have a molecular weight sufficient for melt-spinning into filaments. The term "(co) polyesters" is intended to include both homopolyesters and copolyesters.
Polymerization condition
The (co) polyesters may be prepared by standard melt poymerization techniques from one or more aromatic dicarboxylic acids of the formula
where R2 is defined as above, and one or more diphenols of the formuia HO-R1-OH where r1 is defined as above. Frequently the diphenols are employed in their diester form (e.g., diacetate). The diphenols and diacids are normally combined in substantially equimolar amounts and heated in a reaction vessel under nitrogen with stirring for about 1 to 3 hours. Temperatures employed for the polymerization are above the melting points of the reactants and are generally in the range of 200 to 350"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 of remaining by-products and to complete the polymerization. Polymerization conditions such as temperature, duration of heating, pressures, etc., may be varied according to, e.g., the reactants employed and the degree of polymerization desired.
Filament preparation
The (co)polyesters may be spun into filaments by conventional melt-spinning techniques. A melt of the polymer is extruded through a spinneret into a quenching atmosphere (e.g., air or nitrogen maintained at room temperature) and wound up. General spinning conditions are given in U. S. Pat. No.4,066,620.
As used herein, the term "as-spun" fiber refers to a fiber which has not been drawn or heat treated after extrusion and normal windup.
Heat treatment and utility
The as-spun fibers of this invention may be subjected to heat treatment in an oven while relaxed to provide high strength fibers 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 bobbins) are usually heated in an inert atmosphere that is continuously purged by flow of inert gas through the oven 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.
Measurements and tests
Inherent viscosity (inh) iS defined by the following equation:
wherein (rlrer) represents the relative viscosity and C represents a concentration of 0.5 gram of the polymer in 100 ml of solvent. The relative viscosity (llrel ) is determined by dividing the flow time in a capillary viscometer of the dilute solution by the flow time for the pure solvent. Flow times are determined at 300C, and the solvent is p-chloro-phenol unless otherwise indicated.
Fibertensile properties are reported in customary units first with SI units in parentheses.
Denier (D) in g/9000m. (dtex)
Tenacity (T) in g/denier (dN/tex)
Elongation (E) in percent of un
stretched length
Modulus (Mi) in g/denier (dN/tex)
They are measured using the procedures shown in Morgan U. S. Pat. No. 3,827,998 on fibers that have been conditioned for at least one hour. At least three breaks are averaged.
Thermooptical Test (TOT) is described in U. S. Patent No. 4,066,620. Polymers that pass this test are considered to be optically anisotropic.
The following examples are illustrative of the present invention.
Example I - Synthesis of 4' -diacetoxybenzophenone
The 3,4'-diacetoxybenzophenone used in subsequent polymerizations was prepared in stages starting from m-anisic acid. It was converted first to m-anisoyl chloride, then to 3,4'-dimethyoxy-benzophenone, then to 3,4'-dihydroxybenzophenone, and finally to 3,4'-diacetoxybenzophenone. This example provides the details of one such conversion and, except for changes in scale, was the general procedure for all such preparations.
Preparation of m-anisoyl chloride
A mixture of 100 g of m-anisic acid (0.658 mole), 250 g thionyl chloride (2.10 mole), and 5 ml dimethylformamide was heated under reflux in a round-bottom flask with desiccant in the top of the condenser for exclusion of atmospheric moisture. Excess thionyl chloride was distilled from the product using a rotary film-evaporator at about 200 torr (26.6 kPa). The m-anisoyl chloride was then isolated by fractional distillation through a 25 cm Vigreux column at 109"C/12 torr (1.6 kPa). Yield was 90 g (0.528 mole),
i.e., about 80%.
Preparation of 3, -dimethoxybenzophenone A round-bottom flask was fitted with a stirrer, dropping funnel, nitrogen inlet, and thermometer. It was cooled in an ice/water bath. The initial charge was a mixture of 69.0 g anisole (0.638 mole), 90 g anhydrous aluminum trichloride (0.675 mole), and 108 g tetrachloroethane. It was cooled to below 15"C, with stirring, while a slow current of nitrogen was passed over the mixture. A solution of 90 g m-anisoyl chloride (0.528
mole) in 108 ml tetrachloroethane was added via the dropping funnel at a rate avoiding temperature increase
of the stirred mixture to above 1 5"C (addition period of 1 to 2 hr.).Following mixing, the flask stood two days
at room temperature before ice (ca. 250g) was carefully added to decompose the AICI3 complex. The tetrachloroethane was removed by steam distillation. The organic products were separated from the
aqueous mixture by extracting into 500 ml of methylene chloride followed by drawing off and discarding the
aqueous layer. Two washes of the methylene chloride solution with about 200 ml of 5% aqueous sodium
hydroxide, and one wash with about 200 ml of water followed, removing and discarding the aqueous layer
each time. After distilling off the methylene chloride using a rotary film-evaporator, 102 g of 3,
4'-dimethoxybenzophenone (0.42 mole) remained which crystallized on cooling to room temperature.It was
recrystallized from ethanol to yield 87 g (0.36 mole) of crystals melting at 53-55"C. This material is also
described along with its preparation in J. Am. Chem. Soc. 54 (1932) p. 1449.
Preparation of 3, 4'-dihydroxybenzophenone
Demethylation was accomplished by heating under reflux, for 15 hr., a mixture of 87 g 3,4'
-dimethoxybenzophenone (0.36 mole) and a previously prepared mixture of 240 ml of 48% aqueous
hydrobromic acid, 120 ml acetic anhydride, and 120 ml acetic acid. The dihydroxy product was isolated by
pouring the cooled reaction mixture into about 400 ml water, filtering, washing with water, and drying in an
oveN at 80"C. Melting point was 193-194"C. Yield was 77g (0.36 mole), i.e., about 100%.
Preparation of3,4. 049-diacetoxybenzophenone To a slurry, in a beaker, of 73 g 3, 4'-dihydroxybenzophenone (0.34 mole) in 225 ml acetic anhydride were
added 8 drops of concentrated sulfuric acid, and the mixture was heated 30 min. on a steam bath. The
resultant clear solution was cooled and then poured into about 600 ml water to precipitate the product. It was
filtered, washed with water, and dried in an oven at about 80"C. Recrystallization from methanol yielded 80 g of diacetoxybenzophenone (0.268 mole) melting at 81-83 C.
Example II - Polyterephthalate of 3, 4'-dihydroxybenzophenone
The polymerization apparatus was a 250 ml 3-necked flask equipped with: (1) a glass stirrer mounted in a pressure-tight resin bushing, (2) a nitrogen inlet, (3) a short Vigreux column leading to a water-cooled condenser with a flask for collecting acetic acid, and (4) an electrically heated Woods metal bath mounted for vertical height adjustment. Provision for application of a vacuum was in the distillation adapter.
The flask was charged with 9.57 g of diacetoxybenzophenone (0.032 mole) and 4.98 g of terephthalic acid (0.03 mole) and heated, with stirring, under nitrogen at atmospheric pressure from 238"C to 3100C in 48 min.
Most of the acetic acid by-productwas liberated in this time, Heating at 310 C continued 22 min. more. Then a vacuum of 0.2 torr (0.0266 kPa) was applied, and temperature was raised to 325"C in 8 min. and maintained for 17 min. The cooled polymer had an inherent viscosity, Thnh, of 0.78. Its melt was anisotropic above its flow temperature of 296"C using the TOT test.
The comminuted solid polymer was molded into a cylindrical plug and spun using a press-spinner through a 0.009 inch (0.23 mm) diameter spinneret hole at 3250C under pressure of 700 psi (4830 kPa). Wind-up speed was 1000 ypm (914 m/min). Averaged filament properties were: D/T/E/Mi = 3.54/5.03/1.77/360 (3.92/4.45/1.77/318). The filament was loosely wound on a soft bobbin and heated in an oven in slowly lowing nitrogen as follows: 220 C/1 hr. + 240"C/1 hr. + 260"C/1 hr. + 280"C/1 hr.
+ 300"C/1 hr. After this heating, avereged filament tensile properties were (denier substantially unchanged): T/E/Mi = 11.63/3.76/362 (10.28/3.76/320).
The best single values of tensile properties after heating were: T/E/Mi = 19.98/6.02/426 (17.66/6.02/376.5).
Example III - Poly-2, 6-naphthalenedicarboxylate of 3, 4'-dihydroxybenzophenone
The procedure of Example li was used to polymerize 9.84 g of 3, 4'-diacetoxybenzophenone (0.033 mole) with 6.48 g of 2,6-naphthalenedicarboxylic acid (0.030 mole). Polymerization temperature at atmospheric pressure increased from 235"C to 345"C in 87 minutes, and under vacuum from 345"C to 365"C in 40 minutes.
Inherent viscosity, ninhl was 0.78. In the TOT test, the melt was anisotropic above the flow temperature of 298or.
A plug from the comminuted solid product was molded and spun as in Example II except that extrusion temperature was 360"C and extrusion pressure was 400 psi (2760 kPa). Averaged filament properties were: D/T/E/Mi = 9.11/4.73/1.37/383 (10.12/4.18/1.37/338). Heating under nitrogen, as in Example II, at 225 C/24hr. + 300 C/19hr. improved averaged tensile properties to:
T/E/Mi = 15.88/4.67/349 (14.04/4.67/308).
Example IV - Copoly-2, 6-naphthalenedicarboxylate from 3,4'-dihydroxybenzophenone (90 mol %) and hydroquinone (10 mol /0) Following the procedure of Example II, copolyesterwas prepared from 14.35 g 3,4'-diacetoxybenzophenone (0.048 mole), 1.04 g 1 ,4-diacetoxybenzene (0.0054 mole), and 10.80 g 2,6-naphthalenedicarboxylic acid (0.050 mole). Polymerization temperature at atmospheric pressure increased from 310"e to 352"C in 50 min. and under vacuum maintained at 352"C for 34 min. The comminuted solid polymer was thoroughly washed with acetone to extract materials of low molecular weight. Inherent viscosity, rjjnhl was 0.59.In the TOT test, the melt was an isotropic above the flow temperature of 323"C.
A molded plug of the copolyester was spun as in Example II. The filament, wound at 600 ypm (549 m/min) had averaged properties: D/T/E/Mi = 4.30/ 4.87/1.67/316 (4.78/4.30/1.67/279). It was heated as described in Example II at 225 C/24hr. + 280"C/21 Hr. + 300"C/16hr. to yield tensile properties:
T/E/Mi = 14.03/4.90/344 (12.40/4.90/304).
Example V- Copolyester of 3, 4'-dihydroxybenzophenone with 2, 6-naphthalenedicarboxylic acid (90 mol O/oJ and isophthalic acid (10 mol %)
A mixture of 15.95 g 3, 4'-diacetoxybenzophenone (0.0535 mole), 0.83 g isophthalic acid (0.005 mole), and 9.7 g 2,6-naphthalenedicarboxylic acid (0.045 mole) was polymerized as described in Example II.
Polymerization temperature at atmospheric pressure increased from 305"C to 358"C in 53 min. and under vacuum maintained at 358"C for 17 min. Inherent viscosity, rjnh, was 0.92, and the TOT test showed melt anisotropy above the flow temperature of 303"C.
A plug molded from the comminuted solid copolyester was spun to a filament as described in Example II.
The plug was at 3800C, the spinneret at 385"C, the spinning pressure was 600 psi (4140 kPa), and the windup speed was 600 yd/min. (549 m/min). The as-spun filament had averaged properties: D/T/E/Mi = 5.64/4.78/2.63/283 (6.26/4.22/2.63/250). After heating as in Example II at 200"C/24 hr. + 225"C/3 hr.
+ 250"C/20 hr., the averaged tensile properties were: nE/Mi = 8.34/4.14/269 (7.37/4.14/238).
Example VI - Preparation of 3, 4'-dimethoxy-4-methylbenzophenone The procedures and equipment used in this monomer preparation are as described in Example I. A solution of 94.5 g m-anisoyl chloride (0.554 mole) in 113 ml oftetrachloroethanewas added dropwiseto a stirred, cooled mixture of 80.7 g o-methylanisole (0.661 mole), 94.5 g anhydrous aluminum chloride, and 113 ml tetrachloroethane, keeping the temperature at about 1 5"C. The mixture stood at room temperature for 24hr.After adding ice and extracting with methylene chloride as in the preparation of 3, 4'methoxybenzophenone of Example I, an impure liquid was obtained from which the 3, 4'-dimethoxy-4methylbenzophenone was obtained by fractional distillation in a 25 cm Vigreux column at 1 98"C and 2.0 torr (0.27 kPa) pressure. Yield was 114g (0.445 mole).
Preparation of 3, 4'-dihydroxy-4-methylbenzo-phenone
Demethylation of 114 g 3, 4'-dimethoxy-4-methyl-benzophenone (0.445 mole) was effected by refluxing 15 hr. with a previously prepared mixture of 313.5 ml of 48% aqueous hydrobromic acid, 148 ml of acetic anhydride, and 148 ml of acetic acid. The isolated product melted at 173-174"C. Recrystallization from ethanol/water yielded 79 g (0.346 moie) or 3, 4'-dihydroxy-4-methylbenzophenone melting at 174-175"C.
Preparation of 3, 4'-diacetoxy-4-methylbenzo-phenone
The 79 g of 3, 4'-dihydroxy-4-methyl-benzo-phenone (0.346 mole) was acetylated using 237 ml of acetic anhydride and 8 drops of concentrated sulfuric acid and heating for 30 min. on a steam bath. The product was precipitated in water, filtered, washed and dried at about 80"C. After crystallizing the product from methanol, melting point was 60-640C.
Yield was 87 g (0.279 mole). Before polymerization, this product was once more crystallized from methanol.
Polyester from bibenzoic acid and 3, 4'-diacetoxy-4-methylbenzophenone
Polymerization of 10.89 g bibenzoic acid (0.045 mole) and 14.36 g 3, 4'-diacetoxy-4-methyl-benzophenone (0.046 mole) used the equipment and procedure of Example II. Heating at atmospheric pressure from 290"C to 357"C occurred in 80 min., and heating under vacuum at 357"C was for 19 min. Inherent viscosity, rlinhr of the product was 1.09. The TOT test showed anisotropy of the melt above the flow temperature of 311 C.
A cylindrical molded plug of the comminuted product was spun as described in Example II with the plug at 378"C and under 200 psi (1380 kPa) pressure. Windup speed was 400 yd/min. (366 m/min.). Averaged as-spun filament properties were: D/T/E/Mi = 8.0/4.15/1.15/382 (8.9/3.67/1.15/338). After heating the filament as in Example II at 200"C/ 2 hr. + 250"C/2 hr. + 260"C/1 hr. + 280"C/1 hr. + 305"C/20 hr., the averaged tensile properties were:
T/E/Mi = 8.31/2.90/303 (7.34/2.90/268).
Example VII - Synthesis of 3-hydroxy-4'-r4-hydroxyphenyl-Jbenzophenone
A 1. autoclave was charged with 85.0 g 4-phenylphenol (0.5 mole), 69.0 g 3-hydroxybenzoic acid (0.5 mole) and 500 ml HF (cooled to 0 C). The autoclave was closed, air removed by flushing with BF3. While maintaining the autoclave at 0 C for 6 hr. with shaking, BF3 was applied to the contents at a pressure of 30 psi, (207 kPa).
At the end of this time the reaction mixture was poured into an excess of water (about 2 1.) to precipitate the crude product. This was filtered off, washed well with water and dried.
Yield of crude product 136 g (94%)
M. p. of crude product 213-9 C The above crude product was heated under reflux for 2 hr with about 400 ml acetic anhydride and 0.15 g sulfuric acid. The product was isolated by precipitation of the Ac20 solution into about 2 1. water. Filtered, washed and dried.
Yield of crude product 183 g (theory 187)
M.p. of crude product 95-9 C It was recrystallized from ethanol, m.p. 1 19-121"C.
Example Vlil - Polyterephthalate of 3-h ydroxy-4'-(4-hydroxyphenyl-)benzophenone The polymerization apparatus was similar to that used in Example II. The flask was charged with 15.56 g of the diacetate of 3-hydroxy-4'-(4-hydroxyphenyl-)benzophenone (0.042 mole, 4% excess) and 6.64 g terephthalic acid (0.040 mole) and heated with stirring, under nitrogen at atmospheric pressure from 280"C to 346"C in 35 min. Then a high vacuum was applied and heating was continued at 346"C for 7 min.The cooled polymer had an inherent viscosity, rjinh, of 0.76 (measured in 7.5% trifluoroacetic acid, 17.5% methylene chloride, 12.5% dichlorotetrafluoro acetone hydrate, 12.5% Perclenes and 50% 4-chlorophenol).
The polymer was spun as in Example II at 300"C and the filament wound at 549 m/min. The resulting filament had an average denier of 8.6 dtex and average tensile properties T/E/Mi = 2.21/0.76/448. After heat strengthening as described in Example II at 230"C/2 hr + 2500C/2 hr + 270"C/1 hr + 280"C/18 hr, the following average tensile properties were obtained:
T/E/Mi = 5.85/2.95/226
Example IX - Polyester from 3-hydroxy-4'-r4-hydroxyphenyl-Jbenzophenone and 2,6naphthalenedicarboxylic acid
The polymerization was similar to that of Example VIII except tha 8.64 g of 2, 6-naphthalene-dicarboxylic acid (0.040 mole) was ised inn place of terephthalic acid.The initial heating from 268"C to 3400C was for 31 min under nitrogen at atmospheric pressure. The heating under vacuum was for 2 min at 3400C to 344"C. The polymer had an inherent viscosity, ninth of 0.73 as determined using the solvent employed for this purpose in Example Vlil.
The polymer was melt spun as in Example II at 276"C and the filament was wound up at 366 m/min. The melt spun filaments had an average denier of 7.6 dtex and average tensile properties T/E/Mi = 1.41/0.54/234.
After heat strengthening as described in Example II at2200C/2 hr + 240"C/2 hr + 260"C/2 hr + 280"C/hr + 304"C/18 hr, the following average tensile properties were obtained:
T/E/Mi = 4.79/2.3/231.
Claims (17)
1. A fiber-forming (co)polyester consisting essentially of units having the structural formulas:
wherein R1 in at least 85 mol % of units I is
in which Xis methyl or chloro and n is 1 or 2, wherein R2 in at least 85 mol % of units 11 is selected from the group consisting of p-phenylene, 2,6-naphthyiene and p, p'-biphenylene, and wherein R3 is m- or p-phenylene with units Ill constituting from 0 to 15 mol % of the total of units land Ill and with the proviso that when n is 1 or 2, R2 in at least 85 mol % of units II is 2,6-naphthylene or p,p'-biphenylene.
2. A fiber-forming (co)polyester according to Claim 1 consisting essentially of units having the structural formulas:
wherein R1 in at least 85 mol % of units I is
in which X is methyl or chloro and n is 1, or 2 and wherein R2 in at least 85 mol % of the units 11 is p-phenylene, 2, 6-naphthylene or p,p'-biphenylene with the proviso that when n is 1 or 2, R2 in at least 85 mol % of the units II is 2, 6-naphthylene or p,p'-biphenylene.
3. A (co)polyester according to Claim 1 or Claim 2 wherein R1 in up to 15 mol % of the units I is selected from the group consisting of m-phenylene, p-phenylene, chloro-p-phenylene, methyl-p-phenylene, p, p'-biphenylene, tetramethyl-p, p'-biphenylene, 2, 6-naphthylene and 2,7-naphthylene and wherein R2 in up to 15 mol % of the units II is m-phenylene.
4. A fiber-forming (co)polyester according to Claim 1 consisting essentially of units having the structural formulas:
wherein R1 is
in which Xis methyl or chloro and n is 1 or 2 and werein R2 is p-phenylene, 2,6-naphthylene or p, p'-biphenylene with the proviso that when n is 1 or 2, R2 is 2,6-naphthylene or p,p'-biphenylene.
5. A fiber-forming (co)polyester according to Claim 1 consisting essentially of units having the structural formulas:
in which X is methyl or chloro and n is 0, 1 or 2, R2 is p-phenylene, 2, 6-naphthylene or p,p'-biphenylene and
R3 is m- or p-phenylene with units Ill constituting up to 15 mol % of the total of units I and Ill.
6. A (co)polyester according to any of the preceding Claims wherein Ra is
7. A (co)polyester according to Claim 6 wherein R2 is p-phenylene.
8. A (co)polyester according to any of Claims 1 to 5 wherein R1 is
9. A (co)polyester according to Claim 8 wherein R2 is p-phenylene.
10. A (co)polyester according to any of Claims 1,2 and 4to 8 wherein R2 is 2,6-naphthylene.
11. A (co)polyester according to any of Claims 1,2 and 4 to 8 wherein R2 is p, p'-biphenylene.
12. A (co)polyester according to Claim 1 substantially as herein described.
13. Afiber-forming (co)polyester substantially as herein described in any of the Examples.
14. Afilament of a (co)polyester as claimed in any of the preceding Claims.
15. A heat-treated filament according to Claim 14 having a modulus of greater than 200 g/denier (177dN/tex) and a tenacity in excess of 10 g/denier (8.84dN/tex).
16. Afilament according to Claim 14 substantially as herein described.
17. A filament of a (co)polyester, substantially as herein described in any of the Examples.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US93190678A | 1978-08-08 | 1978-08-08 | |
| US06/054,448 US4245082A (en) | 1979-07-09 | 1979-07-09 | Polyesters derived from 3,4'-dihydroxy-benzophenones or 3-hydroxy-4'-(4-hydroxyphenyl-)benzophenone and certain aromatic dicarboxylic acids and filaments thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2030158A true GB2030158A (en) | 1980-04-02 |
| GB2030158B GB2030158B (en) | 1982-12-01 |
Family
ID=26733046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7927468A Expired GB2030158B (en) | 1978-08-08 | 1979-08-07 | Polyesters derived from 3,4'-dihydroxybenzophenones or 3-hydroxy-4'-(4-hydroxyphenyl-) benzophenone and certain aromatic dicarboxylic acids and filaments thereof |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE2932178C2 (en) |
| GB (1) | GB2030158B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2519974A1 (en) * | 1982-01-21 | 1983-07-22 | Rhone Poulenc Spec Chim | PROCESS FOR THE ACYLATION OF HALOGENO OR TRIHALOGENOMETHYLBENZENES |
| EP0085265A1 (en) * | 1982-01-21 | 1983-08-10 | Rhone-Poulenc Specialites Chimiques | Process for the preparation of alpha,alpha-difluoroalkoxy or alpha,alpha-difluoroalkylthiophenyl ketones |
| EP0102749A1 (en) * | 1982-07-29 | 1984-03-14 | E.I. Du Pont De Nemours And Company | Fiber-forming polyesters of ketodiols |
| US4453012A (en) * | 1982-04-22 | 1984-06-05 | Rhone-Poulenc Specialites Chimiques | Process for the preparation of phenyl ketones |
| US4456746A (en) * | 1981-10-02 | 1984-06-26 | Imperial Chemical Industries Plc | Polyester containing residues of a 1-hydroxy-3-6-bis(hydroxyalkoxy)xanth-9-one, process for preparing same and shaped articles thereof |
| US4552984A (en) * | 1982-01-21 | 1985-11-12 | Rhone-Poulenc Specialites Chimiques | Process for preparation of α,α-difluoroalkoxy or α,.alpha. |
| US4554381A (en) * | 1982-01-21 | 1985-11-19 | Rhone-Poulenc Specialites Chimiques | Process for sulfonylation of halobenzenes |
| EP0169675A1 (en) * | 1984-06-26 | 1986-01-29 | E.I. Du Pont De Nemours And Company | Optically anistropic melt forming copolyesters |
| FR2580276A1 (en) * | 1985-04-16 | 1986-10-17 | Rhone Poulenc Spec Chim | PROCESS FOR THE PREPARATION OF ACYLBIPHENYLES |
| EP0218366A1 (en) * | 1985-09-04 | 1987-04-15 | E.I. Du Pont De Nemours And Company | Polyester polymers of 3-hydroxy-4'-(4-hydroxyphenyl) benzophenone or 3,4'-dihydroxybenzophenone and dicarboxylic acids |
| EP0221316B1 (en) * | 1985-10-04 | 1990-01-03 | Bayer Ag | Thermotropic aromatic polyester having a high dimensional heat stability and excellent mechanical properties, process for their preparation and their use in the production of moulded articles, filaments, fabrics and sheets |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3028364A (en) * | 1957-04-02 | 1962-04-03 | Gevaert Photo Prod Nv | Production of linear aromatic polyesters |
| GB907647A (en) * | 1960-02-29 | 1962-10-10 | Ici Ltd | New aromatic polyesters |
| US4083829A (en) * | 1976-05-13 | 1978-04-11 | Celanese Corporation | Melt processable thermotropic wholly aromatic polyester |
-
1979
- 1979-08-07 GB GB7927468A patent/GB2030158B/en not_active Expired
- 1979-08-08 DE DE19792932178 patent/DE2932178C2/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4456746A (en) * | 1981-10-02 | 1984-06-26 | Imperial Chemical Industries Plc | Polyester containing residues of a 1-hydroxy-3-6-bis(hydroxyalkoxy)xanth-9-one, process for preparing same and shaped articles thereof |
| US4554381A (en) * | 1982-01-21 | 1985-11-19 | Rhone-Poulenc Specialites Chimiques | Process for sulfonylation of halobenzenes |
| US4552984A (en) * | 1982-01-21 | 1985-11-12 | Rhone-Poulenc Specialites Chimiques | Process for preparation of α,α-difluoroalkoxy or α,.alpha. |
| FR2519974A1 (en) * | 1982-01-21 | 1983-07-22 | Rhone Poulenc Spec Chim | PROCESS FOR THE ACYLATION OF HALOGENO OR TRIHALOGENOMETHYLBENZENES |
| US4446078A (en) * | 1982-01-21 | 1984-05-01 | Rhone-Poulenc Specialites Chimiques | Process for the preparation of α,α-difluoroalkyl-thiophenyl ketones |
| EP0085265A1 (en) * | 1982-01-21 | 1983-08-10 | Rhone-Poulenc Specialites Chimiques | Process for the preparation of alpha,alpha-difluoroalkoxy or alpha,alpha-difluoroalkylthiophenyl ketones |
| US4454350A (en) * | 1982-01-21 | 1984-06-12 | Rhone-Poulenc Specialities Chimiques | Process for the acylation of halo- or trihalomethylbenzenes |
| EP0084742A1 (en) * | 1982-01-21 | 1983-08-03 | Rhone-Poulenc Specialites Chimiques | Process for the acylation of halogen or trihalogen methyl benzenes |
| US4453012A (en) * | 1982-04-22 | 1984-06-05 | Rhone-Poulenc Specialites Chimiques | Process for the preparation of phenyl ketones |
| EP0102749A1 (en) * | 1982-07-29 | 1984-03-14 | E.I. Du Pont De Nemours And Company | Fiber-forming polyesters of ketodiols |
| EP0169675A1 (en) * | 1984-06-26 | 1986-01-29 | E.I. Du Pont De Nemours And Company | Optically anistropic melt forming copolyesters |
| FR2580276A1 (en) * | 1985-04-16 | 1986-10-17 | Rhone Poulenc Spec Chim | PROCESS FOR THE PREPARATION OF ACYLBIPHENYLES |
| EP0199661A1 (en) * | 1985-04-16 | 1986-10-29 | Rhone-Poulenc Chimie | Process for the preparation of acylbiphenyl derivatives |
| EP0218366A1 (en) * | 1985-09-04 | 1987-04-15 | E.I. Du Pont De Nemours And Company | Polyester polymers of 3-hydroxy-4'-(4-hydroxyphenyl) benzophenone or 3,4'-dihydroxybenzophenone and dicarboxylic acids |
| EP0221316B1 (en) * | 1985-10-04 | 1990-01-03 | Bayer Ag | Thermotropic aromatic polyester having a high dimensional heat stability and excellent mechanical properties, process for their preparation and their use in the production of moulded articles, filaments, fabrics and sheets |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2030158B (en) | 1982-12-01 |
| DE2932178A1 (en) | 1980-02-21 |
| DE2932178C2 (en) | 1994-03-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960807 |