JPS6254128B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to fiber-forming melt-spun aromatic polyesters and high modulus filaments thereof. A class of aromatic polyesters that can form optically anisotropic melts from which oriented filaments can be made is described in U.S. Patent No. 4,118,372.
(Schaefgen et al). Other aromatic polyesters with this property are patented in the U.S.
4066620. The polyesters described in the above-mentioned literature mainly have para-orientation 2
derived from valent phenols and para-oriented aromatic dicarboxylic acids. Filaments melt spun from such polyesters can be heat treated to provide high tenacity and modulus. The present invention provides different anisotropic melt-forming polyesters that can be melt-spun to obtain filaments of high melt-spun modulus (e.g., greater than 200 g/denier (177 dN/tex)). . The new filament is heat treated to increase its tenacity to a level preferably above 10 g/denier (8.84 dN/tex), while increasing the modulus to 200 g/denier (177 dN/tex).
It can also be maintained at a level exceeding . The present invention exhibits optical anisotropy in the molten state, and substantially equimolar amounts of the structural formula -[O-R ₁ -O]-
and

consisting essentially of units having the formula, where at least -[O-R ₁ -O]- units
R ₁ in 85 mol% is

[Formula] Also teeth

[Formula], where X is methyl, and n is 0, 1 or 2, and where

[Formula] R ₂ in at least 85 mol% of the units is p-phenylene, 2,6
- selected from the group consisting of naphthylene and p,p'-biphenylene, provided that n is 1 or 2;

The formula relates to a fiber-forming (co)polyester characterized in that R ₂ in at least 85 mol % of the units is 2,6-naphthylene or p,p'-biphenylene. -[O-R ₁ -O]- unit up to 15 mol% R ₁ is 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

[Formula] _R2 in up to 15 mol% of the units is m-phenylene. The invention also relates to high modulus filaments of such polyesters. The (co)polyesters of the present invention are derived from -O-R ₁ from substantially equimolar amounts of dihydric phenols.
-O- unit and derived from an aromatic dicarboxylic acid

[Formula] consists essentially of units. At least 85 mol % of the -O -R ₁ -O- units, preferably all

【formula】 or

[Formula], where X is chloro or methyl, and n is 0,
1 or 2. Preferably, n is 0;
That is, the units are not replaced. remaining -O
-R ₁ -O- units, i.e. up to 15 mol%,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] and Beauty

Selected from the group consisting of [Formula].

[Formula] at least 85 mol% of units, preferably Or everything is

【formula】

[expression] and

Selected from the group consisting of [formula] It can be done. Remaining

[Formula] Unit, i.e. 15 mo up to le%

[Formula]. n is 1 or When is 2,

_R2 in at least 85 mole percent of the units must be 2,6-naphthylene or p,p'-biphenylene. Or (co)polyester is (A)

[expression] or

[Formula] where X is methyl or chloro and n is 0,1 or 2, (B) terephthaloyl, 2,6-naphthoyl or p,p'-bibenzoyl and (C) m-oxybenzoyl or It consists essentially of p-oxybenzoyl units in the proportions specified above. The (co)polyesters of the present invention are capable of forming optically anisotropic melts and have sufficient molecular weight for melt spinning into filaments. The term "(co)polyester" is intended to encompass both homopolyesters and copolyesters. (co)polyester is produced by standard melt polymerization techniques with the formula

[Formula] where R ₂ is as defined above, one or more aromatic dicarboxylic acids of the formula HO-R ₁ -OH, where R ₁ is as defined above It can be produced from one or more diphenols.
Diphenols are often used in the form of their diesters (eg acetates). The diphenol and diacid are usually combined in substantially equimolar amounts;
About 1 hour while stirring in a nitrogen atmosphere in the reactor.
Heat for ~3 hours. The temperature used for polymerization is above the melting point of the reactants, generally from 200 to 350°C.
The reactor is equipped with means for removing by-products while polymerization is occurring. Vacuum is usually applied towards the end of the polymerization to facilitate removal of by-products and complete the polymerization.
Polymerization conditions, such as temperature, duration of heating, pressure, etc., can be varied according to, for example, the reactants used and the degree of polymerization desired. Filament Production (Co)polyesters can be spun into filaments by conventional melt spinning techniques. The polymer melt is extruded from a spinneret into a quenching atmosphere (eg, air or nitrogen maintained at room temperature) and wound. General spinning conditions are U.S. Patent No. 4066620
listed in the number. As used herein, "freshly spun" fiber means a fiber that has not been drawn or heat treated after extrusion and normal winding. Heat Treatment and Utility The freshly spun fibers of the present invention can be heat treated with relaxation in an oven to provide high strength fibers that are useful in a variety of industrial applications, such as reinforcing plastics and rubber. In heat treatment methods, a sample of fiber is passed through a furnace as a skein or on a bobbin (preferably a collapsible bobbin), usually in an inert atmosphere, i.e. to remove by-products from the vicinity of the fibers. Heat while continuously purging with a stream of water. A temperature close to the melting point but low enough to prevent fusion between the filaments is used. Preferably, the maximum temperature is reached in stages. Measurements and Tests Intrinsic viscosity (ηinh) is defined by the following equation: ηinh=ln(ηrel)/C where (ηrel) represents the relative viscosity and C is the weight of 0.5 g in 100 ml of solvent. Represents the concentration of coalescence. Relative viscosity (ηrel) is determined by dividing the flow time in a capillary viscometer of a dilute solution by the flow time of pure solvent. Flow times were determined at 30°C and the solvent was p-chlorophenol unless otherwise specified. Tensile properties of fibers are first reported in conventional units with SI units in the cutout. Denier (D) g/9000m (dtex) Strength (T) g/denier (dN/tex) Elongation (E) Percent modulus of unstretched length (Mi) g/denier (dN/tex) They are U.S. patents. No. 3,827,998 (Morgan), the measurements are made on fibers that have been conditioned for at least one hour. Average at least three breaks. Thermo-optical testing (TOT) is described in US Pat. No. 4,066,620. Polymers that pass this test are considered optically anisotropic. The following examples illustrate the invention. Example - Synthesis of 3,4'-diacetoxybenzophenone 3,4'-diacetoxybenzophenone used in the subsequent polymerization was prepared stepwise from m-anisic acid. It was first converted to m-anisoyl chloride, then 3,4'-dimethoxybenzophenone,
It was then changed to 3,4'-dihydroxybenzophenone and finally to 3,4'-diacetoxybenzophenone. This example provides details of one such conversion and, except for the scale of the feed, was a general procedure for all such production. Preparation of m-anisoyl chloride A mixture of 100 g m-anisinic acid (0.658 mol), 250 g thionyl chloride (2.10 mol) and 5 ml dimethylformamide was placed on top of a condenser to remove atmospheric moisture. Heat to reflux in a round bottom flask with the agent. Excess thionyl chloride was distilled from the product using a rotating film-evaporator at approximately 200 torr (26.6 kPa). Next, m-anisoyl chloride was fractionally distilled to 25cm
Vigreau column at 109°C/12 torr (1.6 kPa). The yield was (0.528 mol), or about 80%. Preparation of 3,4'-dimethoxybenzophenone A round bottom flask was equipped with a stirrer, addition funnel, nitrogen inlet, and thermometer. It was cooled in an ice/water bath. The initial feed 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 stream of nitrogen was passed through the mixture.
90g m-anisoyl chloride (0.528 mol)
A solution in 108 ml of tetrachloroethane was passed through a dropping funnel until the temperature of the stirred mixture rose to 15 ml.
It was added at a rate that did not exceed ℃ (addition period 1~
2 hours). After mixing, the flask was left at room temperature for 2 days and then ice (approximately 250 g) was carefully added to decompose the AlCl ₃ complex. Tetrachloroethane was removed by steam distillation. 500% organic product from aqueous mixture
ml of methylene chloride and then drawn off,
The aqueous layer was discarded. 200ml of methylene chloride solution 5
% sodium hydroxide and once with approximately 200 ml of water, each time removing and discarding the aqueous layer. After distilling off methylene chloride using a rotating film evaporator,
102 g of 3,4'-dimethoxybenzophenone (0.42 mol) remained, which crystallized on cooling to room temperature. When it is recrystallized from ethanol, it becomes 87g.
Crystals of (0.36 mol) were formed, melting point 53-55°C. This substance is also known for its manufacture and timing at J.Am.Chem.
Soc. 54 (1932) p.1449. Preparation of 3,4'-dihydroxybenzophenone 87 g of 3,4'-dimethoxybenzophenone (0.36 mol) and 48% of the 240 ml previously prepared
Demethylation was accomplished by heating a mixture of aqueous hydrobromic acid, 120 ml of acetic anhydride, and 120 ml of acetic acid to reflux for 15 hours. The cooled reaction mixture was poured into approximately 400 ml of water, filtered,
The dihydroxy product was isolated by washing with water and drying in an oven at 80°C. Melting point is 193-194℃
It was hot. The yield was 77 g (0.36 mol), i.e.
It was about 100%. Preparation of 3,4'-Diacetoxybenzophenone To a slurry of 73 g of 3,4'-dihydroxybenzophenone (0.34 mol) in 225 ml of acetic anhydride in a beaker, add 8 drops of concentrated sulfuric acid and This mixture was heated on a steam bath for 30 minutes. The resulting clear solution was cooled and then placed in approximately 600 ml of water to precipitate the product. Drain it, wash it with water,
It was dried in an oven at about 80°C. Recrystallization from methanol yields 80 g of diacetoxybenzophenone (0.268 mol), mp 81-83°C. Example - Polyterephthalate of 3,4'-dihydroxybenzophenone The polymerization apparatus was a 250 ml three-necked flask equipped with (1) a glass stirrer placed in a pressure-tight resin housing, (2) a nitrogen inlet, (3) ) a short Vigreux column led to a water-cooled condenser with a flask for collecting acetic acid, and (4) an electrically heated wood alloy bath attached to a vertical height adjustment device. A device for applying vacuum was present in the distillation adapter. A flask was charged with 9.57 g diacetoxybenzophenone (0.032 mol) and 4.98 g terephthalic acid (0.03 mol) and heated with stirring from 238°C to 310°C at atmospheric pressure under a nitrogen atmosphere for 48 minutes. did. Most of the acetic acid byproduct was liberated at this time. Heating at 310°C was continued for 22 minutes. then
A vacuum of 0.2 torr (0.0266 kPa) was applied and the temperature was increased to 325°C within 8 minutes and maintained for 17 minutes. The cooled polymer has an intrinsic viscosity of 0.78, ηinh
It had The melt can be tested using the TOT test.
It was anisotropic above its flow temperature of 296°C. The ground solid polymer was formed into cylindrical plugs and passed through a 0.009 inch (0.23 mm) diameter spinneret hole at 325°C using a press spinner.
It was molded and spun under a pressure of 700 psi (4830 kPa). Winding speed is 1000ypm (914m/min)
It was hot. The average filament properties were as follows: D/T/E/Mi=3.54/5.03/1.77/360 (3.92/
4.45/1.77/318). The filament was wound loosely onto a flexible bobbin and heated in a furnace in slowly flowing nitrogen as follows: 220°C/1 hour + 240°C/1 hour.
Time+260℃/1 hour+280℃/1 hour+300℃/
1 hour. After this heating, the average filament tensile properties were as follows (denier virtually unchanged): T/E/Mi = 11.63/3.76/362 (10.28/3.76/
320). The best single value of tensile properties was as follows after heating: T/E/Mi=19.98/6.62/426 (17.66/6.02/
376.5). Example - Poly-2,6-naphthalene dicarboxylate of 3,4'-dihydroxybenzophenone Using the method of the example, 9.84 g of 3,4'-diacetoxybenzophenone (0.033 mol) was converted to 6.48
g of 2,6-naphthalene dicarboxylic acid (0.030 mol). Polymerization temperature is 235 at atmospheric pressure
℃ to 345℃ within 87 minutes and in vacuum
Increased from 345℃ to 365℃ within 40 minutes. The intrinsic viscosity, ηinh, was 0.78. In the TOT exam,
The melt was anisotropic above the flow temperature of 298°C. Plugs are formed from the ground solid product, and the extrusion temperature is 360°C and the extrusion pressure is
Spun as in the Examples except at 400 psi (2760 kPa). The average filament properties were as follows: D/T/E/Mi=9.11/4.73/1.37/383
(10.12/4.18/1.37/338). When heated under nitrogen atmosphere for 225°C/24 hours + 300°C/19 hours as in the examples, the average tensile properties were improved as follows: T/E/Mi = 15.88/4.67 /349(14.04/4.67/
308) Example - Copoly-2,6-naphthalene dicarboxylate from 3,4'-dihydroxybenzophenone (90 mol%) and hydroquinone (10 mol%) A copolyester was prepared according to the method of the example.
14.35 g of 3,4'-diacetoxybenzophenone (0.048 mol), 1.04 g of 1,4-diacetoxybenzene (0.0054 mol), and 10.80 g of 2,6-
Prepared from naphthalene dicarboxylic acid (0.050 mol). Polymerization temperature from 310℃ to 352℃ at atmospheric pressure
and maintained under vacuum at 352 °C for 34 min. The ground solid polymer was thoroughly washed with acetone to extrude the low molecular weight material. The intrinsic viscosity, ηinh, is
It was 0.59. In the TOT test, the melt is 323
It was anisotropic above the flow temperature of °C. Molded plugs of copolyester were spun as in the examples. Filament is 600ypm
(549 m/min) and had the following average properties: D/T/E/Mi = 4.30/4.87/1.67/316 (4.78/
4.30/1.67/279). It was heated at 225°C/24 hours + 280°C/21 hours as described in the examples to obtain the following tensile properties: T/E/Mi=14.03/4.90/344 (12.40/4.90/
304). Example - Copolyester of 3,4'-dihydroxybenzophenone with 2,6-naphthalene dicarboxylic acid (90 mol%) and isophthalic acid (10 mol%) 15.95 g of 3,4'-diacetoxybenzophenone (0.0535 mol), 0.83 g isophthalic acid (0.005
mol) and 9.7 g of 2,6-naphthalene dicarboxylic acid (0.045 mol) were polymerized as described in the examples. The polymerization temperature at atmospheric pressure is
From 305℃ to 358℃ within 53 minutes and under vacuum
It was maintained at 358°C for 17 minutes. The intrinsic viscosity, ηinh, is
0.92, and the TOT test showed melt anisotropy above the flow temperature of 303°C. Plugs formed from ground solid copolyester were spun into filaments as described in the Examples. The plug is at 380℃ and the spinneret is at
385℃, the spinning pressure was 600psi (4140kPa), and the winding speed was 600yd/min (549m/min).
minute). The freshly spun filament had the following average properties: D/T/E/Mi = 5.64/4.78/2.63/283 (6.26/
4.22/2.63/250). 200℃/24 hours +225 as in the example
After heating at °C/3 hours + 250/20 hours, the average tensile properties were: T/E/Mi=8.34/4.14/269 (7.37/4.14/
238). Example - Preparation of 3,4'-dimethoxy-4-methylbenzophenone The methods and equipment used in the preparation of this monomer were as described in the Examples.
A solution of 94.5 g m-anisoyl chloride (0.554 mol) in 113 ml tetrachloroethane was
80.7 g o-methylanisole (0.661 mol),
94.5 g of anhydrous aluminum chloride and 113 ml of tetrachloroethane were added dropwise to the stirred, cooled mixture, maintaining the temperature at about 15°C. This mixture was allowed to stand at room temperature for 24 hours. After addition of ice and extraction with methylene chloride as in the preparation of 3,4'-methoxybenzophenone in the example, an impure liquid is obtained, from which it is extracted in a 25 c.c. Vigreux column.
3,4′-dimethoxy-4 by fractional distillation at 198°C and a pressure of 2.0 torr (0.27 kPa).
-Methylbenzophenone was obtained. Yield is 114
g (0.445 mol). Preparation of 3,4'-dihydroxy-4-methylbenzophenone Demethylation of 114 g of 3,4'-dimethoxy-4-methyl-benzophenone (0.445 mol) was carried out using 313.5 ml of the previously prepared 48% aqueous solution. hydrobromic acid,
148 ml of acetic anhydride, and a mixture of 148 ml of acetic acid and
This was done by refluxing for 15 minutes. The isolated product melted at 173-174°C. Recrystallization from ethanol/water yielded 79 g (0.346 mol) of 3,4'-dihydroxy-4-methylbenzophenone, mp 174-175°C. Preparation of 3,4'-diacetoxy-4-methylbenzophenone 79 g of 3,4'-dihydroxy-4-methyl-benzophenone (0.346 mol) was mixed with 237 ml of acetic anhydride and 8 drops of concentrated sulfuric acid to give 30 Acetylation was achieved by heating on a steam bath for minutes. The product is precipitated in water, filtered, washed and heated to about 80°C.
It was dried. After crystallizing the product from methanol, the melting point was 60-64°C. The yield was 87 g (0.279 mol). Before polymerization, the product was crystallized once more from methanol. Polyester from bibenzoic acid and 3,4'-diacetoxy-4-methylbenzophenone Using the apparatus and method of the example, 10.89 g
of bibenzoic acid (0.045 mol) and 14.36 g of 3,
4'-Diacetoxy-4-methylbenzophenone (0.046 mol) was polymerized. 290℃ at atmospheric pressure
Heating from to 357°C occurred within 80 minutes and heating to 357°C for 19 minutes under vacuum. The product had an intrinsic viscosity, ηinh, of 1.09. TOT exam is 311
It exhibited anisotropy above the flow temperature of °C. A cylindrical plug of the ground product was heated to 378 °C and
Spun at a pressure of 200 psi (1380 kPa). The winding speed was 400 yd/min (366 m/min).
The average freshly spun filament properties are:
It was as follows: D/T/E/Mi=8.0/4.15/1.15/382 (8.9/
3.67/1.15/338). Filament 200 as in example
℃ / 2 hours + 250℃ / 2 hours + 260℃ / 1 hour +
After heat treatment at 280°C/1 hour + 305°C/20 hours, the average tensile properties were: T/E/Mi=8.31/2.90/303 (7.34/2.90/
268). Example - Synthesis of 3-hydroxy-4'-(4-hydroxyphenyl)benzophenone One autoclave was charged with 85.0 g phenylphenol (0.5 mol), 69.0 g 3-hydroxybenzoic acid (0.5 mol) and 500 ml HF (cooled to 0°C). The autoclave was cooled and the air was removed by flushing with BF ₃ . The autoclave was maintained at 0°C for 6 hours with shaking;
_BF3 was added 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 (approximately 2) to precipitate the crude product. After this, it was thoroughly washed with water and dried. Yield of crude product: 136 g (94%) Melting point of crude product: 213-9°C The above crude product was mixed with approximately 400 ml of acetic anhydride and 0.15
The mixture was heated under reflux for 2 hours with g of sulfuric acid. the product
Isolated by precipitation of Ac ₂ O solution into ca. Filtered, washed and dried. Yield of crude product: 183g (theoretical amount: 187g) Melting point of crude product: 95-9℃ When it is recrystallized from ethanol, the melting point is
The temperature was 119-121℃. EXAMPLE - Polyterephthalate of 3-hydroxy-4'-(4-hydroxyphenyl-)benzophenone The polymerization equipment was similar to that used in the examples. 15.56 g of 3-hydroxy in the flask
diacetate of 4'(4-hydroxyphenyl-)benzophenone (0.042 mol, 4% excess) and
supplying 6.64 g of terephthalic acid (0.040 mol);
Then, while stirring, in a nitrogen atmosphere at atmospheric pressure.
Heated from 280°C to 346°C within 35 minutes. High pressure was then applied and heating continued for 7 minutes at 346°C.
The cooled polymer has an intrinsic viscosity of 0.76, ηinh (7.5%
trifluoroacetic acid, 17.5% methylene chloride,
12.5% dichlorotetrafluoroacetone hydrate,
12.5% Perchene and 50% 4
- measured in chlorophenol). The polymer was spun at 30°C as in the examples and the filament was wound at 549 m/min. The resulting filament has an average denier of 8.6 dtex and an average tensile property of T/E/Mi
= 2.21/0.76/448. 230°C/2 hours + 250°C/2 hours + 270°C as described in the Examples
After heating for 1 hour + 280°C for 18 hours, the following average tensile properties were obtained: T/E/Mi = 5.85/2.95/226 Example - 3-Hydroxy-4'-(4-hydroxyphenyl) -) benzophenone and 2,6
- Polyester from naphthalene dicarboxylic acid The polymerization was similar to that of the example except that 8.64 g of 2,6-naphthalene dicarboxylic acid (0.040 mol) was used instead of terephthalic acid. Initial heating from 268°C to 340°C was in a nitrogen atmosphere at atmospheric pressure for 31 minutes. Heating under vacuum is 340℃~344
℃ for 2 minutes. Intrinsic viscosity of the polymer, η
inh was measured using the solvent used for this purpose in the examples and was 0.73. The polymer was melt spun at 276°C as in the examples and the filament was wound at 366 m/min. The melt spun filament has an average denier of 7.6 dtex and T/E/Mi = 1.41/0.54/
It had an average tensile property of 234. 220°C/2 hours + 240°C/2 hours + as described in the examples.
After heat strengthening at 260°C/2 hours + 280°C/2 hours + 304°C/18 hours, the following average tensile properties were obtained: T/E/Mi = 4.79/2.3/231.

Claims (1)

[Claims] 1 Consisting essentially of units having the structural formula -[O-R ₁ -O]- and [Formula], where at least 85 mol% of the -[O-R ₁ -O]- units in which R ₁ is [Formula] or [Formula], where X is methyl and n is 0, 1 or 2, and at most 15 moles of -[O-R ₁ -O]- units %In
R ₁ is 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 R ₂ in at least 85 mol% of the units of formula is selected from the group consisting of p-phenylene, 2,6-naphthylene and p,p'-biphenylene, with the proviso that n is 1 or 2, R ₂ is 2,6-naphthylene or p,p'-biphenylene, and R ₂ in at most 15 mol % of the units is m-phenylene and has an intrinsic viscosity of at least 0.59. A fiber-forming (co)polyester characterized by: 2. The (co)polyester according to claim 1, wherein R ₁ is [Formula]. 3. The (co)polyester according to claim 2, wherein _R2 is p-phenylene. 4. The (co)polyester according to claim 2, wherein R ₂ is 2,6-naphthalene. 5. The (co)polyester according to claim 1, wherein R ₂ is 2,6-naphthalene. 6. The (co)polyester according to claim 1, wherein R ₂ is p,p'-biphenylene. 7. The (co)polyester according to claim 1, wherein R ₁ is [Formula]. 8. The (co)polyester according to claim 7, wherein R ₂ is p-phenylene.