IE52941B1 - Aromatic polyester and filaments - Google Patents

Description

This invention relates to fiber-forming melt-spinnable aromatic polyesters and to filaments thereof having high tenacity and high modulus.

Aromatic polyesters capable of forming 5 anisotropic melts and containing units derived from both chlorohydroquinone or methylhydroquinone and terephthalic acid have been disclosed in prior art patents,U.S. Specification Nos. 4,118,372; 4,075,262; 3,991,014; 4,066,620; 3,991,013; 4,146,702 and 4,156,070.

In these polyesters, other monomers are present in addition to those mentioned above. For example, in U.S. Patent Specification No. 4,118,372 a portion of the terephthalic acid is replaced by 2,6-naphthalenedicarboxylic acid, however, polyesters with potential for making filaments having high tenacity and modulus require relatively high modification with the expensive 2,6-naphthalenedicarboxylic acid monomer. In U.S.

Patent Specification No. 4,146,702, 3-hydroxybenzoic acid is added. U.S. Patent Specification No. 3,778,410 suggests hydroxyaromatic carboxylic acids as useful components in polyesters from ethylene glycol and terephthalic acid. 6-Hydroxy-2-naphhhoic acid is shown in U.S. Patent Specification No. 4,161,470 as a comonomer with 4-hydroxybenzoic acid.

Chlorohydroquinone and terephthalic acid are relatively inexpensive ingredients, however, polyesters formed entirely from repeat units of these two materials are not melt processable into filaments. Even the addition of 4-hydroxybenzoic acid in small amounts as a comonomer does not result in a polyester that can be melt spun into filaments without degradation.

It has now been found that small amounts of 6-hydroxy-2-naphthoic acid bring the melting point of chlorohydroquinone- or methylhydroquinoneterephthalic acid polyesters into a range suitable for melt spinning and promote homogeneity, thereby making the melts of these polyesters more amenable to processing. Moreover, the filaments from these new polyesters exhibit high modulus as-spun and high tenacity upon heat treatment.

SUMMARY OF THE INVENTION The present invention is directed to polyesters of fiber-forming molecular weight that exhibit optical anisotropy in the melt and consist essentially of units having the following structural formulas: X y—-I 0 III and 0-20 mol t IV a b CO CO and/or wherein X is chloro- or methyl, and Unit IVa is a dioxy unit derived from hydroquinone, resorcinol, 2,5- or 2,6-dichlorohydroquinone, and Unit IVb is isophthaloyl, in the proportions of 75 to 95 mol % of Units X and II and 5-25 mol % Units III and IV of which at least 5 mol % is Unit III. preferably Units IV are 1,3 or 1,4-dioxyphenylene or isophthaloyl units. Dioxy units and dicarbonyl units in the polymer are substantially equimolar in quantity.

Melt-spun and heat strengthened filaments of such polyesters are included in the invention.

DETAILED DESCRIPTION OF THE INVENTION The polyesters of the invention consist essentially of units as described above. Unit I, chloro-l,4-dioxyphenylene is normally provided by the diacetate of chlorohydroquinone and Unit IX, terephthaloyl; by terephthalic acid. Unit III, 6oxy-2-naphthoyl is generally derived from the monoacetate of 6-hydroxy-2-naphthoic acid. It will be apparent that other precursors can be usefully employed.

Hydroquinone, resorcinol or, 2,5-, 2,6-dichloro-hydroquinone may be used to provide 0.-20. mol % of the dioxy units (Unit IV a) in the polyester. Similarly, isophthalic acid may be used to provide .0-20 mol % of dicarbonyl units (Unit IV b) in the polyester.

The particular type and amount of difunctional reactant to be used (other than for Units I, II and III) will be governed by its effect on melting point, melt anisotropy, melt processibility or ultimate tensile strength of filaments from the polyesters. The number of dioxy units present in the polyester are substantially equivalent to the number of dicarbonyl units. The mol % of any unit is calculated based on the total mols of all repeat units present. Preferably, the polyester consists essentially of Units I, II and III.

Conventional polymerization techniques may be employed such as described in the aforementioned U.S. Patent 4,118,372 and more particularly in the examples described below. The precursor reactants are combined in proportions corresponding to the molar proportions of the units desired in the polyester products. Functional equivalents of the precursors may be employed.

In general, a mixture of monomers (preferably with dihydric phenols in the form of their diacetates in up to 7% excess) are heated with stirring, under nitrogen, in a 250 ml 3-necked flask in a Wood's metal bath from approximately 250°C to 330-380°C. Polymerization is continued for up to a total of 0.5 to one hour or longer if necessary until a fiber-forming molecular weight is reached but is terminated before reaching excessive melt viscosity. Usually a vacuum is applied to obtain the final viscosity. The polyesters of the invention exhibit optical anisotropy in the molten state.

Filament Preparation The polyesters may be spun into filaments by conventional melt-spinning techniques. In the examples below, filaments were prepared by melt-spinning into a quenching atmosphere of air or nitrogen and collected at a windup speed specified in the examples. The spinneret employed except in Ex. 6 had either 1 or 10 capillaries (holes), each shaped as a right circular cylinder 0.23 mm in diameter and 0.46 mm long. Melt temperature is the temperature at which the melt was maintained (values in parentheses are temperatures of the spinnerets). Melt pumping speed is adjusted to give a filament tex of about 0.5.

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 Following collection, samples of undrawn (as-spun) monofilament or multifilament yarn were heat-treated substantially free of tension in an oven as described in U.S. 4,183,895. Heating was in stages in a nitrogen atmosphere. Typically, temperature was raised to 200°C in 2 hrs, then to 304°C in another 7 hrs, and finally maintained at 304°C for an additional 7 hrs.

Such a heating sequence is abbreviated as RT-200eC/2 hr + 200-304eC/7 hr + 304eC/7 hr.

The heat-treated fibers of this invention are useful for a variety of industrial applications such as plastics and rubber reinforcement.

Inherent viscosity (ninj,) was computed from ”inh ’ ln (W/C where ηχθ^ is the relative viscosity and C is a solution concentration of 0.5, i.e., 0.5 g Of polymer per deciliter of solvent. Relative viscosity is the ratio of polymer solution flow time to solvent flow time in a capillary viscometer at 30°C. The solvent employed was either (A) a mixture of 7.5% trifluoroacetic acid/17.5% methylene chloride/12.5% dichlorotetrafluoroacetone hydrate/12.5% perchloroethylene/ 50% p-chlorophenol (all percentages by volume); or (B) 100% p-chlorophenol.

The polyesters of this invention are anisotropic in the melt as determined using the thermooptical test (TOT) described in U.S. Patent 4,118,372. The polymers were characterized by stick temperature meaning the temperature of a thermalgradient hot bar at the point at which the polymer first began to stick.

Monofilament tensile properties were measured using a recording stress-strain analyzer at 7G°F (21.1°C) and 65% relative humidity. Sample lengths were 1.0 in (2.54 cm) for monofilaments and 10 in (25.4 cm) for multifilament yarns, and rate of elongation was 10%/min. Results are reported as 32941 D/T/E/M or T/E/M where D is linear density in tex units of the single filament or multifilament bundle, T is break tenacity in dN/tex, E is elongation-atbreak expressed as the percentage by which initial length increased, and M is initial tensile modulus in dN/tex. Since linear density is normally substantially unchanged by heat-treatment, it is reported only for the as-spun filament or yarn.

Fibers of this invention have high heattreated tenacities and high initial moduli (e.g., moduli of about 200 dN/tex or greater). Average tensile properties for at least five heat-treated filaments or yarns are reported in the examples.

EXAMPLES The same general procedure was used in all the examples. It should be understood that the results reported below are believed to be representative and do not constitute all the runs involving the indicated reactants.

In the examples, the diacetate of the dihydric phenol and the monoacetate of the hydroxyaromatic acid were used. The aromatic dicarboxylic acids were used as such rather than as esters or other derivatives.

The monomer ingredients were added to a 3-necked flask or resin kettle in substantially the same molar ratios as desired in the final polymer except that an excess (usually 5 to 7%) of acetylated dihydric phenols was generally used. The resultant polymer is identified, for example, as CHQ/TPA/2,6HNA (42/42/16) meaning it was prepared from 42 mol % of the diacetate of chlorohydroquinone, 42 mol % of terephthalic acid and 16% of the acetate of 6-hydroxy-2-naphthoic acid (excesses of diacetates are not included in these percentages).

The 3-necked flask or resin kettle was fitted with: (1) a-glass stirrer extending through a pressuretight resin bushing, (2) a nitrogen inlet, and (3) a short Vigreux column leading to a water-cooled condenser with a flask for collecting acetic acid by-product.

An attachment for application of vacuum was provided at the end of the condenser. An electrically heated Wood's metal bath mounted for vertical adjustment was used for heating. The reaction mixture was heated to increasing temperatures with stirring at atmospheric pressure under nitrogen purge until essentially all the acetic acid had evolved. Then vacuum was applied and pressure was reduced gradually from atmospheric to less than 1 mm of mercury. Heating under vacuum of less than 1 mm mercury pressure was then continued until viscosity had increased to a level believed satisfactory for melt-spinning. The cooled and solidified polymer was comminuted, and a portion was molded into a cylindrical plug for melt-spinning.

EXAMPLE 1 Filaments From Copolyesters of Chlorohydroquinone (CHQ), Terephthalic Acid (TPA) and 6-Hydroxy-2Naphthoic Acid (2,6HNA) Polymerization Ingredients Grains Used Mol Percent Ex. CHQ TPA 2.6HNA CHQ/TPA/2,6HNA IA 9.6(5%)* 6.64 4.6 40/40/20 IB 119.8(7%) 81.3 48.30 41.2/41.2/17.6 1C 109.2(7%) 74.1 36.22 42.5/42.5/15 ID 11.3(7%) 7.68 1.73 46.25/46.25/7.5 ‘Percent excess Polymerization Conditions Ex. Temp. °C Time, Min. Pressure* IA 270-350 350 28 10 Atmospheric Reducing to below 1 mm Hg (i.e. about 30 inches Hg vacuum) IB 274-311 311-334 334-336 37 30 28 Atmospheric Reducing to below 1 nm Hg (133Pa) 0.4 mm Hg (53 Pa) 1C 283-310 310-332 332-338 31 26 28 Atmospheric Reducing to below 1 nm Hg (133Pa) 0.4 mm Hg (53 Pa) ID 260-360 360-365 45 10 Atmospheric Reducing to below 1 mm Hg (133 Pa) ‘When pressure is indicated as Reducing to below mm Hg a vacuum gauge was used which indicated inches of mercury.

Polymer Characterizations Run Inherent Viscosity Solvent Stick Temp. (' IA Insoluble A 220 IB 3.10 B 218 1C 3.13 B 244 ID Insoluble A 300 Filament Extrusion No. of 'min) Holes Ex. Temp (°C) Melt (Spinneret) Windup Speed (m/ 1A 305 (315) 549 1 IB 324 (324) 500 10 1C 320 (326) 500 10 ID 375 (375) 549 1 Heat Treatment Run Cycle 1A RT-200“C/2 hr + 200-304'C/7 hr + 304'C/7 hr IB RT-200'C/2 hr + 200-304'C/7 hr + 304'C/7 hr 1C RT-200°C/2 hr + 200-304'C/7 hr + 3O4'C/7 hr ID RT-200'C/2 hr + 200-304'C/7 hr + 304«C/7 hr Tensile Properties As-Spun Heat Treated Ex. D/T/E/M T/E/M 1A 0.61/1.1/0.4/207 18.2/5.49/345 IB 64.4/7.3/2.0/463 22.7/4.4/426 (Plied yarn) 1C 67.0/7.3/1.9/485 24.3/4.3/447 (Plied yarn) ID 1.1/5.3/1.4/460 16.6/3.6/517 When the proportion of 6-hydroxy-2naphthoic acid is increased such that 25 mol % of Unit III is present in the polyester, the filament T/E/M is 9.24/3.14/302 after heat treatment at RT2OO'C/2 hr + 22O’C/2 hr + 240°C/2 hr + 260'C/ 10 hr.

It is anticipated that higher percentages of 6-hydroxy 2-naphthoic acid will lead to lower tenacity fibers.

Surprisingly, a control polyester prepared by replacing all of the 6-hydroxy-2-naphthoic acid of Example 1C with an equivalent amount of 3-chloro-4hydroxybenzoic acid or 4-hydroxybenzoic acid could not be melt spun.

Claims (5)

Claims:

1. Polyesters of fiber-forming molecular weight consisting essentially of units having the following structural formulas: IXI 15 IV and 0-20 mol t - O - R x - 0 - CO - R 2 - co and/or wherein X is chloro- or methyl, and wherein Unit IV a is a dioxy unit derived from hydroquinone, resorcinol, 2,5- or 2,5-dichlorohydroquinone, and Unit IVb is isophthaloyl, in the proportions of 75 to 95 mol % of Units I and II and 5-25 mol % of Units III and IV of which at least 5 mol % is Unit III, the dioxy units and the dicarbonyl units in the polymer are substantially equimolar in quantity.

2. A fiber-forming polyester according to Claim 1 consisting essentially of Units I, II and III.

3. A fiber-forming polyester according to Claim 1 wherein Unit IV is 1,3-dioxyphenylene.

4. A fiber-forming polyester according to Claim 1 wherein Unit IV is isophthaloyl. 5. A fiber-forming polyester according to Claim 1 wherein Unit IV is 1,4-dioxyphenylene. 6. A fiber-forming polyester according to Claim 1 wherein X is chloro-. 7. A filament of a polyester according to any one of Claims 1 to 6.

5. 8. A fiber forming polyester according to Claim 1 substantially as herein described, '9. A filament of polyester according to to claim 7, substantially as herein described with reference to any of the Examples.