Source: https://patents.google.com/patent/US4029638?oq=flatulence
Timestamp: 2018-03-19 09:16:48
Document Index: 340849642

Matched Legal Cases: ['arts 1', 'arts 5', 'arts 5', 'arts 5', 'arts 6', 'arts 5']

US4029638A - Copolyester polymer of enhanced dyeability - Google Patents
Copolyester polymer of enhanced dyeability
US4029638A
US4029638A US05572025 US57202575A US4029638A US 4029638 A US4029638 A US 4029638A US 05572025 US05572025 US 05572025 US 57202575 A US57202575 A US 57202575A US 4029638 A US4029638 A US 4029638A
US05572025
Cationic dyeable copolyester polymer and yarns made therefrom having as an integral part of the polymer chain, sulfonamide groups each containing a dye sensitizing unit, derived from alkaline earth or alkali metal salts of sulfonated sulfonamides such as the sodium salt of N-(β-hydroxyethyl)-N-(3-carbomethoxybenzenesulfonyl) taurine.
Polymeric polyesters are readily prepared by heating together dihydric alcohols and dibasic carboxylic acids or polyester-forming derivatives thereof such as acid halides or simple esters of volatile alcohols. Highly polymerized polyesters can be formed into filaments, fibers, films, and the like which can be oriented. The most widely known and most important commercially of the polymeric polyesters is that prepared by the condensation of terephthalic acid or dimethyl terephthalate and ethylene glycol. These polyester materials, in drawn fiber or filament form, cannot be satisfactorily dyed with basic or cationic dyestuffs. It is recognized that unless the fiber-forming polyesters can be readily dyed by a variety of dyestuffs, the utility of the polymer in the textile field will be limited.
It has now been found that polyester yarns having enhanced dyeability can be obtained by modification of the polyester chain with certain difunctional and sulfonated sulfonamide monomers. Compared to previous modified polyesters, there is a significantly lowered tendency toward yellowness in the extruded yarn. The sulfonated sulfonamide monomers react at the single carbomethoxy site and the hydroxy site, thereby forming copolymer polymers in which the sulfonamide group is directly in the chain, rather than attached as a side chain in the main polymer chain. The resulting polymers, therefore, have significantly lowered tendency to yellowness compared to the polymers as disclosed in U.S. Pat. No. 3,856,753, as determined by the Gardner color test. This result can be accomplished, for example, by using as the difunctional monomer a sulfonamide having the following structure: ##STR1## wherein R1 is selected from the group consisting of H and a lower alkyl radical containing from 1 to about 4 carbons, R2 and R3 are alkylene radicals of from 1 to 6 carbons, and M is an alkaline earth or alkali metal. The formula of a typical polyester illustrating incorporating a comonomer dye sensitizing unit containing a sulfonamide group having the above structure as an intralinear part of the polymer chain is as follows:
Yarns produced in the practice of the present invention reflect enhanced basic and disperse dye receptiveness and improved basic dye light fastness properties; they are suitable for the usual textile applications and can be employed in the knitting or weaving of fabrics of all types as well as in the production of non-woven, felt-like products produced by known methods. Their physical properties closely parallel those of their related polyester fibers. However, they have particular sensitivity toward basic dyes. By a "basic dye" is meant a colored cationic organic substance such as those containing sulfonium, oxonium, or quaternary ammonium functional groups. Among the basic dyes which can be applied in accordance with the present invention can be mentioned Victoria Green WB (C.I. 657); Rhodamine B (C.I. 749); Brilliant Green B (C.I. 662); Victoria Pure Blue BO (pr. 198); and the like. The dyes are preferably applied from an aqueous solution, with or without carrier, at a temperature between about 100° and 125° C.
The novel product of this invention is a copolyester polymer, the molecular chains of which consist essentially of alkylene terephthalate or isophthalate segments and as an essential component a minor amount of a sulfonamide comonomer reactant of the formula: ##STR6## wherein R1 is selected from the group consisting of H and a lower alkyl radical containing from 1 to about 4 carbons; R2 and R3 are alkylene radicals of from 1 to about 6 carbons; and M is selected from a group consisting of alkaline earth and alkali metals, preferably Li, Na, or K. The composition of said polyester is such as to provide therein between 0.5 and 10 mole percent of the sulfonamide comonomer reactant, the preferred range being 0.5 to 5.0 mole percent. The alkylene terephthalate segments may also be replaced in part by alkylene diacids or diesters thereof, for example, dimethyl azelate, the substitution ranging up to about 10 mole percent.
A convenient method for preparing the copolyester polymers of this invention involves the blending together of the aromatic diacid or diester thereof, the alkylene diol, and the sulfonamide comonomer reactant, and stirring while heating up to 230° C. in an inert atmosphere. This is followed by heating up to 300° C. under reduced pressure for the period of time required for the desired molecular weight. It is advantageous to employ catalysts to accelerate the reaction rates. Manganous benzoate and calcium acetate are suitable ester interchange catalysts while antimony trioxide and antimony tributylate have been found to be effective polycondensation catalysts.
N-(β-hydroxyethyl)-2-aminoethanesulfonic acid, ##STR7## was prepared as follows: 2250 parts water was saturated with sulfur dioxide at 10° C. in a three-necked, round-bottom flask which was fitted with an electrical stirrer, thermometer, dropping funnel, and a gas inlet tube, 261 parts 1-aziridine-ethanol dissolved in 750 parts water was added via the dropping funnel while sulfur dioxide was bubbled into the flask and the temperature maintained at 10° C. After the addition was completed, the contents of the flask were concentrated to 600 parts and added to 3000 parts ethanol (F-30). The resulting solid was washed with 2000 parts ethanol, filtered, and dried to give 340 parts of the desired product.
The sodium salt of N-(β-hydroxyethyl)-N-(3-carbomethoxybenzensulfonyl) taurine, ##STR8## was prepared as follows: 253.5 parts of the N-(β -hydroxyethyl)-2-aminoethanesulfonic acid, prepared as in Example I, 60.0 parts 5.92 N sodium hydroxide, 79.5 parts sodium carbonate, 875 parts water, and 200 parts acetone were placed in a three-necked, round-bottom flask which was fitted with a stirring rod, thermometer and dropping funnel. 352 parts methyl benzoate-3-sulfonyl chloride dissolved in 1300 parts acetone were added via the dropping funnel at such a rate that the flask temperature did not increase above 40° C. After the addition was completed, two hours, the resulting slurry was stirred for two hours, concentrated to 1600 parts, then added to 5000 parts isopropyl alcohol. This slurry was cooled to 10° C. and filtered to give 506 parts of the desired product after drying under reduced pressure at 70° C.
4.32 parts of the sodium salt of N-(β-hydroxyethyl)-N-(3-carbomethoxybenzenesulfonyl) taurine prepared according to Example II were added to 108 parts of dimethyl terephthalate, 81 parts of ethylene glycol, 0.364 part of manganous benzoate, and 0.110 part of calcium acetate, the ratio of the added comonomer to dimethyl terephthalate being about 2.0 mole percent. The mixture was heated for two hours in a nitrogen atmosphere, the temperature rising to 200° C. with evolution of methanol, 0.0864 part of antimony tributylate and 0.351 part of the glycol ester of phosphoric acid were added and the pressure then reduced to 0.1 mm. of mercury and the temperature was increased to 270° C. After 1.6 hours, a polymer was obtained having an intrinsic viscosity of 0.49.
The yarn exhibited good thermal and light stability having 81.3 % retained tenacity after being heated at 180° C. for 120 minutes and 91.3% retained tenacity after being exposed in a Fade-Ometer for 160 hours. Knit tubes prepared from this yarn were dyed in separate-but-equal dyebaths with 1.0% percent (owf.) of each of the following dyes:
The final dyebath exhaustions were measured spectrophotometrically and the percent exhaustion was better than 90 percent for each basic dyestuff. IIIA AATCC wash tests at 160° F. and lightfastness tests in the Carbon-Arc Fade-Ometer at 10, 20 and 40 hours exposure were performed on each dyed sample and fair to excellent ratings were obtained.
N-(β-hydroxyethyl)-3-aminopropanesulfonic acid, ##STR9## was prepared as follows: 366 parts ethanolamine and 1000 parts methanol were cooled to 10° C. in a three-necked, round-bottom flask which was fitted with a stirring bar, thermometer, and a dropping funnel. 244 parts propane sultone dissolved in 1000 parts methanol were added via the dropping funnel at such a rate that the flask temperature did not increase above 20° C. After the addition was completed, the contents of the flask were stirred for two hours, concentrated to a thick slurry, and then added to 2400 parts isopropyl alcohol. The resulting solid was filtered, rinsed with 500 parts isopropyl alcohol and dried to give 240 parts of the desired product.
The sodium salt of N-(β-hydroxyethyl)-N-(ν-sulfopropyl)-3-carbomethoxybenzenesulfonamide, ##STR10## was prepared as follows: 109.8 parts N-(β-hydroxyethyl)-3 -aminopropane-sulfonic acid, prepared as in Example IV, 24.0 parts 5.92 N sodium hydroxide, and approximately 100 parts water were placed in a three-necked, round-bottom flask which was fitted with an electrical stirrer, thermometer, and a dropping funnel. 70.4 parts methyl benzoate-3-sulfonyl chloride dissolved in 200 parts acetone were added via the dropping funnel at such a rate that the flask temperature did not increase above 10° C. After the addition was completed, a white solid was filtered from the contents of the flask. This solid was recrystallized twice from a 10% solution in 80:20 isopropyl alcohol:water, then dried under reduced pressure to give approximately 95 parts of the desired product.
12.4 parts of the sodium salt of N-(β -hydroxyethyl)-N-(ν-sulfopropyl)-3-carbomethoxybenzenesulfonamide prepared according to Example V were added to 294 parts of dimethyl terephthalate, 216 parts of ethylene glycol, 0.262 part of manganous benzoate, the ratio of the sulfonamide comonomer to dimethyl terephthalate being about 2.0 mole percent. The mixture was heated for one hour, in a nitrogen atmosphere, the temperature rising to 220° C. with evolution of methanol. 0.306 part of the antimony tributylate and 0.994 part of trimethyl phosphate were added and the pressure reduced to 0.1 mm. of mercury and the temperature increased to 265° C. After one hour, a polymer was obtained having an intrinsic viscosity of 0.50. The Gardner "b" value, a measure of polymer yellowness, was 3.7 determined on another sample of polymer prepared in a similar manner at the beginning of the extrusion and 6.1 at the end of the extrusion. This polymer was spun and drawn as 30/6 yarn which had the following properties:
The yarn exhibited good thermal and light stability having 50.4 percent retained tenacity after being heated at 220° C. for 120 minutes and 85.0 percent retained tenacity after being exposed in a Fade-Ometer for 80 hours. Knit tubes prepared from this yarn were dyed in separate-but-equal dyebaths with 1.0 percent (owf.) of each of the following dyes:
The final dyebath exhaustions were measured spectrophotometrically and the percent exhaustion was better than 90 percent for each basic dyestuff. IIIA AATCC wash tests at 160° F. and lightfastness tests in the Carbon-Arc Fade-Ometer at 10, 20 and 40 hours exposure were performed on each dyed sample and good to excellent ratings were obtained.
N-(ν-hydroxypropyl)-3-aminopropanesulfonic acid, ##STR11## was prepared as follows: 150 parts of 3-amino-1-propanol and 2500 parts methanol were placed in a three-necked, round-bottom flask which was fitted with a stirrer, thermometer, and a dropping funnel. 244 parts propane sultone dissolved in 1000 parts methanol were added via the dropping funnel at such a rate that the flask temperature did not increase above 30° C. After the addition was completed, the contents of the flask were stirred for three hours, filtered, and dried to give 136 parts of the desired product.
The sodium salt of N-(ν-hydroxypropyl)-N-(ν-sulfopropyl)-3-carbomethoxybenzensulfonamid ##STR12## was prepared as follows: 134.0 parts N-(ν-hydroxypropyl)-3-aminopropanesulfonic acid prepared as in Example VII, 27.2 parts 5.92 N sodium hydroxide, 36.1 parts sodium carbonate, and 402.4 parts water were placed in a three-necked, round-bottom flask which was fitted with a stirring rod, thermometer, and dropping funnel. 159.5 parts methyl benzoate-3-sulfonyl chloride dissolved in 500 parts acetone were added via the dropping funnel at such a rate that the flask temperature did not increase above 25° C. After the addition was completed, the contents of the flask were stirred for two hours, filtered, and poured into 4800 parts acetone. This mixture was filtered and the filtrate evaporated to 370 parts. The resulting slurry was added to 3000 parts isopropyl alcohol and filtered. This solid was slurried in 3000 parts acetone, filtered, and dried under reduced pressure to give 186 parts of the desired product.
12.9 parts of the sodium salt of N-(ν-hydroxypropyl)-N-(νsulfopropyl)-3-carbomethoxybenzenesulfonamide prepared according to Example VIII were added to 294 parts of dimethyl terephthalate, 241 parts of ethylene glycol, 0.262 part of manganous benzoate, the ratio of the sulfonamide comonomer to dimethyl terephthalate being about 2.0 mole percent. The mixture was heated for one hour, in a nitrogen atmosphere, the temperature rising to 220° C. for evolution of methanol. 0.306 part of antimony tributylate and 0.994 part of trimethyl phosphate were added and pressure reduced to 0.1 mm. of mercury and the temperature increased to 265° C. After one hour, a polymer was obtained having an intrinsic viscosity of 0.46. This polymer was spun and drawn as 30/6 yarn which had the following properties:
The yarn exhibited good thermal and light stability having 53.0 percent retained tenacity after being heated at 220° C. for 120 minutes and 86.7 percent retained tenacity after being exposed in a Fade-Ometer for 80 hours. Knit tubes prepared from this yarn were dyed in separate-but-equal dyebaths with 1.0 percent (owf.) of each of the following dyes:
N-(6-hydroxyethyl)-3-aminopropanesulfonic acid, ##STR13## was prepared as follows: 117.2 parts 6-amino-1-hexanol and 800 parts methanol were placed in a three-necked, round-bottom flask which was fitted with a stirrer, thermometer, and a dropping funnel. 122.2 parts of propane sultone dissolved in 600 parts methanol were added via the dropping funnel. After the addition was completed, the contents of the flask were stirred at 25°-30° C. for three hours, then filtered. The filtrate was concentrated to 400 parts and added to 2000 parts ethanol (F-30). The resultant solid was filtered, combined with the first solid, washed with acetone, and dried to give 112 parts of the desired product.
The sodium salt of N-(6-hydroxyhexyl)-N-(ν-sulfopropyl)-3-carbomethoxybenzenesulfonamide, ##STR14## was prepared as follows: 239 parts of N-(6-hydroxyhexyl)3-amino-propanesulfonic acid, prepared as in Example X, 169 parts 5.92 N sodium hydroxide, 53 parts sodium carbonate, and 150 parts acetone were placed in a three-necked, round-bottom flask which was fitted with a stirrer, thermometer, and dropping funnel. 234.5 parts of methyl benzoate-3-sulfonyl chloride dissolved in 350 parts acetone were added via the dropping funnel between 30 and 35° C. After the addition was completed, the contents of the flask were then evaporated to dryness and the resulting solid recrystallized from methanol and isopropyl alcohol to give 155 parts of the desired product.
14.2 parts of the sodium salt of N-(6-hydroxyhexyl)-N-(ν-sulfopropyl)-3-carbomethoxybenzenesulfonamide prepared according to Example XI were added to 294 parts of dimethyl terephthalate, 241 parts of ethylene glycol, 0.262 part of manganous benzoate, the ratio of the sulfonamide comonomer to dimethyl terephthalate being about 2.0 mole percent. The mixture was heated for one hour, in a nitrogen atmosphere, the temperature rising to 220° C. with evolution of methanol. 0.306 part of antimony tributylate and 0.994 part of trimethyl phosphate were added and the pressure reduced to 0.1 mm. of mercury and the temperature increased to 265° C. After one hour, a polymer was obtained having an intrinsic viscosity of 0.38. This polymer was spun and drawn as 30/6 yarn which had the following properties:
The final dyebath exhaustions were measured spectrophotometrically and the precent exhaustion was better than 90 percent for each basic dyestuff. IIIA AATCC wash tests at 160° F. and lightfastness tests in the Carbon-Arc Fade-Ometer at 10, 20 and 40 hours exposure were performed on each dyed sample, and good to excellent ratings were otained.
The R1 radicals of our dye sensitizing unit can be H or lower alkyl of from 1 to 4 carbon atoms; the methoxy derivative is preferred to minimize process contamination from alcohol given off during polymerization.
1. Copolyester polymer consisting essentially of segments selected from the group consisting of alkylene terephthalate and alkylene isophthalate and containing units derived from about 0.5 to about 10 mole percent sulfonamide comonomer dye sensitizing reactant having the formula: ##STR15## wherein R1 is selected from the group consisting of H and a lower alkyl radical containing from 1 to about 4 carbons; R2 is an alkylene radical of from 1 to about 6 carbons; R3 is an alkylene radical of from 1 to 6 carbons; and M is selected from the group consisting of alkaline earth and alkali metals.
2. Copolyester polymer of claim 1 wherein R1 is methyl, and R2 and R3 are ethyl.
4. Cationic dyeable fiber forming copolyester polymer consisting essentially of segments selected from the group consisting of alkylene terephthalate and alkylene isophthalate and containing units derived from about 0.5 to about 5 mole percent sulfonamide comonomer dye sensitizing reactants containing sulfonamide groups as a repeating intralinear part of the polymer chain, said dye sensitizing reactant having the formula: ##STR16## wherein R1 is selected from the group consisting of H and a lower alkyl radical of from 1 to about 4 carbons; R2 is an alkylene radical of from 1 to about 6 carbons; R3 is an alkylene radical of from 1 to 6 carbons; and M is selected from the group consisting of alkaline earth and alkali metals.
5. The cationic dyeable fiber forming copolyester polymer of claim 4 wherein R1 is methyl, and R2 and R3 are ethyl.
7. The cationic dyeable fiber forming copolyester polymer of claim 4 wherein R1 is methyl, R2 is ethyl, and R3 is propyl.
9. The cationic dyeable fiber forming copolymer polymer of claim 4 wherein R1 is methyl, and R2 and R3 are propyl.
11. Cationic dyeable fiber forming copolyester polymer of claim 4 wherein R1 is methyl, R2 is hexyl, and R3 is propyl.
13. Copolyester polymer having from about 0.5 to about 10 mole percent comonomer dye sensitizing units containing sulfonamide groups as an intralinear part of the polymer chain, said copolymer having the formula: ##STR17## wherein R2 and R3 are alkylene radicals of from 1 to about 6 carbons, M is selected from the group consisting of alkaline earth metals and alkali metals, X is a radical remaining after the removal of a hydroxyl group from a polyester unit and Y is a radical remaining after the removal of a hydrogen atom from a carboxyl group of a polyester unit.
14. Copolyester polymer of claim 13 where R2 and R3 are ethyl.
16. Copolyester polymer of claim 13 wherein R2 is ethyl and R3 is propyl.
18. Copolyester polymer of claim 13 wherein R2 and R3 are propyl.
20. Copolyester polymer of claim 13 wherein R2 is hexyl and R3 is propyl.
22. Cationic dyeable yarn comprising copolyester polymer consisting essentially of segments selected from the group consisting of alkylene terephthalate and alkylene isophthalate and containing units derived from about 0.5 to about 10 mole percent sulfonamide comonomer dye sensitizing reactant having the formula: ##STR18## wherein R1 is selected from the group consisting of H and a lower alkyl radical of from 1 to about 4 carbons; R2 is an alkylene radical of from 1 to about 6 carbons; R3 is an alkylene radical of from 1 to 6 carbons; and M is selected from the group consisting of alkaline earth and alkali metals.
24. Cationic dyeable yarn of claim 23 wherein R1 is methyl; R2 and R3 are ethyl; and M is Na.
25. Cationic dyeable yarn comprising a copolyester polymer having from about 0.5 to about 5 mole percent comonomer dye sensitizing units containing sulfonamide groups as an intralinear part of the polymer chain, said copolyester polymer having the formula: ##STR19## wherein R2 and R3 are alkylene radicals of from 1 to about 6 carbons, M is selected from the group consisting of alkaline earth metals and alkali metals, X is a radical remaining after the removal of a hydroxyl group from a polyester unit and Y is a radical remaining after the removal of a hydrogen atom from a carboxyl group of a polyester unit.
26. Cationic dyeable yarn of claim 25 wherein R2 and R3 are ethyl and M is Na.
27. Cationic dyeable yarn of claim 25 wherein R2 is ethyl; R3 is propyl; and M is Na.
28. Cationic dyeable yarn of claim 25 wherein R2 and R3 are propyl; and M is Na.
29. Cationic dyeable yarn of claim 25 wherein R2 is hexyl; R3 is propyl; and M is Na.
US05572025 1975-04-28 1975-04-28 Copolyester polymer of enhanced dyeability Expired - Lifetime US4029638A (en)
US05572025 US4029638A (en) 1975-04-28 1975-04-28 Copolyester polymer of enhanced dyeability
US4029638A true US4029638A (en) 1977-06-14
ID=24286034
US05572025 Expired - Lifetime US4029638A (en) 1975-04-28 1975-04-28 Copolyester polymer of enhanced dyeability
US (1) US4029638A (en)
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