US3654237A - Aliphatic acid sulfonate modified polyamides - Google Patents
Aliphatic acid sulfonate modified polyamides Download PDFInfo
- Publication number
- US3654237A US3654237A US839661A US3654237DA US3654237A US 3654237 A US3654237 A US 3654237A US 839661 A US839661 A US 839661A US 3654237D A US3654237D A US 3654237DA US 3654237 A US3654237 A US 3654237A
- Authority
- US
- United States
- Prior art keywords
- acid
- polyamide
- grams
- sulfonate
- polyamides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004952 Polyamide Substances 0.000 title abstract description 44
- 229920002647 polyamide Polymers 0.000 title abstract description 44
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title description 15
- 239000002253 acid Substances 0.000 title description 13
- 125000001931 aliphatic group Chemical group 0.000 title description 9
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 17
- 239000000835 fiber Substances 0.000 description 15
- -1 aliphatic sulfonates Chemical class 0.000 description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 13
- 238000006068 polycondensation reaction Methods 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical class OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000000981 basic dye Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- WBGKAOURNYRYBT-UHFFFAOYSA-N 2-sulfopropanoic acid Chemical compound OC(=O)C(C)S(O)(=O)=O WBGKAOURNYRYBT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000980 acid dye Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BVJAYEVDNCCSIN-UHFFFAOYSA-N 2-methyl-2-sulfopropanoic acid Chemical compound OC(=O)C(C)(C)S(O)(=O)=O BVJAYEVDNCCSIN-UHFFFAOYSA-N 0.000 description 2
- CJAJEZSCULAKCB-UHFFFAOYSA-N 2-sulfohexadecanoic acid Chemical compound CCCCCCCCCCCCCCC(C(O)=O)S(O)(=O)=O CJAJEZSCULAKCB-UHFFFAOYSA-N 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- KLBWICGTGJWYMD-UHFFFAOYSA-N 2,5-disulfohexanedioic acid Chemical compound OC(=O)C(S(O)(=O)=O)CCC(C(O)=O)S(O)(=O)=O KLBWICGTGJWYMD-UHFFFAOYSA-N 0.000 description 1
- GLIZCTQNRHOAEH-UHFFFAOYSA-N 2-methoxy-2-oxoethanesulfonic acid Chemical compound COC(=O)CS(O)(=O)=O GLIZCTQNRHOAEH-UHFFFAOYSA-N 0.000 description 1
- FYKCKCYYMXDNHZ-UHFFFAOYSA-N 2-sulfobutanoic acid Chemical compound CCC(C(O)=O)S(O)(=O)=O FYKCKCYYMXDNHZ-UHFFFAOYSA-N 0.000 description 1
- SKBCSCHPOLWLCN-UHFFFAOYSA-N 2-sulfohexanedioic acid Chemical compound OC(=O)CCCC(C(O)=O)S(O)(=O)=O SKBCSCHPOLWLCN-UHFFFAOYSA-N 0.000 description 1
- XQITUXIEASXIMZ-UHFFFAOYSA-N 2-sulfooctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)S(O)(=O)=O XQITUXIEASXIMZ-UHFFFAOYSA-N 0.000 description 1
- OURSFPZPOXNNKX-UHFFFAOYSA-N 3-sulfopropanoic acid Chemical compound OC(=O)CCS(O)(=O)=O OURSFPZPOXNNKX-UHFFFAOYSA-N 0.000 description 1
- ORQDJGSWJKNUKH-UHFFFAOYSA-N 4-sulfobutanoic acid Chemical compound OC(=O)CCCS(O)(=O)=O ORQDJGSWJKNUKH-UHFFFAOYSA-N 0.000 description 1
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Definitions
- the present invention relates to modified polyamides and a process for making them.
- the affinity of polyamides for acid dyestuffs depends on the salt formation with the terminal amino groups.
- the number of the terminal amino groups has therefore been reduced, for example, by a reaction with carboxylic acids or carboxylic acid esters which have been added to the melt.
- strongly acid groups of, for example, sulfuric acid nature must be introduced.
- Modified polyamides the afiinity of which for acid dyestuffs is more or less reduced, but which can be dyed with basic dyes, can be obtained by incorporating aromatic and araliphatic sulfocarboxylic acids or the sulfonates thereof, for example those of the alkali metals.
- the sulfo group is attached to the aromatic nucleus or to an alkoxy side chain.
- the carboxyl groups of the sulfonate esters are esterified with a low aliphatic alcohol with 1 to 6 carbon atoms, for example, methanol, ethanol, nand i-propanol, n-butanol, n-pentanol and n-hexanol.
- a low aliphatic alcohol with 1 to 6 carbon atoms for example, methanol, ethanol, nand i-propanol, n-butanol, n-pentanol and n-hexanol.
- the sulfonate groups particularly the ions of lithium, sodium and potassium form the cations. Mixtures of the sulfonates with sulfonate esters may likewise be used.
- the above number of 2 to 18 carbon atoms of the aliphatic sulfocarboxylic acids is not intended as a limitation, but is the preferable number, i.e. derivatives of aliphatic sulfocarboxylic acids with more than 18 carbon atoms may also be used. It could not be foreseen that sulfonates and sulfonate esters of aliphatic sulfocarboxylic acids also make suitable modifiers for the manufacture of polyamides as the thermostability of these compounds is inferior to that of the derivatives of aromatic and araliphatic sulfonic acids known as polyamide modifiers and since these compounds are exposed to considerable thermal stress during polycondensation.
- suitable polyamide modifiers are the following substances (for clarity, only the basic compounds and not their sulfonates or sulfonate esters have been enumerated): sulfoacetic acid, 2-sulfopropionic acid, 3-sulfopropionic acid, 4 sulfobutyric acid, 2-sulfoisobutyric acid, 2-sulfo-4-hydroxybutyric acid, 2-sulfopalmitic acid, 2-sulfostearic acid, u-sulfophenylacetic acid, Z-sulfoadipic acid, 2,5-disulfoadipic acid and 2-sulfovinyl-acetic acid.
- Compounds of this type may also contain inert substituents, for example, alkyland alkoxy groups or halogen atoms. Particularly good dyeing effects are obtained with the use of derivatives of aliphatic sulfocarboxylic acids containing hydroxyl groups.
- the derivatives of the said compounds may be used as such as in admixture with one another.
- the sulfonates and sulfonate esters of aliphatic sulfocarboxylic acids are easy to obtain.
- Halogenated carboxylic acid esters may, for example, be reacted with metal sulfites, or carboxylic acids may be sulfonated and the sulfocarboxylic acids primarily formed may be converted into the sulfonates or the esters thereof.
- the sulfonate esters are in many cases more easy to obtain synthetically than the free carboxylic acids and are therefore advantageously used for the process of the invention.
- any known polyamide-forming substance may be used, preferably the lactams, aminocarboxylic acids and neutral salts of dicarboxylic acids and diamines commonly used for this purpose, for example, -e-CE1PI'O- lactam, e-aminocaproic acid and the neutral salt of hexamethylene-diamine and adipic acid (hexamethylenediammonium adipate, designated hereinafter AH-salt).
- the modifiers are generally added in the form of the solid, finely powdered substances or in the form of an aqueous solution thereof.
- the addition is advantageously made at the beginning of the polycondensation which is carried out in the same manner as without modifiers. It is also possible to add them at another moment during or after the polycondensation. Small amounts of other substances, for example, dulling agents or substances protecting against the action of light, may also be added.
- the products obtained by the process of the invention are colorless. Their melting points differ only little from those of unmodified polyamides. They can easily be formed by the usual methods, for example spun on extruders to drawable filaments. The extraction with hot water usually carried out to remove proportions of low molecular weight may be carried out before or after forming.
- the shaped articles made from the polyamides of the invention for example, films, fibers and filaments, have substantially no receptivity for acid dyestuffs, but are dyed deep tints by basic dyestuffs. By dyeing mixtures of these fibers with normal polyamide fibers in a single bath, using acid and basic dyes together, contrary multicolor effects of high brilliance can therefore be obtained.
- the following examples serve to illustrate the invention, but are not intended to limit it.
- EXAMPLE 1 In a vessel with stirring means, 40 kilograms of caprolactam were melted under a nitrogen atmosphere. At a temperature of 160 C., 2.4 kilograms of AH salt, 60 grams of titanium dioxide in the form of a aqueous dispersion, 300 grams of the sodium sulfonate of sulfoacetic acid and 3.2 grams of manganese acetate-4H O were added. The temperature was raised to 260 C. within 2 hours, water and a small amount caprolactam being distilled off. The melt was kept at 260 C. until the melt viscosity remained almost unchanged, which could be recognized by the performance of the stirring means. The melt was then discharged into cold water and the solidified white polyamide was made into chips.
- the granular product was extracted three times at 95 C. with three times the amount of distilled water and dried under strongly reduced pressure.
- the relative viscosity determined in a solution of 0.2 gram polyamide in milliliters sulfuric acid of 95.5 strength, was 2.89.
- the chips were spun in known manner from the melt and the resulting tow was drawn at a ratio of 123.6.
- the filament so obtained was dyed only little by acid dyes, but was dyed deep tints by basic dyes.
- excellent contrary multicolor effects were obtained in a single dyebath with combinations of acid and basic dyestuffs. Because of its high relative viscosity, the filament is very suitable for the manufacture of tufted carpets.
- EXAMPLE 2 The polycondensation was carried out in the manner described in Example 1, but while using, instead of the sodium sulfonate of sulfoacetic acid, 280 grams of the sodium sulfonate of sulfoacetic acid methyl ester. A polyamide of a relative viscosity of 2.92 determined in the manner described in Example 1 was obtained which could very well be spun and drawn. The filament had exactly the same good tinctorial properties as the filament of Example 1.
- EXAMPLE 3 A mixture of 550 grams of caprolactam, 33 grams of AH salt and 4.5 grams of the sodium sulfonate of 2- sulfopropionic acid was melted under nitrogen and heated to 270 C. within 2 hours, while stirring. The process was then carried out in a manner analogous to that of Example 1.
- the colorless polyamide so obtained had a relative viscosity of 3.03 determined in the manner described in Example 1 and had the tinctorial properties described in Example 1.
- EXAMPLE 4 In the manner described in Example 3, 550 grams of caprolactam, 33 grams of AH salt and 4.4 grams of the sodium sulfonate of 4-sulfobutyric acid were polycondensed. The resulting polyamide had a relative viscosity of 3.05 determined as described in Example 1, and could very well be dyed different colors in the manner described in Example 1.
- EXAMPLE 5 4.7 grams of the sodium sulfonate of 2-sulfoisobutyric acid were polycondensed in the manner described in Example 3 with the amounts of caprolactam and AH salt also indicated in that example. The resulting polyamide had a relative viscosity of 3.10 determined as described in Example 1 and the same good tinctorial properties as the polyamide of Example 1.
- EXAMPLE 6 The process was carried out in the manner described in Example 3, but while using, instead of the sodium sulfonate of 2-sulfopropionic acid, 8.8 grams of the sodium sulfonate of 2-sulfopalmitic acid.
- the polyamide so obtained had a relative viscosity of 3.00 determined in the manner described in Example 1, and could be excellently dyed in the manner described in Example 1.
- EXAMPLE 8 550 grams of caprolactam, 33 grams of AH salt and grams of the sodium sulfonate of 2-sulfo-4-hydroxybutyric acid were polycondensed in a manner analogous to that of Example 3.
- the polyamide so obtained had a relative viscosity of 2.77 determined as described in Example 1, and could particularly well be dyed in the manner also described in that example.
- EXAMPLE 9 550 grams of caprolactam and 33 grams of AH salt were polycondensed in the manner described in Example 3 while adding 6.1 grams of the sodium sulfonate of 2- sulfoadipic acid. The resulting polyamide had a relative viscosity of 2.80 determined as described in Example 1, and could be dyed different colors in the manner described in Example 1.
- a modified fiber forming aliphatic polycarbonamide produced by polycondensation of aliphatic polycarbonamide-forming substance for said polyamide in the presence of 0.05 to 10 mol percent, calculated on the monomer unit of the unmodified polyamide, of at least one alkali metal snlfonate and/or sulfonate ester of a branched or unbranched aliphatic sulfocarboxylic acid containing 2 to 18 carbon atoms, 1 or 2 sulfonic acid groups and 1 or 2 carboxyl groups.
- Modified polycaprolactam produced by polycondensation of aliphatic polycarbonamide-forming substance for said polyamide in the presence of 0.05 to 10 mol percent, calculated on the monomer unit of the unmodified polyamide, of at least one alkali metal sulfonate and/or sulfonate ester of a branched or unbranched aliphatic sulfocarboxylic acid containing 2 to 18 carbon atoms, 1 or 2 sulfonic acid groups and 1 or 2 carboxyl groups.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681770863 DE1770863A1 (de) | 1968-07-11 | 1968-07-11 | Verfahren zur Herstellung modifizierter Polyamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3654237A true US3654237A (en) | 1972-04-04 |
Family
ID=5700672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US839661A Expired - Lifetime US3654237A (en) | 1968-07-11 | 1969-07-07 | Aliphatic acid sulfonate modified polyamides |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US3654237A (de) |
| AT (1) | AT291580B (de) |
| BE (1) | BE735990A (de) |
| CH (1) | CH520723A (de) |
| DE (1) | DE1770863A1 (de) |
| ES (1) | ES369330A1 (de) |
| FR (1) | FR2012774A1 (de) |
| GB (1) | GB1232323A (de) |
| NL (1) | NL6910303A (de) |
| RO (1) | RO57530A (de) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839294A (en) * | 1972-05-01 | 1974-10-01 | Du Pont | Sulfonation of diamides of meta-phenylenediamine |
| US4093492A (en) * | 1973-05-12 | 1978-06-06 | Plate Bonn Gesellschaft Mit Beschrankter Haftung | Copolyamides containing caprolactam, lauriclactam and 11-aminoundecanoic acid |
| US4391968A (en) * | 1980-02-28 | 1983-07-05 | Montedison S.P.A. | Process for preparing polyamides having a modified dye affinity |
| US5830572A (en) * | 1988-12-14 | 1998-11-03 | E. I. Du Pont De Nemours And Company | Stain-resistant, pigmented nylon fibers |
| US5910587A (en) * | 1997-02-25 | 1999-06-08 | Ausimont S.P.A. | Compounds containing triazine ring |
| WO2005037776A1 (en) * | 2003-10-20 | 2005-04-28 | Council Of Scientific And Industrial Research | Novel molecule for inducing differentiation of dendritic cells |
| WO2011000764A1 (fr) * | 2009-07-03 | 2011-01-06 | Rhodia Operations | Polyamide modifie, procede de preparation, article obtenu a partir de ce polyamide |
| WO2011147739A1 (fr) * | 2010-05-28 | 2011-12-01 | Rhodia Operations | Polyamide modifie sulfonate aux proprietes barrieres ameliorees |
| CN112375218A (zh) * | 2020-09-16 | 2021-02-19 | 贺州学院 | 一种用于碳酸钙表面改性、含尼龙结构的水溶性高分子改性剂及其制备方法 |
-
1968
- 1968-07-11 DE DE19681770863 patent/DE1770863A1/de active Pending
-
1969
- 1969-07-04 NL NL6910303A patent/NL6910303A/xx unknown
- 1969-07-05 RO RO60437A patent/RO57530A/ro unknown
- 1969-07-07 US US839661A patent/US3654237A/en not_active Expired - Lifetime
- 1969-07-09 ES ES369330A patent/ES369330A1/es not_active Expired
- 1969-07-09 CH CH1048169A patent/CH520723A/de not_active IP Right Cessation
- 1969-07-11 BE BE735990D patent/BE735990A/xx unknown
- 1969-07-11 GB GB1232323D patent/GB1232323A/en not_active Expired
- 1969-07-11 AT AT668369A patent/AT291580B/de active
- 1969-07-11 FR FR6923791A patent/FR2012774A1/fr not_active Withdrawn
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839294A (en) * | 1972-05-01 | 1974-10-01 | Du Pont | Sulfonation of diamides of meta-phenylenediamine |
| US4093492A (en) * | 1973-05-12 | 1978-06-06 | Plate Bonn Gesellschaft Mit Beschrankter Haftung | Copolyamides containing caprolactam, lauriclactam and 11-aminoundecanoic acid |
| US4391968A (en) * | 1980-02-28 | 1983-07-05 | Montedison S.P.A. | Process for preparing polyamides having a modified dye affinity |
| US5830572A (en) * | 1988-12-14 | 1998-11-03 | E. I. Du Pont De Nemours And Company | Stain-resistant, pigmented nylon fibers |
| US5910587A (en) * | 1997-02-25 | 1999-06-08 | Ausimont S.P.A. | Compounds containing triazine ring |
| WO2005037776A1 (en) * | 2003-10-20 | 2005-04-28 | Council Of Scientific And Industrial Research | Novel molecule for inducing differentiation of dendritic cells |
| WO2011000764A1 (fr) * | 2009-07-03 | 2011-01-06 | Rhodia Operations | Polyamide modifie, procede de preparation, article obtenu a partir de ce polyamide |
| US8952122B2 (en) | 2009-07-03 | 2015-02-10 | Rhodia Operations | Modified polyamide, preparation method thereof and article obtained from said polyamide |
| WO2011147739A1 (fr) * | 2010-05-28 | 2011-12-01 | Rhodia Operations | Polyamide modifie sulfonate aux proprietes barrieres ameliorees |
| FR2960545A1 (fr) * | 2010-05-28 | 2011-12-02 | Rhodia Operations | Polyamide modifie sulfonate aux proprietes barrieres ameliorees |
| CN102918083A (zh) * | 2010-05-28 | 2013-02-06 | 罗地亚经营管理公司 | 具有改善的阻隔性能的磺酸(盐)改性聚酰胺 |
| CN102918083B (zh) * | 2010-05-28 | 2016-01-06 | 罗地亚经营管理公司 | 具有改善的阻隔性能的磺酸(盐)改性聚酰胺 |
| US10513581B2 (en) | 2010-05-28 | 2019-12-24 | Rhodia Operations | Sulfonate-modified polyamide having improved barrier properties |
| CN112375218A (zh) * | 2020-09-16 | 2021-02-19 | 贺州学院 | 一种用于碳酸钙表面改性、含尼龙结构的水溶性高分子改性剂及其制备方法 |
| CN112375218B (zh) * | 2020-09-16 | 2022-10-28 | 贺州学院 | 一种用于碳酸钙表面改性、含尼龙结构的水溶性高分子改性剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| BE735990A (de) | 1970-01-12 |
| GB1232323A (de) | 1971-05-19 |
| RO57530A (de) | 1975-02-15 |
| NL6910303A (de) | 1970-01-13 |
| ES369330A1 (es) | 1971-06-01 |
| DE1770863A1 (de) | 1972-01-13 |
| CH520723A (de) | 1972-03-31 |
| AT291580B (de) | 1971-07-26 |
| FR2012774A1 (de) | 1970-03-20 |
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