US2750306A - Treatment of textile materials with quaternary ammonium compounds - Google Patents
Treatment of textile materials with quaternary ammonium compounds Download PDFInfo
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- US2750306A US2750306A US43912854A US2750306A US 2750306 A US2750306 A US 2750306A US 43912854 A US43912854 A US 43912854A US 2750306 A US2750306 A US 2750306A
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- US
- United States
- Prior art keywords
- quaternary ammonium
- water
- temperature
- ammonium compound
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- Prior art date
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- Expired - Lifetime
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- 239000000463 material Substances 0.000 title claims description 49
- 239000004753 textile Substances 0.000 title claims description 44
- 150000003856 quaternary ammonium compounds Chemical class 0.000 title claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 29
- -1 CHLOROMETHYL ACID AMIDE Chemical class 0.000 claims description 27
- 239000005871 repellent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 32
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 31
- 125000004432 carbon atom Chemical group C* 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 17
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 17
- 239000013067 intermediate product Substances 0.000 description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000835 fiber Substances 0.000 description 13
- 239000000376 reactant Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 150000003222 pyridines Chemical class 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 150000003512 tertiary amines Chemical class 0.000 description 8
- 229930040373 Paraformaldehyde Natural products 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 229920002866 paraformaldehyde Polymers 0.000 description 7
- RHSBIGNQEIPSCT-UHFFFAOYSA-N stearonitrile Chemical compound CCCCCCCCCCCCCCCCCC#N RHSBIGNQEIPSCT-UHFFFAOYSA-N 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 229940050176 methyl chloride Drugs 0.000 description 6
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000002028 premature Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004900 laundering Methods 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229940037312 stearamide Drugs 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 2
- NWARXSLOMAMHRV-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)(=O)NCCl Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)NCCl NWARXSLOMAMHRV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 238000007265 chloromethylation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 2
- 238000005108 dry cleaning Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- WGXGAUQEMYSVJM-UHFFFAOYSA-N hexadecanenitrile Chemical compound CCCCCCCCCCCCCCCC#N WGXGAUQEMYSVJM-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MLRCLPRHEOPXLL-UHFFFAOYSA-N tetradecanenitrile Chemical compound CCCCCCCCCCCCCC#N MLRCLPRHEOPXLL-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N Amide-Hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- VXCUURYYWGCLIH-UHFFFAOYSA-N Dodecanenitrile Chemical compound CCCCCCCCCCCC#N VXCUURYYWGCLIH-UHFFFAOYSA-N 0.000 description 1
- 229920002466 Dynel Polymers 0.000 description 1
- 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 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000220010 Rhode Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Chemical class CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Chemical class CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Chemical class CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- AWHJJWHFDBOELT-UHFFFAOYSA-N hexacosanenitrile Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC#N AWHJJWHFDBOELT-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229940023462 paste product Drugs 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Chemical class CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S55/00—Gas separation
- Y10S55/24—Viscous coated filter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2164—Coating or impregnation specified as water repellent
- Y10T442/2197—Nitrogen containing
Definitions
- This invention relates to the treatment of textile materials including fabrics, yarns and threads whereby there is imparted thereto permanent water-repellent characteristics.
- the fibers of the textile to which this property can be conferred include cellulosic (cotton, linen, regenerated celluolse rayons, etc.), protein (wool Vicara, silk), cellulose esters (acetate rayon), polyamide fibers (nylon), acrylic type (Acrilan, Orlon, Dynel) and polyester type (Dacron).
- Satisfactory water-repellent characteristic can be con-- ferred to the fabric by depositing on the fabric 1.0 to 4.0% of these quaternary ammonium compounds.
- the steps of the reaction are preferably carried out in the presence of an inert, volatile organic solvent for the reactants such as benzene, dioxane, ethylene dichloride, isoheptane or ethyl acetate, which solvents prevent the mass from solidifying during the process, thus facilitating handling and control.
- an inert, volatile organic solvent for the reactants such as benzene, dioxane, ethylene dichloride, isoheptane or ethyl acetate, which solvents prevent the mass from solidifying during the process, thus facilitating handling and control.
- hydrochloric acid other compounds of chlorine capable of releasing HCl, such as PCls, PCls, SOClz may be used.
- those new, water-dispersible quaternary ammonium compounds can be prepared by other alternative procedures.
- Formaldehyde is preferably used in a polymeric form, as paraformaldehyde.
- the substituted pyridines include all the is
- Suitable proportions in preparing the quaternary ammonium compounds which are the treating agents of the present invention and the intermediates in the synthesis thereof are 1 mol equivalent of the chloromethyl acyl amide, approximately 0.5-1.5 mol equivalents of the straight chain alkyl nitrile, approximately 0.51.5 mol equivalents of formaldehyde and 0.5-1.5 mol equivalents of a chlorinating agent which may be hydrogen chloride or others mentioned herein, and approximately 0.5-1.5 mol equivalents of a tertiary amine from the group consisting of pyridine and C-alkyl substituted pyridines.
- Preferred temperature range for the reaction between the chloromethyl acyl amide and the alkyl nitriles, and also for the chloromethylation of this intermediate with formaldehyde and hydrogen chloride is 60 to 75 C. inclusive.
- Formation of the final product, the pyridinium compound, takes place readily at temperatures of 50 to 75 C. inclusive. No advantage has been observed by conducting these reactions at any specific temperatures within the limits stated. These temperatures should not be considered as critical. Below the lowest temperatures the mentioned supra speed of reaction tends to slacken. Generally speaking, temperatures above the highest in these ranges offer no advantage in yield, and increase of temperature entails a costlier condition of operation.
- the reaction temperature necessary to give optimum yields varies with the reactants and proportions.
- acyl amido methyl chloride reactant need not be that of one fatty acid, since mixtures of two or more of the general formula R.CONH.CH2X
- R denotes a paraffin hydrocarbon and X a halogen
- X a halogen
- Those water-dispersible quaternary ammonium compounds which are formed from paraflin organic acid amides and aikyi nitriles, the amide of which former specified reactant is substituted by chloromethyl, each of which reactants has a chain length of 16 carbon atoms and above up to and including 22 carbon atoms, are preferred.
- Specific members of these amides are: chloromethyl stearamide (stearyl amido methyl chloride), chlorc-methyl palmitamide (palmityl amido methyl chloride) and chlorornethyl laurarnide (lauryl amido methyl chloride).
- alkyl nitriles are: lauronitrile (dodecane nitrile), myristonitrile (tetradecane nitrile), palmitonitrile (hexadecane nitrile), stearonitrile (octadecane nitrile), and cerotonitrile (hexacosane nitrile).
- lauronitrile dodecane nitrile
- myristonitrile tetradecane nitrile
- palmitonitrile hexadecane nitrile
- stearonitrile octadecane nitrile
- cerotonitrile hexacosane nitrile
- Unsaturated hydrocarbon acid amides and nitriles may be tolerated in mixtures with the fully saturated compounds.
- Commercial amides and nitriles containing up to of oleic acid derivatives have been successfully used in the process. Appreciably higher percentages of the unsaturated hydrocarbon compounds cause a serious loss of water repellancy in the performance of the resulting quaternary ammonium compounds.
- the temperature of the aqueous treating bath or solution should preferably not be higher than 50 C., inasmuch as higher temperatures may cause premature decomposition of the quaternary ammonium treating agent.
- the treated moist textile may be dried at conventional drying temperatures (100-150 C.).
- Decomposition of the impregnating agent on the textile material, which in practice is termed curing, to form a water-repellent residue thereon, is a function of time v. temperature. It may be accomplished in about two minutes at 150 C., which is about a practical minimum temperature, or at the other extreme, i. e., upper temperature range, in about thirty seconds at 230 C., which is about a practical maximum temperature. In between these temperatures the time will vary inversely with the temperature, there being a corresponding decrease in time with the rise in temperature.
- hydrochloric acid is liberated in the decomposition of the quaternary ammonium compound. This will cause serious damage to the fiber in the nature of its being somewhat tendered, i. e., its tensile strength is dimenished; this is believed to be due to contact of the fiber with free hot hydrochloric acid.
- an agent capable of neutralization By including in the treating liquid an agent capable of neutralization, this destructive action is eliminated.
- Suitabie water-soluble, neutralizing agents are the salts of strong bases and weak acids such as the sodium or potassium salts of acetic or lactic acids. These salts are incorporated in the aqueous treating bath in an amount sufficient to prevent fiber degradation, commonly termed tenderizing.
- EXAMPLE I A. Preparation of the quaternary ammonium compound Three hundred thirteen (313) grams of methylol stearamide is mixed with six hundred (600) grams of benzene to form a slurry. While agitating vigorously and maintaining the temperature at 40 to 60 C., forty (40) grams of hydrogen chloride gas is slowly bubbled beneath the surface. Stirring is continued for 10 minutes after the hydrogen chloride has been added.
- Example II Treatment of fabric Forty (40) grams of the product prepared in Example I is dispersed by stirring into two hundred (200) cubic centimenters of water at 65 C. When completely dispersed-one hundred fifty-five (155) cubic centimeters of cold water and five (5) grams of sodium acetate are added. A piece of cotton poplin is immersed in this treating bath until thoroughly wetted and then the excess liquid is removed by passing between a pair of squeeze rolls. The cloth is then placed in an oven held at C. until just barely dry. It is then placed in a second oven held at a temperature of to C. for a period of 90 seconds.
- the cloth After this heat treatment the cloth is immersed for a few seconds in an aqueous solution containing 0.1% sodium carbonate and 0.1% sodium lauryl sulfate, at about 40 'C., to neutralize residual acidity and remove water-soluble decomposition products. It is then rinsed thoroughly in warm Water and dried at 110 to .1 20 C. After being permitted'to regain its normal moisture content the treated cloth is found to and.
- EXAMPLE II A. Preparation of quaternary ammonium compound Two hundred eighty-three (283) grams of stearamide and two hundred sixty-five (265) grams of octadecane nitrile are mixed with two hundred (200) grams of dioxane and two hundred (200) grams of benzene. The mixture is heated to about 70 C. and stirred until the amide and nitrile are dissolved. The solution is then cooled to about 55 C. and thirty-two (32) grams of 95% paraformaldehyde is added. While stirring vigorously forty-six (46) grams of phosphorus trichloride is slowly added and the temperature allowed to rise to 65 to 75 C.
- Example II-A Treatment of fabric
- Thirty (30) grams of the product prepared in Example II-A is dispersed by stirring into one hundred fifty (150) cubic centimeters of water at 55 C.
- two hundred seventeen (217) cubic centimeters of cold water and three (3) grams of sodium acetate are added.
- a piece of spun viscose rayon challis is immersed in this treating bath until thoroughly wetted and then the excess liquid is removed by squeezing.
- the cloth is then placed in a ventilated oven held at 150 to 160 C. for 4 minutes. It is then immersed for a few seconds in an aqueous solution containing 0.1% sodium carbonate and 0.5% isopropanol, after which it is rinsed thoroughly in warm water and dried at about 110 C. After regaining its normal moisture content the treated cloth is found to possess a high degree of water repellency.
- formaldehyde shall be understood as covering gaseous formaldehyde, paraformaldehyde or any other compounds which yield formaldehyde in chemical reactions.
- hydrogen chloride appears in the claims, it will be understood as covering it per se or any other compounds which yield hydrogen chloride or in chemical reactions under the conditions used in the present process.
- step 1 the quaternary ammonium compound is decomposed and hydrochloric acid released and a water-repellent residue left on the textile material
- step 2 the said water-dispersible quaternary ammonium compound being prepared by the steps which comprise reacting 1 mol equivalent of a chloromethyl acid amide of the general formula RCON O HzX wherein R designates a saturated aliphatic hydrocarbon radical of 9 to 21 carbon atoms inclusive and X stands for chlorine, with approximately 0.5-4.5 mols of a straight chain alkyl nitrile containing 10 to 22 carbon atoms inclusive, then reacting this intermediate product with approximately 0.5-1.5 mol equivalents of formaldehyde and approximately 0.5-1.5 mol equivalents of hydrogen chloride to form a second intermediate product, the temperature of reaction in forming these aforesaid intermediate products being substantially 60 to C.
- step the quaternary ammonium compound is decomposed and hydrochloric acid released and a water-repellent residue left on the textile material
- the said water-dispersible quaternary ammonium compound being prepared by the steps which comprise reacting 1 mol equivalent of a chloromethyl acid amide of the general formula /H RCON CHzX to 1.5 mol equivalents of formaldehyde and approxi-' mately 0.5 to 1.5 mol equivalents of hydrogen chloride to form a second intermediate, the temperature of reaction in forming these aforesaid intermediate products being substantially 60 to 75 C. inclusive, and thereafter reacting this latter product at temperatures of substantially 50 to 75 C. inclusive with a tertiary amine from the group consisting of pyridine and C-alkyl substituted pyridines the alkyl group of which does not contain more than 3 carbon atoms.
- this last mentioned compound being prepared by the steps which comprise reacting 1 mol equivalent of chloromethyl stearamide with approximately 0.5 to 1.5 mol equivalents of stearonitrile, then reacting this intermediate product with approximately 0.5 to 1.5 mol equivalents of paraformaldehyde and approximately 0.5 to 1.5 mol equivalents of hydrogen chloride gas, the reactions being carried out at substantially 60 to 75 C.
- this last mentioned compound being prepared by the steps which comprise reacting 1 molequivalent of stearamide, approximately 0.5-1.5 mol equivalents of octadecane nitrile, and approximately 1.5-2.5 mol equivalents of paraformaldehyde in the presence of approximately 0.50.85 mol equivalents of a phorphorus chloride, at temperatures of substantially 60 to 75 C., inclusive, and under good agitation while the organic reactants are dissolved in a volatile organic solvent therefor, then removing much of the solvent, and adding and reacting approximately 0.51.5 mol equivalents of pyridine with this product while continuing to stir and to react at temperatures of approximately to 75 C., inclusive until a firm homogeneous paste product upon cooling is secured,
- R designates an aliphatic hydrocarbon radical 9-21 carbon atoms inclusive
- X stands for chlorine
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Description
United States Patent TREATMENT OF TEXTILE MATERIALS WITH QUATERNARY AMMONIUM COMPOUNDS Raymond A. Pingree, Cranston, and Chester U. Stevens,
Saylesville, R. L, assignors to Crown Chemical Corporation, Providence, R. L, a corporation of Rhode Island No Drawing. Application June 24, 1954, Serial No. 439,128
8 Claims. (Cl. 117-121) This invention relates to the treatment of textile materials including fabrics, yarns and threads whereby there is imparted thereto permanent water-repellent characteristics. The fibers of the textile to which this property can be conferred include cellulosic (cotton, linen, regenerated celluolse rayons, etc.), protein (wool Vicara, silk), cellulose esters (acetate rayon), polyamide fibers (nylon), acrylic type (Acrilan, Orlon, Dynel) and polyester type (Dacron).
It is an object of the present invention to provide an improved process for imparting a high degree of waterrepellency to any of the aforesaid types of textile fibers, and which property is not seriously reduced by repeated launderings and/or dry cleanings wherein conventional solvents are employed in these two distinctly different cleaning operations.
It is a further object of this invention to provide an improved process for imparting a high degree of waterrepellency to the various types of textile fibers without causing fiber degradation.
Other and further important objects of this invention will become apparent from reading the description below.
In British Patent No. 477,991, granted to Baldwin, Evans and Salkeld and their assignees, there is described a process for treating cellulosic materials in aqueous solution with a compound of the general formula whereby there is imparted to the fibers water-repellent properties. In that formula R stands for the alkyl radical of a long chain fatty acid, N(tert) stands for a molecule of a tertiary base, such as pyridine, quinoline or trirnethyl amine, while X stands for a monovalent acid group, such as Cl. Some of the specific treating agents in this patent are stearamidomethylpyridinium sulfate or chloride and laurylamidomethylpyridinium chloride. However, the process of this patent using these compounds will not impart a sufiiciently high degree of initial and durable water repellency nor will the treated textile materials withstand laundering and dry cleaning to the high degree required to meet the more recent Government and civilian specifications.
We have found that the above objects of the present invention can be accomplished by treating the textile fibers with an aqueous bath of a new, water-dispersible quaternary ammonium compound presently to be described, squeezing the fibers to remove surplus liquid, drying to remove most of the' moisture left therein, and finally subjecting to an elevated temperature to form the water-repellent residue on the fibers. As pointed out in fit 2 the initial paragraph, the imparting of a high degree of Water-repellency is not confined to natuural or regenerated cellulosic fibers but embraces the protein and cellulose ester types and the more recently discovered synthetic types mentioned herein.
Satisfactory water-repellent characteristic can be con-- ferred to the fabric by depositing on the fabric 1.0 to 4.0% of these quaternary ammonium compounds.
The compounds which we employ for the purpose of' this invention are in themselves novel compounds and are more fully described and claimed in our copending; patent application Serial No. 439,127 of even date here-- with. Briefly stated, the synthesis of these compounds, which are water-dispersible quaternary ammonium com-- pounds, the structural formula of which has not been established, is as follows: a chloromethyl acyl amide of' the general formula R.CONH.CH2X, where R is a parafiin hydrocarbon radical and the acyl group has a: chain length of 10 to 22 carbon atoms inclusive and X is chlorine, is reacted with a straight chain alkyl nitrile whose alkyl group has a length of 10 to 22 carbon atoms inclusive; this resulting compound is treated with formaldehyde and hydrogen chloride to form a chloromethyl derivative of this first intermediate; and this second intermediate is then reacted with either pyridine or the C-alkyl substituted pyridines to form the water-dispersible quaternary ammonium compounds. The steps of the reaction, particularly the first two steps, are preferably carried out in the presence of an inert, volatile organic solvent for the reactants such as benzene, dioxane, ethylene dichloride, isoheptane or ethyl acetate, which solvents prevent the mass from solidifying during the process, thus facilitating handling and control. In place of hydrochloric acid other compounds of chlorine capable of releasing HCl, such as PCls, PCls, SOClz may be used. Furthermore, as explained in that invention, those new, water-dispersible quaternary ammonium compounds can be prepared by other alternative procedures. Formaldehyde is preferably used in a polymeric form, as paraformaldehyde. The substituted pyridines include all the isomers of picoline, lutidine, collidine and such disubstituted specific compounds as 2-methyl-5-ethyl pyridine.
We have not been able to establish proof of the structure of the compounds formed in our process. We believe, however, that the reaction between the alkyl nitrile and the chloromethylacylamide does proceed to form an imino chloride, thus:
and that the chloromethylation of the imino chloride proceeds:
RC=NOH2NHCOR HCHO H0] CH2C1 The final quaternary compound would be:
OHzN (tert) Cl RC=NOH2NC O R The advantages which our process of treating textile materials possesses over the British Patent No. 477,991 referred to previously reside in the fact that the waterrepellent elfect is more durable to laundering.
Suitable proportions in preparing the quaternary ammonium compounds which are the treating agents of the present invention and the intermediates in the synthesis thereof are 1 mol equivalent of the chloromethyl acyl amide, approximately 0.5-1.5 mol equivalents of the straight chain alkyl nitrile, approximately 0.51.5 mol equivalents of formaldehyde and 0.5-1.5 mol equivalents of a chlorinating agent which may be hydrogen chloride or others mentioned herein, and approximately 0.5-1.5 mol equivalents of a tertiary amine from the group consisting of pyridine and C-alkyl substituted pyridines.
Preferred temperature range for the reaction between the chloromethyl acyl amide and the alkyl nitriles, and also for the chloromethylation of this intermediate with formaldehyde and hydrogen chloride is 60 to 75 C. inclusive. Formation of the final product, the pyridinium compound, takes place readily at temperatures of 50 to 75 C. inclusive. No advantage has been observed by conducting these reactions at any specific temperatures within the limits stated. These temperatures should not be considered as critical. Below the lowest temperatures the mentioned supra speed of reaction tends to slacken. Generally speaking, temperatures above the highest in these ranges offer no advantage in yield, and increase of temperature entails a costlier condition of operation. The reaction temperature necessary to give optimum yields varies with the reactants and proportions.
It will be understood that the acyl amido methyl chloride reactant need not be that of one fatty acid, since mixtures of two or more of the general formula R.CONH.CH2X
where R denotes a paraffin hydrocarbon and X a halogen, may be employed. And mixtures of the other reactants, to wit, the alkyl nitrile and the tertiary amine, etc., may be employed. To confer latitude in properties this may be desirable.
Those water-dispersible quaternary ammonium compounds, which are formed from paraflin organic acid amides and aikyi nitriles, the amide of which former specified reactant is substituted by chloromethyl, each of which reactants has a chain length of 16 carbon atoms and above up to and including 22 carbon atoms, are preferred. Specific members of these amides are: chloromethyl stearamide (stearyl amido methyl chloride), chlorc-methyl palmitamide (palmityl amido methyl chloride) and chlorornethyl laurarnide (lauryl amido methyl chloride). Specific alkyl nitriles are: lauronitrile (dodecane nitrile), myristonitrile (tetradecane nitrile), palmitonitrile (hexadecane nitrile), stearonitrile (octadecane nitrile), and cerotonitrile (hexacosane nitrile). As the chain length of the acid amide and the alkyl nitrilc falls below C16 the Water-repellency diminishes.
Unsaturated hydrocarbon acid amides and nitriles may be tolerated in mixtures with the fully saturated compounds. Commercial amides and nitriles containing up to of oleic acid derivatives have been successfully used in the process. Appreciably higher percentages of the unsaturated hydrocarbon compounds cause a serious loss of water repellancy in the performance of the resulting quaternary ammonium compounds.
In applying these quaternary ammonium compounds to textiles, the temperature of the aqueous treating bath or solution should preferably not be higher than 50 C., inasmuch as higher temperatures may cause premature decomposition of the quaternary ammonium treating agent. In the drying step which follows in its sequence the squeezing step, the treated moist textile may be dried at conventional drying temperatures (100-150 C.). Decomposition of the impregnating agent on the textile material, which in practice is termed curing, to form a water-repellent residue thereon, is a function of time v. temperature. It may be accomplished in about two minutes at 150 C., which is about a practical minimum temperature, or at the other extreme, i. e., upper temperature range, in about thirty seconds at 230 C., which is about a practical maximum temperature. In between these temperatures the time will vary inversely with the temperature, there being a corresponding decrease in time with the rise in temperature.
During the baking step hydrochloric acid is liberated in the decomposition of the quaternary ammonium compound. This will cause serious damage to the fiber in the nature of its being somewhat tendered, i. e., its tensile strength is dimenished; this is believed to be due to contact of the fiber with free hot hydrochloric acid. By including in the treating liquid an agent capable of neutralization, this destructive action is eliminated. Suitabie water-soluble, neutralizing agents are the salts of strong bases and weak acids such as the sodium or potassium salts of acetic or lactic acids. These salts are incorporated in the aqueous treating bath in an amount sufficient to prevent fiber degradation, commonly termed tenderizing.
Without limiting our invention to any particular procedure, the following examples will serve to illustrate our preferred mode of operation.
EXAMPLE I A. Preparation of the quaternary ammonium compound Three hundred thirteen (313) grams of methylol stearamide is mixed with six hundred (600) grams of benzene to form a slurry. While agitating vigorously and maintaining the temperature at 40 to 60 C., forty (40) grams of hydrogen chloride gas is slowly bubbled beneath the surface. Stirring is continued for 10 minutes after the hydrogen chloride has been added.
To the chlorornethyl stearamide (stearyl amido methyl chloride) thus formed is added two hundred sixty-five (265) grams of octadecane nitrile (stearonitrile). The temperature is raised to 65 to 70 C. and stirring is continued for one 1) hour. At the end of this time thirty-four (34) grams of paraformaldehyde is added, and then thirty-six (36) grams of hydrogen chloride gas is bubbled in slowly beneath the surface of the mixture while the temperature is maintained at 65 to 7 C. Stirring is continued for thirty (30) minutes after the hydrogen chloride has been added, and the temperature is then lowered to about 50 C. The mixture is then placed under partial vacuum until about five hundred (500) grams of benzene has been stripped off.
To the remaining material is then slowly added ninetyfive (9.5) grams of pyridine while maintaining the temperature at 65 to 70 C. Stirring is continued for thirty (30) minutes after the pyridine has been added. The reaction .is then complete; and the product when cooled to room temperature is a firm homogeneous paste having a slight odor of pyridine. It is readily dispersible in Water at 60 C.
In this example, the preparation of the stearyl amido methyl chloride in situ forms no part of the present invention.
B. Treatment of fabric Forty (40) grams of the product prepared in Example I is dispersed by stirring into two hundred (200) cubic centimenters of water at 65 C. When completely dispersed-one hundred fifty-five (155) cubic centimeters of cold water and five (5) grams of sodium acetate are added. A piece of cotton poplin is immersed in this treating bath until thoroughly wetted and then the excess liquid is removed by passing between a pair of squeeze rolls. The cloth is then placed in an oven held at C. until just barely dry. It is then placed in a second oven held at a temperature of to C. for a period of 90 seconds. After this heat treatment the cloth is immersed for a few seconds in an aqueous solution containing 0.1% sodium carbonate and 0.1% sodium lauryl sulfate, at about 40 'C., to neutralize residual acidity and remove water-soluble decomposition products. It is then rinsed thoroughly in warm Water and dried at 110 to .1 20 C. After being permitted'to regain its normal moisture content the treated cloth is found to and.
EXAMPLE II A. Preparation of quaternary ammonium compound Two hundred eighty-three (283) grams of stearamide and two hundred sixty-five (265) grams of octadecane nitrile are mixed with two hundred (200) grams of dioxane and two hundred (200) grams of benzene. The mixture is heated to about 70 C. and stirred until the amide and nitrile are dissolved. The solution is then cooled to about 55 C. and thirty-two (32) grams of 95% paraformaldehyde is added. While stirring vigorously forty-six (46) grams of phosphorus trichloride is slowly added and the temperature allowed to rise to 65 to 75 C. Stirring is continued for 15 minutes after the phosphorus trichloride has been added. The mixture is cooled to about 55 C., then thirty-two (32) grams of 95% paraformaldehyde and forty-six (46) grams of phosphorus trichloride are added and the reaction is continued at 65 to 75 C. for 30 minutes. The mixture is then cooled to 50 to 60 C. and approximately two hundred (200) grams of mixed solvent is distilled off under reduced pressure.
To the remaining material is then slowly added ninetyfive (95) grams of pyridine while maintaining the temperature at 65 to 75 C. Stirring is continued for 15 minutes after the pyridine has been added and the mixture is then cooled to room temperature. The final product is a firm homogeneous paste which is readily dispersible in warm water.
B. Treatment of fabric Thirty (30) grams of the product prepared in Example II-A is dispersed by stirring into one hundred fifty (150) cubic centimeters of water at 55 C. When completely dispersed, two hundred seventeen (217) cubic centimeters of cold water and three (3) grams of sodium acetate are added. A piece of spun viscose rayon challis is immersed in this treating bath until thoroughly wetted and then the excess liquid is removed by squeezing. The cloth is then placed in a ventilated oven held at 150 to 160 C. for 4 minutes. It is then immersed for a few seconds in an aqueous solution containing 0.1% sodium carbonate and 0.5% isopropanol, after which it is rinsed thoroughly in warm water and dried at about 110 C. After regaining its normal moisture content the treated cloth is found to possess a high degree of water repellency.
The same procedure is given supra, wherein the fabric was cotton and regenerated cellulose, can be used on wool, silk, cellulose acetate, and the various other synthetic fibers.
It is understood that the details set forth in the above examples of treating textile materials may be varied within wide limits without departing from the spirit of this invention as defined in the appended claims.
In the claims the term formaldehyde shall be understood as covering gaseous formaldehyde, paraformaldehyde or any other compounds which yield formaldehyde in chemical reactions. Where the term hydrogen chloride appears in the claims, it will be understood as covering it per se or any other compounds which yield hydrogen chloride or in chemical reactions under the conditions used in the present process.
We'claim:
1. The process of treating textile materials to impart thereto permanent water-repellent properties, which cornprises impregnating the same with an aqueous dispersion of a quaternary ammonium compound until the textile materialis substantially thoroughly wetted, squeezing out excess liquid, then subjecting this squeezed material to heat treatment in the absence of added moisture andincreasing the temperature after it is dry to between about 150 C. and 230 C., in which step the quaternary ammonium compound is decomposed and hydrochloric acid released and a water-repellent residue left on the textile material, the said water-dispersible quaternary ammonium compound being prepared by the steps which comprise reacting 1 mol equivalent of a chloromethyl acid amide of the general formula RCON O HzX wherein R designates a saturated aliphatic hydrocarbon radical of 9 to 21 carbon atoms inclusive and X stands for chlorine, with approximately 0.5-4.5 mols of a straight chain alkyl nitrile containing 10 to 22 carbon atoms inclusive, then reacting this intermediate product with approximately 0.5-1.5 mol equivalents of formaldehyde and approximately 0.5-1.5 mol equivalents of hydrogen chloride to form a second intermediate product, the temperature of reaction in forming these aforesaid intermediate products being substantially 60 to C. inclusive, and thereafter reacting this latter product at temperatures 50 to 75 C. inclusive with 0.5-1.5 mol equivalents of a tertiary amine from the group consisting of pyridine and the C-alkyl substituted pyridines the alkyl group of which does not contain more than 3 carbon atoms.
2. The process of treating textile materials to impart thereto permanent water-repellent properties, which comprises impregnating the same with an aqueous dispersion of a quaternary ammonium compound until the textile material is substantially thoroughly wetted, squeezing out excess liquid, then subjecting this squeezed material to heat treatment in the absence of added moisture and increasing the temperature after it is dry to between about C. and 230 C., in which step the quaternary ammonium compound is decomposed and hydrochloric acid released and a water-repellent residue left on the textile material, the said water-dispersible quaternary ammonium compound being prepared by the steps which comprise reacting 1 mol equivalent of a chloromethyl acid amide of the general formula /H RCON CHzX to 1.5 mol equivalents of formaldehyde and approxi-' mately 0.5 to 1.5 mol equivalents of hydrogen chloride to form a second intermediate, the temperature of reaction in forming these aforesaid intermediate products being substantially 60 to 75 C. inclusive, and thereafter reacting this latter product at temperatures of substantially 50 to 75 C. inclusive with a tertiary amine from the group consisting of pyridine and C-alkyl substituted pyridines the alkyl group of which does not contain more than 3 carbon atoms.
3. The process of treating textile materials to impart thereto permanent water-repellent properties, which comprises impregnating the same with an aqueous dispersion of a quaternary ammonium compound and the watersoluble, alkaline reacting salt of a strong base with a weak acid held at a temperature not above substantially 50 C. to avoid premature decomposition of said treating agent, and after the textile material is substantially thoroughly wetted, squeezing out excess liquid, then subjecting this squeezed material to heat treatment in the absence of added moisture and increasing the temperature after it is dry to about 150 C. and 230 C., the time varying inversely with the temperature, in which step the quaternary ammonium compound is decomposed and a water-repellent residue left on the textile material, the amount of the quaternary ammonium compound which is deposited on the textile material in the said impregnation step being 1.0 to 4.0%., this said last mentioned compound being prepared by the steps which comprise reacting 1 mol equivalent of a chloromethyl acid amide of the general formula /H RC ON CHzX wherein R designates a saturated :aliphatic hydrocarbon radical of at least 9 to 21 carbon atoms inclusive, and X stands for chlorine with approximately 0.5 to 1.5 mols of a straight chain alkyl nitrile containing not less than 16 carbon atoms but not over 22 carbon atoms, then reacting this intermediate product with approximately 0.5 to 1.5 mol equivalents of formaldehyde and approximately 0.5 to 1.5 mol equivalents of hydrogen chloride to form a second intermediate, the temperature of reaction in forming these aforesaid intermediate products being substantially 60 to 75 C. inclusive, and thereafter reacting this latter product temperatures of substantially 50 to 75 C. inclusive with a tertiary amine from the group consisting of pyridine and C-alkyl substituted pyridines the alkyl group of which does not contain more than 3 carbon atoms.
4. The process of treating textile materials to impart thereto permanent water-repellent properties, which comprises impregnating the same with an aqueous dispersion of a quaternary ammonium compound and a water-soluble alkaline reacting alkali metal salt of a weak acid held at a temperature not above substantially 50 C. to avoid premature decomposition of said treating agent, and after the textile material is substantially thoroughly Wetted squeezing out excess liquid, then subjecting this squeezed material to a temperature slightly above the boiling point of water until barely dry, then to an oven temperature of about 150 C. for about two minutes to 230 C. for about seconds, in which heating operation the quaternary ammonium compound is decomposed and a water-repellent residue left on the textile material, the amount of the quaternary ammonium compound which is deposited on the textile material in the said impregnation step being 1.0 to 4.0%, this last mentioned compound being prepared by the steps which comprise reacting 1 mol equivalent of chloromethyl stearamide with approximately 0.5 to 1.5 mol equivalents of stearonitrile, then reacting this intermediate product with approximately 0.5 to 1.5 mol equivalents of paraformaldehyde and approximately 0.5 to 1.5 mol equivalents of hydrogen chloride gas, the reactions being carried out at substantially 60 to 75 C. inclusive and in the presence of a volatile organic solvent for the reactants and with good agitation, removing the major portion of the solvent and thereafter thoroughly mixing pyridine with the second intermediate product and reacting therewith at temperatures of substantially 50 to 75 C. inclusive until the reaction is substantially complete and a mass which is pasty on cooling is secured the alkyl group of which does not contain more than 3 carbon atoms.
5. The process of treating textile materials to impart thereto permanent water-repellent properties, which comprises impregnating the same with an aqueous dispersion of a quaternary ammonium compound and a water-soluble alkaline reacting alkali nietal'salt of a weak acid held at a temperature not above substantially 50 C. to avoid premature decomposition of said'trea'ting agent, and after the textile material is substantially throughly wetted squeezing out excess liquid, then subjecting this squeezed material to a temperature slightly above the boiling point of water until barely dry, then to an oven temperature of about 150 C. for about two minutes to 230 C. for about 30 seconds, in which heating operation the quaternary ammonium compound is decomposed and a Water-repellent residue left on the textile material, the amount of the quaternary ammonium compound which is deposited on the textile material in the said impregnation step being 1.0 to 4.0%, this last mentioned compound being prepared by the steps which comprise reacting 1 molequivalent of stearamide, approximately 0.5-1.5 mol equivalents of octadecane nitrile, and approximately 1.5-2.5 mol equivalents of paraformaldehyde in the presence of approximately 0.50.85 mol equivalents of a phorphorus chloride, at temperatures of substantially 60 to 75 C., inclusive, and under good agitation while the organic reactants are dissolved in a volatile organic solvent therefor, then removing much of the solvent, and adding and reacting approximately 0.51.5 mol equivalents of pyridine with this product while continuing to stir and to react at temperatures of approximately to 75 C., inclusive until a firm homogeneous paste product upon cooling is secured, the steps of reaction to secure the quaternary ammonium compound being characterized by the application of heat.
6. The process of treating textile materials to impart permanent water-repellent properties, which comprises impregnating the same with an aqueous dispersion of a quaternary ammonium compound and a water-soluble alkaline neutralizing agent until the textile material is substantially wetted, squeezing out excess liquid, then subjecting this squeezed material to heat treatment in the absence of added moisture and increasing the temperature after it is dry to between 150 C. and 230 C., the time varying inversely with the temperature, in which step the quaternary ammonium compound is decomposed and a water repellent residue left on the textile material, the amount of the quaternary ammonium compound which is deposited on the textile material in the impregnation step being about 1.0 to 4.0%, this said last mentioned compound being prepared by the steps which comprise reacting a chloromethyl acid amide of the general formula RC ON OHzX wherein R designates a saturated aliphatic hydrocarbon radical of at least 15 carbon atoms but not over 21 carbon atoms, and X stands for chlorine, with a straight :chain alkyl nitrile containing not less than 16 carbon atoms but not over 22 carbon atoms, then reactingthis intermediate product with formaldehyde and hydrogen chloride to form a second intermediate, the temperature of reaction in forming these aforesaid intermediate products being substantially to C. inclusive, and thereafterreacting this latter product at temperatures of substantially 50 to 75 C. inclusive with a tertiary amine 'from the group consisting of pyridine and C-alkyl substituted pyridines, the alkyl group of which does not contain more than 3 carbon atoms, reactants being 1 mol equivalent of the chloromethyl acid amides to substantially 0.5-1.5 mol equivalents of each of the other reactants.
7. The process of treating textile materials to impart permanent water-repellent properties, which comprises impregnating the same with an aqueous dispersion of a quaternary ammonium compound and a water-solubletalkaline neutralizing agent until the textile material is :substantially wetted, squeezing out excess liquid, then subjecting this squeezed material to heat treatment in :the absence of added moisture and increasing the temperature after it is dry to between C. and 230 C., the time varying inversely with the temperature, in which step the quaternary ammonium compound is decomposed and a water repellent residue left on the textile material, the amount of the quaternary ammonium compound which is deposited on the textile material in the impregnation step being about 1.0 to 4.0%, this said last mentioned compound being prepared by the steps which comprise reacting one mol equivalent of a chloromethyl acid amide of the general formula RCON CHzX
wherein R designates an aliphatic hydrocarbon radical 9-21 carbon atoms inclusive, and X stands for chlorine, with approximately 0.5-1.5 mol equivalents of a straight chain alkyl nitrile containing 9-21 carbon atoms inclusive, then reacting this intermediate product with approximately 0.5-1.5 mol equivalents of hydrogen chloride to form a second intermediate product, the temperature of reaction in forming these intermediate products being substantially 60 to 75 C. inclusive, thereafter reacting this latter product at temperatures of substantially 50 to 75 C. inclusive with substantially 0.51.5 mol equivalents of a tertiary amine from the group consisting of pyridine and the C-alkyl substituted pyridines, the alkyl group of which does not contain more than 3 carbon atoms, reactants being 1 mol of the chloromethyl acid amides to substantially 0.51.5 mol equivalents of each of the other reactants.
8. The process of treating textile materials to impart permanent water-repellent properties, which comprises impregnating the same with an aqueous dispersion of a quaternary ammonium compound and a water-soluble alkaline neutralizing agent until the textile material is substantially wetted, squeezing out excess liquid, then subjecting this squeezed material to heat treatment in the absence of added moisture and increasing the temperareacting one mol equivalent of a chloromethyl acid amide of the general formula RCON wherein R designates an aliphatic hydrocarbon radical 9-21 carbon atoms inclusive, and X stands for chlorine, with approximately 05-15 mol equivalents of a straight chain alkyl nitrile containing 9-21 carbon atoms inclusive, then reacting this intermediate product with approximately 0.5-1.5 mol equivalents of hydrogen chloride to form a second intermediate product, these two reaction steps being carried out at substantially to C. inclusive under good agitation in the presence of a volatile organic solvent for the reactants followed by removal of the major portion of the solvent, thereafter reacting this second intermediate product at temperatures of substantially 50 to 75 C. inclusive with substantially 0.51.5 mol equivalents of a tertiary amine from the group consisting of pyridine and the C-alkyl substituted pyridines.
References Cited in the file of this patent UNITED STATES PATENTS 2,250,930 Evans et a1. July 29, 1941 FOREIGN PATENTS 477,991 Great Britain Jan. 10, 1938
Claims (1)
1. THE PROCESS OF TREATING TEXTILE MATERIALS TO IMPART THERETO PERMANENT WATER-REPELLENT PROPERTIES, WHICH COMPRISES IMPREGNATING THE SAME WITH AN AQUEOUS DISPERSION OF A QUATERNARY AMMONIUM COMPOUND UNTIL THE TEXTILE MATERIAL IS SUBSTANTIALLY THOROUGHLY WETTED, SQUEEZING OUT EXCESS LIQUID, THEN SUBJECTING THIS SQUEEZED MATERIAL TO HEAT TREATMENT IN THE ABSENCE OF ADDED MOISTURE AND INCREASING THE TEMPERATURE AFTER IT IS DRY TO BETWEEN ABOUT 150* C. AND 230* C., IN WHICH STEP THE QUATERNARY AMMONIUM COMPOUND IS DECOMPOSED AND HYDROCHLORIC ACID RELEASED AND A WATER-REPELLENT RESIDUE LEFT ON THE TEXTILE MATERIAL, THE SAID WATER-DISPERSIBLE QUATERNARY AMMONIUM COMPOUND BEING PREPARED BY THE STEPS WHICH COMPRISE REACTING 1 MOL EQUIVALENT OF A CHLOROMETHYL ACID AMIDE OF THE GENERAL FORMULA
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3868789A1 (en) | 2020-02-18 | 2021-08-25 | The Hong Kong Research Institute of Textiles and Apparel Limited | Method for preparing water repellent textile substrates and products thereof |
| US12209358B2 (en) | 2020-02-18 | 2025-01-28 | The Hong Kong Research Institute Of Textiles And Apparel Limited | Method for preparing water repellent textile substrates and products thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB477991A (en) * | 1936-06-08 | 1938-01-10 | Alfred William Baldwin | Treatment of cellulosic textile materials, paper, films and the like |
| US2250930A (en) * | 1937-04-16 | 1941-07-29 | Ici Ltd | Treatment of wool and silk |
-
1954
- 1954-06-24 US US43912854 patent/US2750306A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB477991A (en) * | 1936-06-08 | 1938-01-10 | Alfred William Baldwin | Treatment of cellulosic textile materials, paper, films and the like |
| US2250930A (en) * | 1937-04-16 | 1941-07-29 | Ici Ltd | Treatment of wool and silk |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3868789A1 (en) | 2020-02-18 | 2021-08-25 | The Hong Kong Research Institute of Textiles and Apparel Limited | Method for preparing water repellent textile substrates and products thereof |
| US12209358B2 (en) | 2020-02-18 | 2025-01-28 | The Hong Kong Research Institute Of Textiles And Apparel Limited | Method for preparing water repellent textile substrates and products thereof |
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