US2696448A - Shrinkproofed wool and method for producing same - Google Patents
Shrinkproofed wool and method for producing same Download PDFInfo
- Publication number
- US2696448A US2696448A US82025A US8202549A US2696448A US 2696448 A US2696448 A US 2696448A US 82025 A US82025 A US 82025A US 8202549 A US8202549 A US 8202549A US 2696448 A US2696448 A US 2696448A
- Authority
- US
- United States
- Prior art keywords
- polyamide
- wool
- derivative
- parts
- acid
- 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
- 210000002268 wool Anatomy 0.000 title claims description 98
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000004952 Polyamide Substances 0.000 claims description 133
- 229920002647 polyamide Polymers 0.000 claims description 133
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 150000003839 salts Chemical class 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 208000027418 Wounds and injury Diseases 0.000 claims description 6
- 230000006378 damage Effects 0.000 claims description 6
- 208000014674 injury Diseases 0.000 claims description 6
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical class [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 39
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 33
- -1 trimethyl methyl Chemical group 0.000 description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- 229910052739 hydrogen Inorganic materials 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 22
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 17
- 235000019253 formic acid Nutrition 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 150000001408 amides Chemical class 0.000 description 14
- 125000001931 aliphatic group Chemical group 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229920002866 paraformaldehyde Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229920002302 Nylon 6,6 Polymers 0.000 description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 238000004900 laundering Methods 0.000 description 7
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 125000005521 carbonamide group Chemical group 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000001414 amino alcohols Chemical class 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Chemical group 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 3
- 229940100630 metacresol Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Chemical group 0.000 description 3
- 239000011574 phosphorus Chemical group 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 description 2
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229960002684 aminocaproic acid Drugs 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- XGIKILRODBEJIL-UHFFFAOYSA-N 1-(ethylamino)ethanol Chemical class CCNC(C)O XGIKILRODBEJIL-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-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
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 241000947840 Alteromonadales Species 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MZFOALBFXAVJLK-UHFFFAOYSA-N C(CCCCCCCCC(=O)[O-])(=O)[O-].[NH4+].[NH4+].C=C Chemical compound C(CCCCCCCCC(=O)[O-])(=O)[O-].[NH4+].[NH4+].C=C MZFOALBFXAVJLK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 101100481695 Mus musculus Tmie gene Proteins 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229920001273 Polyhydroxy acid Polymers 0.000 description 1
- 240000000037 Prosopis spicigera Species 0.000 description 1
- 235000006629 Prosopis spicigera Nutrition 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- VDBXLXRWMYNMHL-UHFFFAOYSA-N decanediamide Chemical compound NC(=O)CCCCCCCCC(N)=O VDBXLXRWMYNMHL-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- GSJFXBNYJCXDGI-UHFFFAOYSA-N methyl 2-hydroxyacetate Chemical compound COC(=O)CO GSJFXBNYJCXDGI-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
-
- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2971—Impregnation
Definitions
- the wool be-coinmerleiallyfeasible e.,l that'thetiine -fofftreatment'bereasbnablyeshrt, etc.
- Curingf Iin any -desiredj--waymay be usedffbut usually will vinvolve aheat'treatfment #at elevated ⁇ temperature sufeient to insolubilize -the.polyamide-derivative.
- Such temperatures Willm'suallyrexeeedl O0 1 and may desirably be in the rangeof from 120? to 150 C.
- Many of the polyamide derivatives cnbe subjected to much higher temperatures 'asfforfexample 250 'tof-285 C., but such elevated temperatures are not ⁇ usually desirable with treated wool products.
- N-disubstituted aminoalcohols in which the substituent groups on the nitrogen are saturated aliphatic groups of less than six carbon atoms as for example alkyl groups below hexane, including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, trimethyl methyl, and the various pentyl (amyl) groups, and such alkyl groups carrying substituent groups like hydroxy, which do not interfere with the desired water solubility.
- the stated water soluble salts are new entities in the art of great value since they may be used in solution in water or in aqueous emulsions.
- the salts per se may be recovered from the reaction medium in which they are produced by precipitation therefrom by means of an organic liquid capable of precipitating such salt from the solution in the form of a water soluble salt.
- the salt should not be neutralized as by addition of inorganic bases such as the caustic alkalis or ammonia, since such neutralization will destroy the water solubility of the modified polyamide.
- the formation of the water soluble salt may take place by reaction of the polyamide in solution, as in formic acid, with formaldehyde and the aminoalcohol.
- the formaldehyde may first be reacted with the polyamide followed by reaction with the aminoalcohol, or these reactants namely polyamide, formaldehyde and aminoalcohol may be reacted simultaneously in the presence of the acid, followed by precipitation of the salt by a convenient organic solvent, and the precipitated polymer is then readily soluble in water.
- R is an alkvlene while R1 and R, are the N-disubstitnent groups. While the illustrated mechanism is believed to be correct, it is not intended as limiting.
- the polyamide employed may be any synthetic linear polyamide bearing recurring carbonamide groups as an integral part of the main polymer chain.
- the said recurring groups generally are separated by an average number of carbon atoms of at least 2.
- the number of such recurring groups which are modified and converted in the N-alkoxv methyl derivatives will vary with the proportions of the reactants used, but should be suii'icient to yield water solubility of the salt ultimately prepared therefrom.
- the recurring groups will be at least of the amide groups in the main polymer chain. Extent of conversion of NH groups in the polyamides to N-alkoxy methyl groups is dependent on the anhydrous condition of the solvent (formic acid) as well as the proportions of reactants used. Thus greater conversion is obtained with 100% formic acid than with 90% formic.
- the polyamide employed may be of various types, for example. a polymethylene amide of a polymethylene dicarboxylic acid, or a poly omega-amino acid, or copolymers of these polyamides just mentioned, etc.
- Exemplary polyamides are polyhexamethylene adipamide, polyhexarnethylene sebacamide, or polymers from epsiloni aminocaproic acid, including poly-epsilon-arninocaproic acid derived from epsilon caprolactam, copolymers such as that from ethylene diammonium sebacate and epsiloncaprolactam, etc.
- the molecular weight of the polymers should be rather high, that is, those which have an intrinsic viscosity above 0.4.
- any formaldehydeyielding material may be employed. Paraform is conveniently employed. aqueous formaldehyde may be used. The amount of formaldehyde is desirably from 0.5 to 2.0 parts to one part of polyamide, dependent on the extent of reaction desired.
- the N-disubstituted aminoalcohol should be one capable of neutralizing formic acid. lts general characteristics have been indicated above. As exemplary of such aminoalcohols there may be mentioned alkylolamines containing tertiary nitrogen, the alkylene group having for example from l to 4 and higher C chains. For example there may be mentioned dimethylaminoethanol, diethyl aminoethanol, methyl diethanol-amine, dimethyl isopropanolamine, triethanolamine, similar butanolamines, etc., and related compounds where the two substituents on the nitrogen may form a ring as in the morpholines such as hydroxyethyl morpholine.
- Certain disubstituted aminoalcohols such as phenyl diethanolamine, have a pH of about 7 (aqueous solution) and consequently are so weakly basic that they do not react sufficiently with formic acid. Therefore the nylon derivatives produced with such amines are either waterinsoluble or only very slightly water-soluble.
- Other amines in this category are ethyl phenyl ethanolaminc and di-2-ethyl hexyl ethanolamine.
- the molar ratio of aminoalcohol to formaldehyde will be equi-molar but may vary as from 3:1 to 1:2.
- Formic acid has been particularly referred to as the reaction solvent.
- Other organic acids which are solvents for polyamides may be used.
- Carboxylic acids such as formic, acetic, hydroxyacetic, and chloracetic, may be mentioned.
- Formic acid is desirably employed; and may be used in any concentration, such as 70% to 100%, in which it is a solvent for the polyamide used. Commercially available formic acid may be employed conveniently.
- the temperature of reaction may be any temperature at which the stated reaction takes place, for example above 30 C., but should be below that at which undesired degradation of the polyamide takes place.
- the organic liquid solvent employed for precipitation of the water-soluble salt may be of any convenient solvent which gives the precipitated polymer.
- Acetone may be used as well as other ketones such as methyl ethyl ketone, diethyl ketone, etc.
- EXAMPLE B parts of a polyhexamethylene adipamide, prepared from hexamethylene diammonium adipate, which had an intrinsic viscosity in meta-cresol of 0.47 was reacted with 87 parts of 90% formic acid, l0 parts paraform and 29.3 parts of diethylaminoethanol in the same manner as described in Example A.
- the reaction product was a deep red solution.
- EXAMPLE C 10 parts of a commercial sample of polyhexamethylene adipamide which had an intrinsic viscosity in metacresol of 0.96 was reacted in the same fashion as described in Example A except that 137 parts of 90% formic acid was used instead of 87 parts.
- EXAMPLE E A solution of l0 parts of a commercial sample of a polyhexamethylene adipamide (intrinsic viscosity in metaacresol of 0.96) was prepared in 137 parts of 90% formic acid at 60-65 C. A solution of 10 parts of paraform in 35 parts of triethanolamine was reacted with the nylon-formic acid solution employing the general procedure outlined in Example A. The reaction product was fluid at room temperature. Treatment of a portion of the above-mentioned reaction product with a large volume of acetone resulted in the separation of a fine granular precipitate which was easily soluble in water at 50-60" C.
- EXAMPLE F A solution of 10 parts of a polyamide made from e-caprolactam (intrinsic viscosity in meta-cresci of 0.91) in 87 parts of 90% formic acid was reacted with 10 parts of paraformaldehyde and 30 parts of methyl diethanolamine employing the general procedure described in Example A.
- the precipitated product obtained ⁇ by ⁇ treating a portion of the reaction mixture with a large volume of acetone was easily soluble in water.
- EXAMPLE G A reaction mixture was prepared from l0 parts of a polyamide made from e-caprolactam (intrinsic viscosity 0.91), 87 parts of 90% formie acid, 10 parts of paraformaldehyde, and 26 parts of dimethyl isopro ⁇ panolarnine by the general procedure described in Example A.
- the precipitated product (with acetone) was partially soluble in Water at 5060 C.
- Example G was repeated except that the poly e-amino caproic acid used had an intrinsic viscosity of 0-.79 and 33 parts of hydroxyethyl morpholine instead of the dimethyl isopropanolamine.
- the precipitated product (with acetone) was easily soluble in water at 50-60" C.
- the treated sample along with a similarly measured untreated wool sample was then immersed in a 1% soap solution (l liter) at 25 C. for a period of 2 hours.
- the samples were then rinsed, dried and remeasured and the relaxation shrinkage calculated.
- the samples were then laundered for 3 hours in a mechanical washing machine containing 13 liters of water at 60 C. and 35 grams of soap.
- the wool samples were again rinsed, dried, and remeasured and total shrinkage calculated.
- the area shrinkage obtained for the samples was as follows.
- the finished wool sample had a dry, normal hand and good draping characteristics.
- Example 2 A sample of wool, measured as described in Example 1, was immersed in the 3.3% aqueous solution of the poly hexamethylene adipamide diethylaminoethanol derivative prepared in Example B. After the excess pad liquor was squeezed out, the Weight increase of the wool indicated that the amount of polyamide applied was 3.3%. The sample was dried at 75-80 C. and cured for 15 minutes at 130 C.
- the treated sample along with an untreated measured Wool sample was subjected to relaxation and laundering as described in Example l, area measurements being taken after each process.
- the results obtained were as follows.
- the finished wool sample had a dry, normal hand and good draping characteristics.
- Example 3 The treated sample together with untreated sample was relaxedand"r laundered in the mannen described in. Example 1 exceptthat. the laundering.v was for 2- hours. TheA shrinkage; dataobtained wasv asfollowsz.
- the finished. wool sample has a dry, normal hand and good draping ⁇ characteristics.
- Example 4 An ⁇ aqueous solution of a commercial poly hexa- Inethylene adipamideftriethanolamine derivative was prepared in the manner. described in. Example E. The concentration of'. the solution was 3.3%, basedon the weight of the polyamide.r A sample of wool, measured in the usual. fashion, was immersed in the solution. The weight increase of the wool sample, after removing ⁇ the excess pad liquor, ⁇ indicated that 3.3% of the resin had been applied.V The sample was dried at 75 C.. and cured at 130 C. for 15y minutes.v
- the finished wool sample had a dry,y normal hand and good draping characteristics.
- Example 5 Anaqueous solution of a poly e-arnino caproic acidmethyl diethanolamine derivative was prepared' in the manner described in Example F. The concentration of the solution was 3.3% basedi on the weight of the polyamide. A measured sample of wool was treated with the solution in the usual fashion and subsequent to the removal of excess'pad liquor, the sample was dried and cured under the same conditions as described in Example 4. The weight pick-up of the wool sample after padding indicated that 3.4% of ⁇ the polyamide had been applied to the wool.
- the finished wool sample had a dry, normal ⁇ hand and good draping characteristics.
- The; iinishedwool. sample had a dry, normalV hand and good draping,v characteristics.
- One such group is a water soluble polyamide derivative having a group or groups in the polymer chain,l of the formula in which R5 is a ⁇ saturated aliphatic divalent hydrocarbon radical', such as alkylene, containing from 1 to 17 carbon atoms and Re is a cation such as hydrogen, metals, the ammonium radical, or monovalent hydrocarbon radicals containing from 1, to 7 carbon atoms;
- R5 is a ⁇ saturated aliphatic divalent hydrocarbon radical', such as alkylene, containing from 1 to 17 carbon atoms and Re is a cation such as hydrogen, metals, the ammonium radical, or monovalent hydrocarbon radicals containing from 1, to 7 carbon atoms
- the water soluble salts with for example alkali metals, NH4, etc., or with complex organic ammonium groups such as quaternary trimethyl benzyl' ammonium hydroxide may be used. They are produced by reacting a synthetic linear polyamide.
- reaction products may be converted into water-soluble salts where the ⁇ nylon residue is in the anion.
- the synthetic linear polyamides used may be those set forth above for theA production of the cation type water soluble derivatives.
- the oxygen containing acid catalysts include fatty acids and substituted fatty acids such as formic, acetic, chloroacet-ic, trimethyl acetic, aromatic acids such as benzoic, sulfonic acids such as p-toluene sulfonic, dibasic acids such as oxalic, maleic, etc., and even inorganic acids such as phosphoric.
- fatty acids and substituted fatty acids such as formic, acetic, chloroacet-ic, trimethyl acetic, aromatic acids such as benzoic, sulfonic acids such as p-toluene sulfonic, dibasic acids such as oxalic, maleic, etc., and even inorganic acids such as phosphoric.
- Such acid catalyst should have an ionization constant of at least 9.6 106.
- formaldehydel has been referred to, it is generally used in the ⁇ form of paraformaldehyde, but the same considerations apply here, as to formaldehyde and the ratio of formaldehyde to synthetic linear polyamide as given above for the cation type water soluble salts.
- the hydroxy carboxylic acids are generally the monohydroxy aliphatic acids of for example 2 to 17 carbon atom saturated chains, such as glycolic, lactic, 10-hydroxydecanoic, 12 hydroxy stearic, etc., although polyhydroxy acids of this type, such as tartaric, etc., may be used.
- the esters are those of the stated acids with alkanols and alkoxy alkanels such as methyl, ethyl, butyl and methoxymethyl alcohols, as welly as esters of cycloaliphatic alcohols such as cyclohexyl alcohol, and esters of aralkyl alcohols such as benzyl alcohol. lt will be noted that generally the hydroxyl group is attachedA to an aliphatic carbon.
- the amounts of acid orester will usually be determined on the formaldehyde, equi-molar ratios being preferred, but molar ratios of 1:2 to 2:1 may be used.
- the reactions are carried out at any temperature from room (20 C.) to 15.0 C. and higher, but of course belowy temperatures undesirably affectingr the polyamide.
- EXAMPLE J' A. mixture of 50 parts polyhexamethylene adipamide (intrinsic viscosity above 0.4), 5.0 parts paraformaldehyde, 200. parts, methyl glycolate, 7.5 parts water, and 1.7 parts phosphoric acid was heated in a closed vessel with agitation to C. and f or l5 ⁇ minutes at 12S-135 C., and then cooled to room temperature rapidly.l The solution obtained was diluted with 2 00 parts of ethanol and water (4:1 ⁇ byfvolume) and.v sufticient ammonia t0 neutralize the phosphoric.
- niumg .adipateffandihexamethylene .adiamrnonium .fsebacate 37.
- This solution was heated to .'FifG-lfonilzminutes with 10 parts of paraformaldehyde and 56 parts of methylhydroxy acetate.
- the N-carbomet-hoxy methoxymethyl polyamide may.. be ..preipita-pecl ⁇ by pouring the solution into aqueous sodium hydroxide.
- the water soluble potassium salt may be prepared by the procedure of Example I.
- ammonium radical and monovalent hydrocarbon radicals containing from 1 to 7 carbon atoms.
- Shrinkproofed wool as set forth in claim 9 in which the polyamide derivative contains recurring groups of the formula is in the form of a salt with a fatty acid.
- Shrinkproofed wool of substantially normal hand carrying an insolubilized deposit of water-soluble polyamide derivative of a synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, in an amount of from about 2.5 to 10% by weight on the wool insufficient to modify the normal hand of the wool substantially but sufficient to give shrinkproong, in which the Water soluble polyamide derivative contains as an integral part of the polyamide chain recurring groups of formula which recurring groups are separated by an average number of carbon atoms of at least 2, and in which X is selected from the group consisting of oxygen, sulphur, nitrogen, and phosphorus and R7 is an organic radical containing an aliphatic carbon atom attached to X, said recurring groups constituting at least 10% of the amide groups in the polyamide chain.
- Shrinkproofed wool of substantially normal hand carrying an insolubilized deposit of a water-soluble polyamide derivative of a synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, in an amount of from about 2.5 to 10% by Weight on the wool insucient to modify the normal hand of the Wool substantially but sufficient to give shrinkproong, in which the polyamide is selected from the group consisting of a polymethylene amide of a polymethylene dicarboxylic acid, a poly-e-amino acid and interpolymers of the aforesaid specific polyamides.
- Shrinkproofed wool of substantially normal hand carrying an insolubilized deposit of a water-soluble polyamide derivative of a synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, in an amount of from about 2.5 to 10% by weight on the wool insuicient to modify the normal hand of the Wool substantially but sufcient to give shrinkprooiing, in which the polyamide is a polyepsilon-amino caproic acid.
- the method of shrinkproong wool While retaining substantially normal hand by impregnating wool from an aqueous solution with from about 2.5 to 10% by weight on the Wool of a water soluble polyamide derivative of a polyamide which contains hydrogen-bearing amide nitrogen atoms of intrinsic viscosity above 0.4, said deposit being insuicient to modify the normal hand of the wool but sul'lcient to give shrinkproong and curing by heating the product at a temperature below that of substantial injury to wool or polyamide derivative, in which the polyamide is a polymethylene amide of a polymethylene dicarboxylic acid and the Water soluble polyamide derivative is an acid salt of a disubstituted -N-alkoxy methyl polyamide the polyamide being a synthetic polyamide having carbonamide groups as an integral part of the main polymer chain, the method including drying the impregnated wool by Vheating at a temperature not exceeding 100 C. before the curing step, and clziiingcat a temperature between about 100 C
- R is an alkylene and R1 and R2 are saturated aliphatic groups of less than six carbon atoms.
- nitrogen and phosphorus and 'Rv 1s an organic radical is the residue of aminoalcohol sufficiently basic to react with formic acid the said recurring groups being separated by an average number of carbon atoms of at least 2.
- the shrinkproofed Wool of substantially normal hand carrying an insolubilized deposit of a water-soluble polyamide derivative of a synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, in an amount of from about 2.5 to 10% by weight on the wool insuicient to modify the normal hand of the wool substantially but sufficient to give shrinkproofing, in which the polyamide is a polymethylene amide of a polymethylene dicarboxylic acid and the water soluble polyamide derivative is an acid salt of a disubstituted -N-alkoxy methyl polyamide the polyamide being a synthetic polyamide having carbon amide groups as an integral part of the main polymer chain.
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Description
United States Patenti() SHR'INKPROOFD iWOOL? AND METHODSFOR 4iPRODUCING SAME llljviiigfll.fHanimer,lelleville, land John BRust, fgEast Hanover, N. J., ssiguorsfbyfedihre'ct Jand#inesneassignments, iofone-'half-o.MontclaireResearchorporaton, a @corporation olil New Jersey, 1 and zone-halfV fto Ellis FosterfGompanyf/acorporation of- NewfJersey Nolnr'awing, Apblicfiau.Mafhimliws,
the wool be-coinmerleiallyfeasible,e.,l that'thetiine -fofftreatment'bereasbnablyeshrt, etc.
yAmong lthe-objects` of =the present 'invention is "lthe ,1 production offshrinknroofed LWool'ofsubstarrt-ially -nrnial -handfby'fcommerciallyfeasible-fprocesses.
Other objects include the production of fsuh @Shrink- :proofed wool which =retais :itsrimproved characteristics resistant to Ilaun'derng, fdryicleanng etc.
Still further objects and advantages of the present invention will appear frorntlienore detailed description @set:forthfbelowfit-being understoodthat 'sueh'tmie detiledadscriptin fis ,.'gven k"by cvWayl of 'r-fillutration @and r,explanation nly,-"a`d notfibyyvayfof'v` `nitati`6n,`lsi'ce `vvarious vvchanges thcreinjsniay Abe 'in'iade "by1th's`e' skilled infitheart withoutdepaif'ting-iifromtlie scp'efanid' spiritfof ther; present 'invention flnaceordnce fyi/ith"tlleJPrEeSentinventionV Wool while `retaining lits :substantially @normal h'ndfis ffgiven ishrfinkfproof yproperties iby y:the utiliiation fof water soluble nylon lderivatives applid yJby y-enimercially ffed'sible processes -in simple itreatrents requiring yrelatively"",short perods o'f timeffor'such'ltreatments vAppli'altionfb the --water soluble inyl'nhbr polyzmidef'derivtives isi'a'ried out IAdesiIably-fin aquousfsolution 1followed by 'simple treatment tolcnvt-the twaterisoliible derivativento ICC i12 -fthe;water"soluble polyamide derivative, removing Zexcess padf liquor,- and curing 'thev impregnated wool :usually with aV dryingk S'tepvpreeedingl curing. The-amountsfof iWater y' solb'lezpolyami'dederivative 'vinthe-*aqueous fsolution' lmay 5 Ivary and =Willfdepend-in-part To'n 'fthe-solubilityof 'the polyamide derivative. Aqueous Y solutions f #l to :25% fby Weight of polyamide, de'rivativesmayfbe'used. @Since A'it is necessary to use-fbnly very-fsmall'amountsorpoly- `amide derivative to-obtain fshfrinkafg'efeontrol, rythefpadfding fbathsmay bedilute cont-aiding@fr-exampledrm i12 to `fl0%*by AvWei-ghi :of -theshrinkproohgffagent, "With baths l eotainirg2i3 to 3,.-5 by Weight desirablyy employed. The impregnating step v may 'be-=0f Vfthe usual :padding bath technique, lftheywool being-linirnersed'dnltheqpad liquor, and excess pad liquor removedfasfbyesqueefzerolls. f The :padding operation-may ;be fearried out at 'ffany stemperature which i causeswno undesred changep-in the vwater #soluble :polyamide derivative at ,thisdstage. Theamount of shrinkproong agentedepositedon f or in vthej bers f or @the sealesfthereof :should not'jbefsuicientftovinte-rferewith theA desired#handifofethe wo'ol. -Sinee-small amounts of kshrinkprooiltxgfagents --Lare -all`--that are fneeded, 'the 'end gsought vTis teasily 'accomplished In gener'stl,` they'weight increase in-thewoolwillnotexceedfaboutflo, although The f padded" woo1- may fthen rbe-ffsubjected to drying*v for @removal of fmoisture vprior; to euring whemthe flatteryY is 30 f usedyor for insolubilizing -when-euringis not used. Any `.drying procedure may heemployedprovidedtemperatures :do not` reach-:those Wherefthefpolyamide derivativeds fun- -desirablyfvaected. 4 Drying vwillusuallybe` at -vtemperatures=below3lf00 (Af-ranges of 70-80? -C.beinguseful, fand -if=desiredvaeuumarnaybelemployed. i L
Curingf Iin :any -desiredj--waymay be usedffbut usually will vinvolve aheat'treatfment #at elevated {temperature sufeient to insolubilize -the.polyamide-derivative. Such temperatures Willm'suallyrexeeedl O0 1 and may desirably be in the rangeof from 120? to 150 C. Many of the polyamide derivatives cnbe subjected to much higher temperatures 'asfforfexample 250 'tof-285 C., but such elevated temperatures are not `usually desirable with treated wool products. However'it`=shou ld bemnoted that the curing 'frelrn'ent'i'irelatively shotj-'forixample l5 minutes yat 130 C. is generally sucient, while shorter treatments suice at higher temperatures, forme'xample kl0 minutes at 135 C.,afe'\v"1ninits"'at1-l40'`-C., ie't'c.,""so that exposures at theahighertemperatresfor a fraction of the stated time pieiiods `Will sulcg, but temperatures and times df--the-ordr giveninther examples below are more desirable.
insured by the use of N-disubstituted aminoalcohols in which the substituent groups on the nitrogen are saturated aliphatic groups of less than six carbon atoms as for example alkyl groups below hexane, including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, trimethyl methyl, and the various pentyl (amyl) groups, and such alkyl groups carrying substituent groups like hydroxy, which do not interfere with the desired water solubility. The stated water soluble salts are new entities in the art of great value since they may be used in solution in water or in aqueous emulsions. The salts per se may be recovered from the reaction medium in which they are produced by precipitation therefrom by means of an organic liquid capable of precipitating such salt from the solution in the form of a water soluble salt. The salt should not be neutralized as by addition of inorganic bases such as the caustic alkalis or ammonia, since such neutralization will destroy the water solubility of the modified polyamide.
The formation of the water soluble salt may take place by reaction of the polyamide in solution, as in formic acid, with formaldehyde and the aminoalcohol. The formaldehyde may first be reacted with the polyamide followed by reaction with the aminoalcohol, or these reactants namely polyamide, formaldehyde and aminoalcohol may be reacted simultaneously in the presence of the acid, followed by precipitation of the salt by a convenient organic solvent, and the precipitated polymer is then readily soluble in water.
The following mechanism is believed to illustrate the formation of the water soluble salt, but is offered by way of explanation only without limitation thereto, since regardless of the explanation, water soluble salts are formed. The reactions probably involve the initial reaction between the formaldehyde and the amide nitrogen to form a methylol compound. The methylol group then condenses with the hydroxy group of the N-disubstituted aminoalcohol to form an ether link. When carried out in the presence of the acid, a salt of the alkvlated aminegroup with such acid is formed. Upon precipitation with the organic solvent, this acid salt is deposited and is soluble in water. Assuming formic acid as the acid ernployed, the reactions may be formulated as follows:
-o=o HCHO :0
NH -NCHQOH /Rl CFO /R1 HO-R-N -N-CHQORN R2 Rz which forms the formic acid salt C=o H R, i
l o -N-CHQORN u R HC-o The salt of the N-alkylated amine probably forms prior to etheriticaton. In these formulas R is an alkvlene while R1 and R, are the N-disubstitnent groups. While the illustrated mechanism is believed to be correct, it is not intended as limiting.
The polyamide employed may be any synthetic linear polyamide bearing recurring carbonamide groups as an integral part of the main polymer chain. The said recurring groups generally are separated by an average number of carbon atoms of at least 2. The number of such recurring groups which are modified and converted in the N-alkoxv methyl derivatives will vary with the proportions of the reactants used, but should be suii'icient to yield water solubility of the salt ultimately prepared therefrom. For this purpose. generally. the recurring groups will be at least of the amide groups in the main polymer chain. Extent of conversion of NH groups in the polyamides to N-alkoxy methyl groups is dependent on the anhydrous condition of the solvent (formic acid) as well as the proportions of reactants used. Thus greater conversion is obtained with 100% formic acid than with 90% formic.
The polyamide employed may be of various types, for example. a polymethylene amide of a polymethylene dicarboxylic acid, or a poly omega-amino acid, or copolymers of these polyamides just mentioned, etc. Exemplary polyamides are polyhexamethylene adipamide, polyhexarnethylene sebacamide, or polymers from epsiloni aminocaproic acid, including poly-epsilon-arninocaproic acid derived from epsilon caprolactam, copolymers such as that from ethylene diammonium sebacate and epsiloncaprolactam, etc. Generally, the molecular weight of the polymers should be rather high, that is, those which have an intrinsic viscosity above 0.4.
As to the formaldehyde reactant, any formaldehydeyielding material may be employed. Paraform is conveniently employed. aqueous formaldehyde may be used. The amount of formaldehyde is desirably from 0.5 to 2.0 parts to one part of polyamide, dependent on the extent of reaction desired.
The N-disubstituted aminoalcohol should be one capable of neutralizing formic acid. lts general characteristics have been indicated above. As exemplary of such aminoalcohols there may be mentioned alkylolamines containing tertiary nitrogen, the alkylene group having for example from l to 4 and higher C chains. For example there may be mentioned dimethylaminoethanol, diethyl aminoethanol, methyl diethanol-amine, dimethyl isopropanolamine, triethanolamine, similar butanolamines, etc., and related compounds where the two substituents on the nitrogen may form a ring as in the morpholines such as hydroxyethyl morpholine. Certain disubstituted aminoalcohols such as phenyl diethanolamine, have a pH of about 7 (aqueous solution) and consequently are so weakly basic that they do not react sufficiently with formic acid. Therefore the nylon derivatives produced with such amines are either waterinsoluble or only very slightly water-soluble. Other amines in this category are ethyl phenyl ethanolaminc and di-2-ethyl hexyl ethanolamine. In general the molar ratio of aminoalcohol to formaldehyde will be equi-molar but may vary as from 3:1 to 1:2.
Formic acid has been particularly referred to as the reaction solvent. Other organic acids which are solvents for polyamides may be used. Carboxylic acids such as formic, acetic, hydroxyacetic, and chloracetic, may be mentioned. Formic acid is desirably employed; and may be used in any concentration, such as 70% to 100%, in which it is a solvent for the polyamide used. Commercially available formic acid may be employed conveniently.
The temperature of reaction may be any temperature at which the stated reaction takes place, for example above 30 C., but should be below that at which undesired degradation of the polyamide takes place.
The organic liquid solvent employed for precipitation of the water-soluble salt may be of any convenient solvent which gives the precipitated polymer. Acetone may be used as well as other ketones such as methyl ethyl ketone, diethyl ketone, etc.
The following examples illustrate the invention, parts being by weight unless otherwise indicated.
EXAMPLE A 10 parts of a poly e-amino caproic acid which has an intrinsic viscosity in meta-cresol of 0.79 was dissolved in 87 parts of 90% formic acid at 60-70 C. in a reaction iiask fitted with a thermometer, stirrer and air condenser. When dissolution had occurred the solution was cooled to 30 C. by external cooling. A solution of l0 parts of paraform in 29.3 parts of diethylamino ethanol was prepared by heating the mixture until solution of the paraform was effected. The paraformdiethylaminoethanol solution was cooled to 30 C. and added dropwise to the polyamide solution with rapid stirring. During the course of the addition, dense white fumes were evolved; white salt-like particles were formed in the reaction mixture; and the temperature rose rapidly. The reaction ternperature was maintained at 35-40" C. by means of a cold water bath until the dropwise addition was completed. Stirring was maintained and the reaction mixture which still contained salt-like particles, was heated to 60 C. and the reaction continued at that temperature until complete solution had occurred. The reaction was then continued at 60 C. for an additional 1/2 hour and then cooled to yield a pink uid solution at room temperature.
45 parts of the above reaction product was treated with 158 parts of acetone with vigorous stirring to yield a faintly cloudy solution. The addition of 515 parts more acetone with `constant stirring, caused the precipitation of a fibrous precipitate, The mixture was allowed to stand for 10 minutes to allow the precipitate to harden and then filtered. The filtered precipitate, still wet with acetone and equivalent to 3.3 parts ofpoly e-amino caproic acid, was easily soluble in 97 parts of water at room temperature. The rate of solution in water was appreciably faster at 5060I C. The final solution obtained had a concentration of approximately 3.3% based on the poly e-amino caproic acid.
EXAMPLE B parts of a polyhexamethylene adipamide, prepared from hexamethylene diammonium adipate, which had an intrinsic viscosity in meta-cresol of 0.47 was reacted with 87 parts of 90% formic acid, l0 parts paraform and 29.3 parts of diethylaminoethanol in the same manner as described in Example A. The reaction product was a deep red solution.
45 parts of the above solution was poured into 238 parts of acetone with vigorous stirring. A fibrous precinitate was formed which was filtered and washed with 39.5 parts of acetone. The acetone-wet precipitate, which contained the equivalent of 3.3 parts of polyhexamethylene adipamide, was dissolved in 95 parts of water at 40-50 C. with stirring. The aqueous solution was colored red.
EXAMPLE C 10 parts of a commercial sample of polyhexamethylene adipamide which had an intrinsic viscosity in metacresol of 0.96 was reacted in the same fashion as described in Example A except that 137 parts of 90% formic acid was used instead of 87 parts.
57.1 parts of the final cooled reaction mixture (equivalent to 3.3 parts of the polyhexamethylene adipamide) was poured into 182 parts of acetone. A clear solution resulted. The addition of 365 parts of acetone to this solution caused the precipitation of a fibrous precipitate which was easily soluble in 97 parts of water at 60-70" C. to yield a 3.1% solution based on the original polymer.
EXAMPLE D solution.
EXAMPLE E A solution of l0 parts of a commercial sample of a polyhexamethylene adipamide (intrinsic viscosity in metaacresol of 0.96) was prepared in 137 parts of 90% formic acid at 60-65 C. A solution of 10 parts of paraform in 35 parts of triethanolamine was reacted with the nylon-formic acid solution employing the general procedure outlined in Example A. The reaction product was fluid at room temperature. Treatment of a portion of the above-mentioned reaction product with a large volume of acetone resulted in the separation of a fine granular precipitate which was easily soluble in water at 50-60" C.
EXAMPLE F A solution of 10 parts of a polyamide made from e-caprolactam (intrinsic viscosity in meta-cresci of 0.91) in 87 parts of 90% formic acid was reacted with 10 parts of paraformaldehyde and 30 parts of methyl diethanolamine employing the general procedure described in Example A. The precipitated product obtained `by` treating a portion of the reaction mixture with a large volume of acetone was easily soluble in water.
EXAMPLE G A reaction mixture was prepared from l0 parts of a polyamide made from e-caprolactam (intrinsic viscosity 0.91), 87 parts of 90% formie acid, 10 parts of paraformaldehyde, and 26 parts of dimethyl isopro` panolarnine by the general procedure described in Example A. The precipitated product (with acetone) was partially soluble in Water at 5060 C.
` EXAMPLE H Example G was repeated except that the poly e-amino caproic acid used had an intrinsic viscosity of 0-.79 and 33 parts of hydroxyethyl morpholine instead of the dimethyl isopropanolamine. The precipitated product (with acetone) was easily soluble in water at 50-60" C.
Four lengths of 8" each were marked on a piece of wool annel measuring l0 x v10 in size; two in the direction of the warp and two in the direction of the ll. From these measurements the area in square inches was calculated. The sample was then immersed in the 3.3% aqueous solution of the poly e-amino caproic acid di ethylaminoethanol derivative prepared in Example A and the excess pad liquor was removed by passing the fabric through squeeze rollers. The weight of the wool sample was noted before and after padding and from the weight increase the amount of polyamide applied to the fabric was calculated to be 3.4%. The sample was dried at 75-80 C. and then cured at 130 C. for l5 minutes.
The treated sample along with a similarly measured untreated wool sample was then immersed in a 1% soap solution (l liter) at 25 C. for a period of 2 hours. The samples were then rinsed, dried and remeasured and the relaxation shrinkage calculated. The samples were then laundered for 3 hours in a mechanical washing machine containing 13 liters of water at 60 C. and 35 grams of soap. The wool samples were again rinsed, dried, and remeasured and total shrinkage calculated. The area shrinkage obtained for the samples was as follows.
The finished wool sample had a dry, normal hand and good draping characteristics.
Example 2 A sample of wool, measured as described in Example 1, was immersed in the 3.3% aqueous solution of the poly hexamethylene adipamide diethylaminoethanol derivative prepared in Example B. After the excess pad liquor was squeezed out, the Weight increase of the wool indicated that the amount of polyamide applied was 3.3%. The sample was dried at 75-80 C. and cured for 15 minutes at 130 C.
The treated sample along with an untreated measured Wool sample was subjected to relaxation and laundering as described in Example l, area measurements being taken after each process. The results obtained were as follows.
Percent Relaxation Total Laundering Sample Polyamide Shrinkage, shrinkage, Shrlnkage,
on Fabric Percent Percent Percent Treated 3. 3 5.0 9. 4 4. 4 Untreated 0.0 11.0 41. l 30. 4
The finished wool sample had a dry, normal hand and good draping characteristics.
Example 3 The treated sample together with untreated sample was relaxedand"r laundered in the mannen described in. Example 1 exceptthat. the laundering.v was for 2- hours. TheA shrinkage; dataobtained wasv asfollowsz.
The finished. wool sample has a dry, normal hand and good draping` characteristics.
Example 4 An` aqueous solution of a commercial poly hexa- Inethylene adipamideftriethanolamine derivative was prepared in the manner. described in. Example E. The concentration of'. the solution was 3.3%, basedon the weight of the polyamide.r A sample of wool, measured in the usual. fashion, was immersed in the solution. The weight increase of the wool sample, after removing` the excess pad liquor,` indicated that 3.3% of the resin had been applied.V The sample was dried at 75 C.. and cured at 130 C. for 15y minutes.v
The cured sample together with, an untreated. Wool sample, was, relaxed and laundered in theA manner de.- scribed. in` Example 1 except that the4 laundering was for 2hours. The shrinkage data obtained waslas, follows:
The finished wool sample had a dry,y normal hand and good draping characteristics.
Example 5 Anaqueous solution of a poly e-arnino caproic acidmethyl diethanolamine derivative was prepared' in the manner described in Example F. The concentration of the solution was 3.3% basedi on the weight of the polyamide. A measured sample of wool was treated with the solution in the usual fashion and subsequent to the removal of excess'pad liquor, the sample was dried and cured under the same conditions as described in Example 4. The weight pick-up of the wool sample after padding indicated that 3.4% of` the polyamide had been applied to the wool.
After the relaxation and laundering processes were carried out as` described in4 Example 4, the shrinkage data was as follows:
- Percent .Relaxation Total Laundering Sample Polyamide Shrinkage, shrinkage, shrinkage,
on Fabric 1 Percent Percentl t Percent Treated 3.4 4.9 6.4 4 1.5 Untreatod 0.0 10.1 39. 2 29. l
The finished wool sample had a dry, normal` hand and good draping characteristics.
Example 6 Percent i Relaxatior Total l l laundering Sample `Polyamide shrinkage, Shrnkage, shrinkage,
on Fabric Percent Percent 1 Percentv Treated 3.3 7.9 10.3v 21,4 Untreated 0.o 11.0 41.4 30.4
The; iinishedwool. sample had a dry, normalV hand and good draping,v characteristics.
In the. Water solublel polyamide derivatives of the type speciiically emphasizedfabove,` the modied polyamide or nylon residue insuch water soluble salts, is probably the cation as the formulations given above indicate. Such derivatives are completely different in nature from water soluble polyamide derivatives where the nylon residue is the anion. Whil'e the cation type are particularly valuable for shrinkprooiing wool, thev anion type though quite diiferent may also be employed in shrinkproofing operations and the following material is concerned with such anion types'. They will for the most part fall into two general groups.
One such group is a water soluble polyamide derivative having a group or groups in the polymer chain,l of the formula in which R5 is a` saturated aliphatic divalent hydrocarbon radical', such as alkylene, containing from 1 to 17 carbon atoms and Re is a cation such as hydrogen, metals, the ammonium radical, or monovalent hydrocarbon radicals containing from 1, to 7 carbon atoms; The water soluble salts. with for example alkali metals, NH4, etc., or with complex organic ammonium groups such as quaternary trimethyl benzyl' ammonium hydroxide may be used. They are produced by reacting a synthetic linear polyamide. having a hydrogen bearing amide group, in the presence of an oxygen containing acid catalyst, with formaldehyde and a hydroxy carboxylic acid or an ester of a hydroxy carboxylic acid or mixtures of such acids and esters. Such reaction products may be converted into water-soluble salts where the` nylon residue is in the anion.
The synthetic linear polyamides used may be those set forth above for theA production of the cation type water soluble derivatives.
The oxygen containing acid catalysts include fatty acids and substituted fatty acids such as formic, acetic, chloroacet-ic, trimethyl acetic, aromatic acids such as benzoic, sulfonic acids such as p-toluene sulfonic, dibasic acids such as oxalic, maleic, etc., and even inorganic acids such as phosphoric. Such acid catalyst should have an ionization constant of at least 9.6 106.
While formaldehydel has been referred to, it is generally used in the` form of paraformaldehyde, but the same considerations apply here, as to formaldehyde and the ratio of formaldehyde to synthetic linear polyamide as given above for the cation type water soluble salts.
The hydroxy carboxylic acids are generally the monohydroxy aliphatic acids of for example 2 to 17 carbon atom saturated chains, such as glycolic, lactic, 10-hydroxydecanoic, 12 hydroxy stearic, etc., although polyhydroxy acids of this type, such as tartaric, etc., may be used. The esters are those of the stated acids with alkanols and alkoxy alkanels such as methyl, ethyl, butyl and methoxymethyl alcohols, as welly as esters of cycloaliphatic alcohols such as cyclohexyl alcohol, and esters of aralkyl alcohols such as benzyl alcohol. lt will be noted that generally the hydroxyl group is attachedA to an aliphatic carbon. The amounts of acid orester will usually be determined on the formaldehyde, equi-molar ratios being preferred, but molar ratios of 1:2 to 2:1 may be used.
The reactions are carried out at any temperature from room (20 C.) to 15.0 C. and higher, but of course belowy temperatures undesirably affectingr the polyamide.
The following examples illustrate these water soluble derivatives7 parts being by` Weight unless otherwise indicated.
EXAMPLE J' A. mixture of 50 parts polyhexamethylene adipamide (intrinsic viscosity above 0.4), 5.0 parts paraformaldehyde, 200. parts, methyl glycolate, 7.5 parts water, and 1.7 parts phosphoric acid was heated in a closed vessel with agitation to C. and f or l5` minutes at 12S-135 C., and then cooled to room temperature rapidly.l The solution obtained was diluted with 2 00 parts of ethanol and water (4:1 `byfvolume) and.v sufticient ammonia t0 neutralize the phosphoric. acid, and iiltered., To the clear filtrate water (3000 parts) `was `added to precipitate the N-carbomethoxy methyl polyhexamethylene adipamide algdi ztlialatte'n washed: with;` watega 'Ih-isproduet; mayL be. converted into. the.: waterlisqluble potassium salt first dissolYngtin-.methanol.atfabona 60?- G; (5.0.ipartsfad1panude to; lOO/partstmethanolt); Botassium. hydroxide.: ("7v parts )l was added and the. solutionaevaporated under reduced pressure to.` dryness.. 'Ehe tesultiu}=.1salt,y is; readily,v .soluble in water.
' EXAMPLE K 175 parts of polyhexamethylener adipamide was dissolved in 700 parts .of a-1I1i2tt11. 1=eofg formi acid and acetic anhydride (1.5:1) at 65 C. A suspension of 215 parts paraformaldahydeiiaaatisfmatiiyi smaltata.
a sont;
ing a.y trage of walsia e add wiwi aaa@ botfiii.
Of. ihelpoii .ivm Stili" Oft V. having the d'iii. t follows. Thepolymereha theformula where X is oxygen or sulphur preferably but may be nitrogen. x ahaspitqwa. and.A Kals. organisa.
. a mais Zerewitinoi palyamide lowing. example.; siiiiicignil illusiiaied. these;
- v parts'fof. .anginterpelymep (intninsi-viseosify-fof 0.8)'
wasdissolved in,6.0f.par;ts -formieacid :(sp. gr.'V 1:20)-,V The intel-polymerwas derivedwfrom: heXa-methylene ldiammo.-
niumg .adipateffandihexamethylene .adiamrnonium .fsebacate (37.). This solution was heated to .'FifG-lfonilzminutes with 10 parts of paraformaldehyde and 56 parts of methylhydroxy acetate. The N-carbomet-hoxy methoxymethyl polyamide may.. be ..preipita-pecl` by pouring the solution into aqueous sodium hydroxide. The water soluble potassium salt may be prepared by the procedure of Example I.
@disal- Any of these anion type water soluble polyamide kdeferivatves may be used in shrinkproofng wool by the procedures set forth abve in Examples 1-6 for the cation type. The same considerations as to solution concentration, weight of deposit on wool, temperature of treatment, etc., apply, asi-well as the considerations for drying and curing the impregnated wool. However the Catioiif was derivata/estuve@ :batte.rffshrin.kproofftds-Prodi --S Havingthus.` set-v .forth our.- invention, We; clairri:
substantially normalhand by.'A impregnatin'g wool from an aqueousxsolution with fromz'abo'utsZj to:` 101%` by weight on. 'the-Wool of# aV wa'ter vsoluble polyamide derivative I of a polyamide. which'. contains. hydrogen-bearing amide nitrogen;4 atoms of.A viscosityabovef 0:4; 4said deposit., being insuiieient; to modify the normal hand.
of: the wool;r butj sufficient; to.' give. shrinlcproofiiig7 and4 curing-hy.vv heatingythe'.-pijoduct. at'f atern'perature` below' thatofsubstantiaglinjury! to .wool/or polyamide derivative; in: whichathe-.water soluble-i polyamide derivative is'tan' aeidi'- salt; of; azdisubs'tituted' Naalkoxy methyl polyamide the. polyamide: being. at synthetic. polyamideA havin g1 cari.l
bonamide groups as an integral part of the? main polymer chain.
2. The method of shrinkproong wool While retaining substantially normal handlby impregnating wool from an aqiiousysolutioa with `fiom; about. v 2.25. to- 19% by.r weight- Oa the Wal-Ofi 'awaiar salublefpolyamidfe. derivative. of
a 29Min .Q which: con ms; hydrogenfbearing: amide. nitraat@ atomen@ intrisa visosit d@ .Osit being .inSiiiiaisnt. t0.-
. .he normal hand e vvcfzolv but; sulpcvientwto. give Shrinkproong and curing by heating the prodygtpatfaiternperaturef belowl that 0f -Siibsiaiifiai iniuryftofwool. o
polyamide derivative, i111: th
i` with,1 formio. .acida their. saidt4 recurrin'g groups being' separated-byzan average:numberoiircarb'onatoms' of aty leastl2: 3,.; The-.method iofficlairmZ Iinzawliieh.t Ri isva'n: allgyleneand Ri and Rz are saturated aliphatieigifoupsv'iof lessi' thanis-.slxcaizbon atoms.-
" is maremma-agen .with aifnytaaiai 5.- Themethod/:of:shninkproongrwool while.'retaining-fA --on the wool of a water soluble.;polyamider'derivativef of la. polyamidezfwhc-hfi.contains hydrogenbeaningnamide nitrogen? atomsyofaintrinsieaviscosityf: above? 0.4;: said't deposit being insufficient to modify the normalhandA of the Wool but sufficient to give shrinkproong and curing by heating the. product at a temperature below that of substantial injuryfto wool orpolyamide derivative, in which the impregnated wool is subjected to a drying operation by heating at a temperature not exceeding C. before the curing step, and the curing step is carried` tigt) oa; a temperature above 100 C. but below about 6. The method of shrinkproong wool while retaining substantially normal hand by mpregnating Wool from an aqueous solution with from about 2.5 to 10% byA weight .i onf: the Woolz: of a" f Water.' `slub11er-polyamide*derivative of arpolyamide'fwhich :contains hydrogen-hearing amide' nitrogenI atomsxfofffintrinsic viscosityabove' 014" said' deposit E bemg'fs msuci'enb: to @modify th no'rrnalt i' hand of E the-:wool :i butt` sufficient 'l tofl g-iye shrinkproong, and* euring by heating theoproduct'fat' al'temperatiur'e b eloyv thatoti Substantialxinjury to.woo1 oripolyarrid vative;
in which the Water soluble palyamide deriva-t e-contairis" in the polymer chain a .group having the formula .(l3=0 -N-oienfo-Rsooom in which R5 is a saturatedla i radicalrfcontainingfromlilto! 1172I carb'onll atom andi Refis1 a cation :selected-fromfthe group "consistingofy hydrogen,
,abave 0.4:.. Qaida..
f mixamidet derivative? Contains.' recurriing-.
metals, the ammonium radical and monovalent hydrocarbon radicals containing from 1 to 7 carbon atoms.
7. The method of shrinkprooiing Wool while retaining substantially normal hand by impregnating Wool from an aqueous solution with from about 2.5 to by weight on the wool of a Water soluble polyamide derivative of a polyamide which contains hydrogen-bearing amide nitrogen atoms of intrinsic viscosity above 0.4, said deposit being insuicient to modify the normal hand of the wool but suicient to give shrinkproong and curing by heating the product at a temperature below that of substantial injury to Wool or polyamide derivative, in which the water soluble polyamide derivative contains as an integral part of the polyamide chain recurring groups ofv formula -N-CHzXRr which recurring groups are separated by an average number of carbon atoms of at least 2, and in which X is polyamide derivative of a synthetic polyamide which contains hydrogen-bearing amide nitrogen atoms and .of intrinsic viscosity above 0.4 which derivative contains 1n the polymer chain a group having the formula in which R3 is a saturated aliphatic divalent hydrocarbon radical containing from 1 to 17 carbon atoms and Re is a cation selected from the group consisting of hydrogen, metals, the ammonium radical and monovalent hydrocarbon radicals containing from 1 to 7 carbon atoms, in an amount of from about 2.5 to 10% vby weight on the `voel insuflicient to produce a continuous protective coating on the Wool but suicient to produce shrinkproong, and drying the impregnated Wool.
9. Shrinkproofed wool of substantially normal hand carrying an insolubilized deposit vof a water-soluble polyamide derivative of a synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, in an amount of from about 2.5 to 10% by Weight on the Wool insuicient to modify the normal hand of the Wool substantially but suicient to give shrinkproong in which the water-soluble polyamide derivative is an acid salt of a disubstituted -N-allroxy methyl polyamide the polyamide being a synthetic polyamide having carbonamide groups as an integral part of the main polymer chain.
10. Shrinkproofed wool as set forth in claim 9 in which the polyamide derivative contains recurring groups of the formula is in the form of a salt with a fatty acid.
13. Shrinkproofed wool of substantially normal hand carrying an linsolubilized deposit of a Water-soluble polyamide derivative of a synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, in an amount of from about 2.5 to 10% by Weight on the wool insufficient to modify the normal hand of the wool substantially but sutcient to give shrinkproong, in which the Water soluble polyamide derivative contains in the polymer chain a group having the formula in which Rs is a saturated aliphatic divalent hydrocarbon radical containing from l to 17 carbon atoms and Rs is a cation selected from the group consisting of hydrogen, metals, the ammonium radical and monovalent hydrocarbon radicals containing from 1 to 7 carbon atoms.
14. Shrinkproofed wool of substantially normal hand carrying an insolubilized deposit of water-soluble polyamide derivative of a synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, in an amount of from about 2.5 to 10% by weight on the wool insufficient to modify the normal hand of the wool substantially but sufficient to give shrinkproong, in which the Water soluble polyamide derivative contains as an integral part of the polyamide chain recurring groups of formula which recurring groups are separated by an average number of carbon atoms of at least 2, and in which X is selected from the group consisting of oxygen, sulphur, nitrogen, and phosphorus and R7 is an organic radical containing an aliphatic carbon atom attached to X, said recurring groups constituting at least 10% of the amide groups in the polyamide chain.
15. Shrinkproofed wool of substantially normal hand carrying an insolubilized deposit of a water-soluble polyamide derivative of a synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, in an amount of from about 2.5 to 10% by Weight on the wool insucient to modify the normal hand of the Wool substantially but sufficient to give shrinkproong, in which the polyamide is selected from the group consisting of a polymethylene amide of a polymethylene dicarboxylic acid, a poly-e-amino acid and interpolymers of the aforesaid specific polyamides.
16. Shrinkproofed wool of substantially normal hand carrying an insolubilized deposit of a water-soluble polyamide derivative of a synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, in an amount of from about 2.5 to 10% by weight on the wool insuicient to modify the normal hand of the Wool substantially but sufcient to give shrinkprooiing, in which the polyamide is a polyepsilon-amino caproic acid.
17. The method of shrinkprooting wool while retaining substantially normal hand by impregnating Wool from an aqueous solution with from about 2.5 to 10% by weight on the wool of a Water soluble polyamide derivative of a polyamide which contains hydrogen-bearing amide nitrogen atoms of intrinsic viscosity above 0.4, said deposit being insuicient to modify the normal hand of the Wool but suflcient to give shrinkproong and curing by heating the product at a temperature below that of substantial injury to Wool or polyamide derivative, in which the polyamide derivative contains recurring groups of the formula is the residue of aminoalcohol sufciently basic to react with formic acid the said recurring groups being sepa- 13 ratedv by an average number of carbon atoms of at least 2, and in which the Nin the /Rl I OR-N is in the form of a salt with a fatty acid.
l8. The method of shrinkproong wool While retaining substantially normal hand by impregnating wool from an aqueous solution with from about 2.5 to 10% by weight on the Wool of a water soluble polyamide derivative of a polyamide which contains hydrogen-bearing amide nitrogen atoms of intrinsic viscosity above 0.4, said deposit being insuicient to modify the normal hand of the wool but sul'lcient to give shrinkproong and curing by heating the product at a temperature below that of substantial injury to wool or polyamide derivative, in which the polyamide is a polymethylene amide of a polymethylene dicarboxylic acid and the Water soluble polyamide derivative is an acid salt of a disubstituted -N-alkoxy methyl polyamide the polyamide being a synthetic polyamide having carbonamide groups as an integral part of the main polymer chain, the method including drying the impregnated wool by Vheating at a temperature not exceeding 100 C. before the curing step, and clziiingcat a temperature between about 100 C. and
19. The method of claim 18 in which the polyamide derivative contains recurring groups of the formula -C=o R1 -IlT-CHQ-O-R-N/ Ri where l Ri -O-R-N/ is the residue of aminoalcohol sufficiently basic to react with formic acid the said recurring groups being sepa- 'atedZby an average number of carbon atoms of at east 20. The method of claim 19 in which R is an alkylene and R1 and R2 are saturated aliphatic groups of less than six carbon atoms. v
21. The method of claim 20 in which the N in the is in the form of a salt with a fatty acid.
22. The method of shrinkprooing wool while retaining substantially normal hand by impregnating wool from an aqueous solution with from about 2.5 to 10% by weight on the wool of a water soluble polyamide derivative of a polyamide which contains hydrogen-bearing amide nitrogen atoms of intrinsic viscosity above 0.4, said deposit being insufficient to modify the normal hand of the wool but su'lcient to give shrinkproong and curing by heating the product at a temperature below that of substantial injury to wool or polyamide derivative, in which the polyamide is a polymethylene amide of a polymethylene dicarboxylic acid and the water soluble polyamide derivative is an acid salt of a disubstituted -N-alkoxy methyl polyamide, the polyamide being a synthetic polyamide having carbonamide groups as an integral part of the main polymer chain, and in which the water soluble polyamide derivative contains in the polymer chain a group having the formula in which R5 is a saturated aliphatic divalent hydrocarbon radical containing from 1 to 17 carbon atoms and Re is a cation selected from the group consisting of hydrogen, metals, the ammonium radical and monovalent hydrocarbon radicals containing from 1 to 7 carbon atoms.
23. The method of shrinkproong wool while retaining substantially normal hand by impregnating wool from an aqueous solution with from about 2.5 to by weight on the Wool of a water soluble polyamide derivative of a polyamide which contains hydrogen-bearing amide nitrogen atoms of intrinsic viscosity above* 0.4,' said deposit being insulcient to modify the normal hand of the wool but suflicient to give shrinkproong and curing by heating the product at a temperature below that of substantial injury to Wool or polyamide derivative, in which the polyamide is a polymethylene amide `of a polymethylene dicarboxylic acid and the water soluble polyamide derivative is an acid salt of a disubstituted -N-alkoxy methyl polyamide, the polyamide being a synthetic polyamide having carbonamide groups as an integral part of the main polymer chain, and in which the water soluble polyamide derivative contains as an integral part of the polyamide chain recurring groups of the formula -N-CHrXR'i which recurring groups are separated by an average num- Der of carbon atoms of at least 2, and in which X is selected from the group consisting of oxygen, sulphur,
nitrogen and phosphorus and 'Rv 1s an organic radical is the residue of aminoalcohol sufficiently basic to react with formic acid the said recurring groups being separated by an average number of carbon atoms of at least 2.
25. Shrinkproofed wool as in claim 24 in which R is an alkylene and R1 and R2 are saturated aliphatic groups of less than six carbon atoms.
26. Shrinkproofed wool as in claim 25 in which the N in the is in the form of a salt with a fatty acid.
27. The shrinkproofed Wool of substantially normal hand carrying an insolubilized deposit of a water-soluble polyamide derivative of a synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, in an amount of from about 2.5 to 10% by weight on the wool insuicient to modify the normal hand of the wool substantially but sufficient to give shrinkproofing, in which the polyamide is a polymethylene amide of a polymethylene dicarboxylic acid and the water soluble polyamide derivative is an acid salt of a disubstituted -N-alkoxy methyl polyamide the polyamide being a synthetic polyamide having carbon amide groups as an integral part of the main polymer chain.
28. Shrinkproofed wool as in claim 27 in which the polyamide derivative contains recurring groups of the formula -C=O Ri -llI-CHz-o-R-N/ where Ri -o-a-N/ is the residue of aminoalcohol suciently basic to react armena@ with for-mic ,acid the gsaid recurring groups :beingsepanv ratedbyanaverage number of carboxtatomspfat least2.
.29. Shrinlsproofed twool ,as :in;claim 28 ,in which JR is an alkylene .and 'TR1 and sRz .are r`saturated aliphatic groups o f ,less than sire carbon ratoms.
30.Sl1rinkproofed iwoolas in @claim 29 in iwhich the Ndnit'he 3l. Shrinkproofed wool of substantially normal hand carrylng an insolubilized deposit of a water-soluble poly* amide derivative of a ,synthetic polyamide containing hydrogen-bearing amide nitrogen atoms and of intrinsic viscosityaboyeiOA, in .an :amountrqf from :about 12.15 .to 10% by .weightfon the wool ,insucient to 4-modiiy the normal 2handgof ithe wool :substantially 'but suicientrto l give :shrinkproong, .iinvwhich the polyamide is a vpolymethylene amide :of ,a ,-polymethylene dicarboxylic .acid and .the awater .soluble 4apolyamide ,derivative ,is Yan acid salt of a disubstituted Nfallcoxy methyl l,polyamide the polyamide ,being -.a ,synthetic polyamide :having Icarbon amide `groups :as .an :integral part ,of :the main polymer chain Aand the ,water soluble ip olyamide derivative ,contains :in the polymer .ichain .a group :having ythe formula 'Nv-rQ-lhfa Q0 0231. in Iwhich #Rsais afsaturated aliphatic -divalent' hydrocarbon radical containing from 1 =to rx1f7earbonatomseand Re is a cation selected from the group consisting of hydrogen, metals, the ammonium radical tand monovalent hydrocarbon radicals containing from l to'7 carbon atoms.
32. Shrinkproofed wool of substantially normal hand lil) '126 carrying ian ;.insc111bil ized ,deposit .cf a watereoluble polyamide derivative of a synthetic llltamde ;.Q0utaining hydrogen-bearing amide nitrogen atoms and of intrinsic viscosity above 0.4, inan amount of from about 2.5 to 10% by weight on the Wool -insufcient to modify the normal hand of the wool substantially but suicient to give shrinkproong, in which the vpolyamide is a polymethylene amide of -a -polymethylene dicarboxylic acid and the `water soluble `polyamide derivative `is Van acid salt=of afdisu'bstituted `N-a1koxy methyl polyamide the polyamide being a synthetic `polyamide having -carbon amide groups Vas an integral part of the ymain vpolymer chain -and lthe water Y-soluble polyamide derivative contains as an integral :party-of the polyamide ,chain recurring groups fo'fformu'la TC=.,.O fille-,GHzXR which recurring groul'is areseparatedjby an average number of c arbonatoms `of atleast :2, land in [which X is Selected ffQm 3th,@ ,group consitincf'f Oxygen, .,sulphur, nitrogen and ,phosphorus and jRf/is an :organic radical containing `an aliphatic'carbon 4 atom Tattached to X said recurring groups.coustituting Vatleast *10% offtbe'amide groups in thepolyarnidechain.
'References x('ited *in 'the le of-this patent STATES yBMS-ELVIS Number -`Name Date 2,347,024 Beer` Apr. 18, 1944 2,406,958 McQueen ,n Sept. 3, 1946 2,412,993 Larchar Dec. 24, 1946 2,430,907 Cairns Nov. 18, 1947 2,443,450 Graham et al June l5, x1948 2,526,637 Cuperyg. Oct. 24, 1950
Claims (1)
1. THE METHOD OF SHRINKPROOFING WOOL WHILE RETAINING SUBSTANTIALLY NORMAL HAND BY IMPREGNATING WOOL FROM AN AQUEOUS SOLUTION WITH FROM ABOUT 2.5 TO 10% BY WEIGHT ON THE WOOL OF A WATER SOLUBLE POLYAMIDE DERIVATIVE OF A POLYAMIDE WHICH CONTAINS HYDROGEN-BEARING AMIDE NITROGEN ATOMS AND INTRINSIC VISCOSITY ABOVE 0.4, AND DEPOSIT BEING INSUFFICIENT TO MODIFY THE NORMAL HAND OF THE WOOL BUT SUFFICIENT TO GIVE SHRINKPROOFING AND CURING BY HEATING THE PRODUCT AT A TEMPERATURE BELOW THAT OF SUBSTANTIALLY INJURY TO WOOL OR POLYAMIDE DERIVATIVE, IN WHICH THE WATER SOLUBLE POLYAMIDE DERIVATIVE IS AN ACID SALT OF A DISUBSTITUTED -N-ALKOXY METHYL POLYAMIDE THE POLYAMIDE BEING A SYNTHETIC POLYAMIDE HAVING CARBONAMIDE GROUPS AS AN INTEGRAL PART OF THE MAIN POLYMER CHAIN.
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2882185A (en) * | 1956-04-13 | 1959-04-14 | Onyx Oil & Chemical Company | Water soluble basic polyamides and their alkylation products |
US2925317A (en) * | 1956-09-18 | 1960-02-16 | Joseph E Moore | Shrinkproofing of protein fibers with polyalkyleneimines |
US2953482A (en) * | 1957-07-18 | 1960-09-20 | Du Pont | Process of coating regenerated cellulose film with polyethylene and resultant article |
US2961347A (en) * | 1957-11-13 | 1960-11-22 | Hercules Powder Co Ltd | Process for preventing shrinkage and felting of wool |
US3011915A (en) * | 1958-03-17 | 1961-12-05 | Capskar Inc | Method of coating cloth with a nylon solution |
US3019076A (en) * | 1958-07-22 | 1962-01-30 | Jr Clay E Pardo | Treatment of textiles with polyepoxides and polyamides |
US3033706A (en) * | 1959-08-28 | 1962-05-08 | Jr Clay E Pardo | Shrinkproofing woolen textiles with aqueous emulsions of polyamides and polyepoxides |
DE1142337B (en) * | 1957-12-30 | 1963-01-17 | Kureha Spinning Co Ltd | Process for the production of folds or hems on cotton fabrics equipped with an aminoplast resin |
US3077423A (en) * | 1960-02-19 | 1963-02-12 | Chicopee Mfg Corp | Wiping materials and methods of making the same |
US3078138A (en) * | 1960-04-15 | 1963-02-19 | Lowell A Miller | Shrinkproofing wool with polyamides |
US3084018A (en) * | 1961-03-29 | 1963-04-02 | Robert E Whitfield | Shrinkproofing wool with polyurethanes |
US3455735A (en) * | 1966-05-12 | 1969-07-15 | Du Pont | Process for rendering a synthetic polymeric textile material antistatic and the resulting material |
US3484272A (en) * | 1965-10-09 | 1969-12-16 | Iws Nominee Co Ltd | Process for coating a substrate of keratinous fibers with polyamide |
US3657002A (en) * | 1969-08-05 | 1972-04-18 | Wyandotte Chemicals Corp | Shrinkproofing wool fabrics |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2347024A (en) * | 1943-04-24 | 1944-04-18 | Beer Leo | Impregnating composition for textile materials |
US2406958A (en) * | 1943-07-09 | 1946-09-03 | Du Pont | Chemically modified wool |
US2412993A (en) * | 1943-07-19 | 1946-12-24 | Du Pont | Polymeric materials |
US2430907A (en) * | 1944-06-08 | 1947-11-18 | Du Pont | Nitrogen-substituted polyamides and process for obtaining same |
US2443450A (en) * | 1943-07-01 | 1948-06-15 | Du Pont | Article coated with nu-alkoxymethyl polyamide and process of making same |
US2526637A (en) * | 1948-04-02 | 1950-10-24 | Du Pont | Shrinkproofed wool and method of producing same |
-
1949
- 1949-03-17 US US82025A patent/US2696448A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2347024A (en) * | 1943-04-24 | 1944-04-18 | Beer Leo | Impregnating composition for textile materials |
US2443450A (en) * | 1943-07-01 | 1948-06-15 | Du Pont | Article coated with nu-alkoxymethyl polyamide and process of making same |
US2406958A (en) * | 1943-07-09 | 1946-09-03 | Du Pont | Chemically modified wool |
US2412993A (en) * | 1943-07-19 | 1946-12-24 | Du Pont | Polymeric materials |
US2430907A (en) * | 1944-06-08 | 1947-11-18 | Du Pont | Nitrogen-substituted polyamides and process for obtaining same |
US2526637A (en) * | 1948-04-02 | 1950-10-24 | Du Pont | Shrinkproofed wool and method of producing same |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2882185A (en) * | 1956-04-13 | 1959-04-14 | Onyx Oil & Chemical Company | Water soluble basic polyamides and their alkylation products |
US2925317A (en) * | 1956-09-18 | 1960-02-16 | Joseph E Moore | Shrinkproofing of protein fibers with polyalkyleneimines |
US2953482A (en) * | 1957-07-18 | 1960-09-20 | Du Pont | Process of coating regenerated cellulose film with polyethylene and resultant article |
US2961347A (en) * | 1957-11-13 | 1960-11-22 | Hercules Powder Co Ltd | Process for preventing shrinkage and felting of wool |
DE1142337B (en) * | 1957-12-30 | 1963-01-17 | Kureha Spinning Co Ltd | Process for the production of folds or hems on cotton fabrics equipped with an aminoplast resin |
US3011915A (en) * | 1958-03-17 | 1961-12-05 | Capskar Inc | Method of coating cloth with a nylon solution |
US3019076A (en) * | 1958-07-22 | 1962-01-30 | Jr Clay E Pardo | Treatment of textiles with polyepoxides and polyamides |
US3033706A (en) * | 1959-08-28 | 1962-05-08 | Jr Clay E Pardo | Shrinkproofing woolen textiles with aqueous emulsions of polyamides and polyepoxides |
US3077423A (en) * | 1960-02-19 | 1963-02-12 | Chicopee Mfg Corp | Wiping materials and methods of making the same |
US3078138A (en) * | 1960-04-15 | 1963-02-19 | Lowell A Miller | Shrinkproofing wool with polyamides |
US3084018A (en) * | 1961-03-29 | 1963-04-02 | Robert E Whitfield | Shrinkproofing wool with polyurethanes |
US3484272A (en) * | 1965-10-09 | 1969-12-16 | Iws Nominee Co Ltd | Process for coating a substrate of keratinous fibers with polyamide |
US3455735A (en) * | 1966-05-12 | 1969-07-15 | Du Pont | Process for rendering a synthetic polymeric textile material antistatic and the resulting material |
US3657002A (en) * | 1969-08-05 | 1972-04-18 | Wyandotte Chemicals Corp | Shrinkproofing wool fabrics |
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