US3094718A - Process of treating filaments and yarns of thermoplastic addition polymers - Google Patents
Process of treating filaments and yarns of thermoplastic addition polymers Download PDFInfo
- Publication number
- US3094718A US3094718A US13731A US1373160A US3094718A US 3094718 A US3094718 A US 3094718A US 13731 A US13731 A US 13731A US 1373160 A US1373160 A US 1373160A US 3094718 A US3094718 A US 3094718A
- Authority
- US
- United States
- Prior art keywords
- bobbin
- polymer
- temperature
- groups
- cross
- 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
- 229920000642 polymer Polymers 0.000 title claims description 74
- 238000000034 method Methods 0.000 title claims description 26
- 230000008569 process Effects 0.000 title claims description 22
- 229920001169 thermoplastic Polymers 0.000 title claims description 13
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 13
- 239000000463 material Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 27
- 230000007704 transition Effects 0.000 claims description 25
- 230000000694 effects Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000007385 chemical modification Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 description 34
- 238000004132 cross linking Methods 0.000 description 27
- 238000004804 winding Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- -1 N-mono-substituted acrylamides Chemical class 0.000 description 17
- 238000011282 treatment Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- MDTWMVVAWKKRLC-UHFFFAOYSA-N methoxymethylsulfanylethene Chemical class COCSC=C MDTWMVVAWKKRLC-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001408 amides Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 4
- 238000005956 quaternization reaction Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 2
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 2
- BCTDCDYHRUIHSF-UHFFFAOYSA-N 5-ethenoxypentan-1-ol Chemical compound OCCCCCOC=C BCTDCDYHRUIHSF-UHFFFAOYSA-N 0.000 description 2
- XIKVLURTARLGEJ-UHFFFAOYSA-N 5-ethenoxypentylurea Chemical compound NC(=O)NCCCCCOC=C XIKVLURTARLGEJ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 150000004662 dithiols Chemical class 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 2
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 2
- 229950005308 oxymethurea Drugs 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- HRJGVTGPXHBUTI-UHFFFAOYSA-N (1-ethenoxy-2-methylpropyl)urea Chemical compound C(=C)OC(C(C)C)NC(=O)N HRJGVTGPXHBUTI-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- LABXBOIPJOUEHG-UHFFFAOYSA-N 2-(carbamoylamino)ethyl prop-2-enoate Chemical compound NC(=O)NCCOC(=O)C=C LABXBOIPJOUEHG-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- XHJRWVTZUOPCBI-UHFFFAOYSA-N 2-ethenoxyethylurea Chemical compound NC(=O)NCCOC=C XHJRWVTZUOPCBI-UHFFFAOYSA-N 0.000 description 1
- JDTUPLBMGDDPJS-UHFFFAOYSA-N 2-methoxy-2-phenylethanol Chemical compound COC(CO)C1=CC=CC=C1 JDTUPLBMGDDPJS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- MOYKHGMNXAOIAT-JGWLITMVSA-N isosorbide dinitrate Chemical compound [O-][N+](=O)O[C@H]1CO[C@@H]2[C@H](O[N+](=O)[O-])CO[C@@H]21 MOYKHGMNXAOIAT-JGWLITMVSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 231100000897 loss of orientation Toxicity 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- NYIODHFKZFKMSU-UHFFFAOYSA-N n,n-bis(methylamino)ethanamine Chemical compound CCN(NC)NC NYIODHFKZFKMSU-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000006839 xylylene group Chemical group 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/09—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with free halogens or interhalogen compounds
-
- 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
- D06M13/10—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 oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts 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
- D06M13/325—Amines
- D06M13/332—Di- or polyamines
-
- 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
- D06M13/395—Isocyanates
-
- 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
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- 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
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/10—Polyvinyl halide esters or alcohol fiber modification
-
- 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
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/21—Nylon
Definitions
- the modification contemplated is one involving chemical reaction with the filamentous material so as to modify its physical characteristics such as its hand, dyeability, moisture-regain, resistance to shrinkage, stabilization against shrinkage on Washing or scouring, or to introduce ion-exchange groups of either cationor anion-exchange types.
- the invention is particularly concerned with processes involving chemical modification of the linear polymeric fiber or yarn by a treatment which involves subjecting the filamentous material to an elevated temperature appreciably above the apparent second order transition temperature as defined hereinafter.
- the modification generally requires application of a separate reactant; and the heating step may occur prior to, during, or after impregnation or other application of a chemical re-agent which serves to modify the filamentous material by reaction therewith.
- the apparent second order transition temperature here symbolized as T is defined as that temperature at which the first derivative of thermodynamic variables, such as coefficient of expansion or heat capacity, undergoes a sudden change.
- the transition temperature is observed as an inflection temperature which is conveniently found by plotting the log of the modulus of rigidity against temperat-ure. A suitable method for determining such modulus and transition temperature is described by Williamson in British Plastics 23, 87-90.
- the T, values here used are generally those temperatures at which the modulus is 300 kg./cm.
- the T, values referred to are for polymers as such in a dry state unless otherwise designated.
- silicone oils have been applied after application of the chemical reagent and before the heating operation in an attempt to overcome the difliculty with cementation.
- the chemical modification including the step of subjecting the fibrous material to elevated temperatures above the T value of the material can be effected without cementation when the treatment is applied to the fibers, filaments, or yarns while they are wound so that the windings in the bobbins are close together and form a compact package or body. It is surprising that treatment of such a tightly wound body wherein the yarns are in contact with each other does not aggravate the cementation tendencies.
- the cementation is caused by a solvation and swelling of the individual fibers by the liquid medium containing the reagent or remaining in the bobbin after impregnation with Patented June 25, 1963 ice 2- the re-agent and through the heat treating stage and this swelling or solvation is prevented or limited by the compactness of the windings which prevents the entry or limits the entry of excess amounts of the liquid media into contact with the fibers of the winding.
- the treatment of the fibers or yarns in the form of a wound bobbin also has the effect of maintaining the fibers under tension so that they cannot shrink appreciably dur ing the treatment. This is particularly important in the treatment of fibers in which the molecules of polymer are oriented to a substantial extent in the direction of the axis of the fiber.
- the linear addition polymers with which the present invention is concerned may be homopolymers or copolymers formed of one or more monoethylenically unsaturated compounds, such as esters of acrylic or methacrylic acid with alcohols having 1 to 10 carbon atoms, vinyl ethers or esters such as vinyl chloride, vinyl acetate, vinyl methyl ether, acryl-onitrile, acrylamide, vinylidene chloride, styrene, butadiene, and the like.
- the processes of chemical modification contemplated by the present invention are those involving the cross-linking of such linear polymers by reaction with polyfunctional and particularly difunctional re-agents.
- agents whichserve to convert units in the polymer into modified units including amine units for the purpose of improving dye-ability; hydroxyl or carboxyl units to increase the hydrophilicity of the polymer; and the introduction of thiol, carboxyl, amine, quaternary ammonium, and sulfonic acid units, or salts of any of these units for the purpose of producing ion-exchange fibers.
- the linear polymers thus may include units adapted to be cross-linked.
- the monomers which provide the crosslinkable units in the coplymer include glycidyl acrylate and methacrylate, ureidoalkyl esters, such as ureidoethyl acrylate .and methacrylate, ureidoethyl vinyl ether, ureidopentyl vinyl ether, ureidoisobutyl vinyl ether, N-vinylo-xyalkyl carbamates, such .as N-B-vinyloxyethyl carbarnate, acrylamides, methacrylamides, N-mono-substituted acrylamides and methacrylamides, such as acrylamide per se, methacrylarnide per se, N-methylor N-ethyl acrylamide or metha'crylamide, hydroxyethyl vinyl ether or sulfide, hydroxypentyl vinyl ether or
- the cross-linkable monomer is a monoethylenically unsaturated compound containing a reactive substituent, such as carboxyl, hydroxyl, amido, amino, epoxy, isocyanato, or ureido groups, and the like.
- the cross-linking may be efiected by reacting with polyamines containing atleast two primary, secondary, or tertiary aminenitrogen atoms at a temperature from 50 C. to 250 C., the upper limit being dependent upon the other comonomers present and being insufliciently high to destroy the fiber structure.
- the time generally used is inversely proportional to the temperature. For example, a period of a few secondsto 15 seconds may be proper in the upper regions of the temperature range given, whereas a period of time of a half an hour to sev-.
- eral days maybedesirable at lower temperatures in the range cited. It is believed that the cross-linking action obtained with the polyamines when they contain tertiary amine nitrogen groups is attributable to quaternization.
- the diamine may be applied in a solvent, such as Water, at a concentration of to but when it is a liquid it may be applied directly without dilution in a solvent.
- the fibers may be impregnated with the diamine by simple immersion or by spraying, or in any other suitable manner.
- polyamines examples include ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, N,N-dimethyl-ethylenediamine, N,N, N,N' tetramethyl ethylenediamine, N,N,N',N tetraethyl-ethylenediamine, and N,N,N,N' tetraethyl hexamethylenediarnine.
- cross-linking may be effected by reaction with aldehydes, especially formaldehyde, or by urea or methylol derivatives of urea, such as dimethylol urea.
- aldehydes especially formaldehyde
- urea or methylol derivatives of urea such as dimethylol urea.
- the formah dehyde or urea or derivatives of urea may be applied from solutions in water or alcohol, and the impregnated structure is heated to effect cross-linking at temperatures ranging from 50 to 250 C. for times of the same general range as outlined hereinabove in respect to the crosslinking of polymers of glycidyl acrylates with polyamines.
- polyisocyanates or polyisothiocyanates such as toluene-2,4-diisocyanate, hexamethylenediisocyanate, and the like may be used for efiecting crosslinking.
- temperatures from 50 C. up to 250 C. may be employed, depending upon the particular polyisocyanate and the particular polymer. The times may be as above, in any case the time employed being suificient to give the desired cross-linking.
- the cross-linking may be efiected by any compound having at least two reactive hydrogen atoms, including aldehydes, polyamines, such as those mentioned hereinabove for cross-linking the polymers of glycidyl acrylates, polyhydric alcohols, such as glycols, including ethylene glycol, diethylene glycol, hexamethylene glycol, glycerol, sorbitol, sorbitan, and sorbide, polythiols, especially the dithiols such as ethylene dithiol, pxylylene dithiol, p-olyhydroxyphenols, such as resorcinol, pyrocatechol, orcinol, tannic acid, polycarboxylic acids, and especially dicarboxylic acids, such as succinic acid, adipic acid, sebacic acid, o-phthalic acid, terephthalic acids, and so on.
- polyhydric alcohols such as glycols, including ethylene glycol,
- Treatment may be efiected by immersion or spraying in the polyfunctional reactant if it is a liquid or molten at the temperature employed, or by immersion or spraying of a solution of the polyfunctional reactant.
- the heating may be elfected while the polymeric structure is immersed in the body of reagent, but preferably excess reagent is removed and the polymer structure is heated at temperatures from about 50 C. up to 100 C. or more, such as up to 200 C. for a sufiicient time to efiect cross-linking which may amount to a few seconds at the high temperature up to a quarter of an hour or more at the lower temperature of the range.
- cross-linking may be effected by polycarboxylic acids or polyisocyanates, such as any of those mentioned above, and the reaction may be effected at the temperatures mentioned hereinabove.
- the cross-linkable units may contain amine groups having tertiary nitrogen atoms
- the cross-linking may be efiected by quaternization by means of poly-halides and especially di-halides, including ethylene dichloride, xylylene dichloride, hexamethylene dichloride.
- the cross-linking may be effected by means of aldehydes, such as formaldehyde, acetaldehyde, glyoxal, and the like; also aldehyde derivatives of urea, such as dimethylol urea, reaction being efrected at temperatures of about 50 C. to 250 C. for periods of an hour at the lower temperature to a few seconds at the higher temperatures.
- aldehydes such as formaldehyde, acetaldehyde, glyoxal, and the like
- aldehyde derivatives of urea such as dimethylol urea
- cross-linking may be efiected by polyisocyanates or polyisothiocyanates, such as those mentioned hereinabove, polycarboxylic acids, such as those mentioned hereinabove, and by polybasic acid halides, such as succinyl chloride, adipyl chloride, and so on. These reactions may be eflected within the temperature ranges mentioned hereinabove and in similar time periods.
- the cross-linkable units of the polymer may consist of alkoxymethyl vinyl sulfide units, and especially methoxymethyl vinyl sulfide, which can be converted to thiol units by hydrolysis and the thiol units then converted to disulfide linkages by mild oxidation.
- the alkoxymethyl vinyl sulfide compounds that may be used as monomers have the structure of Formula I:
- R is a methylene, ethylidene, or isopropylidene group
- R is an alkyl group having 1 to 8 carbon atoms, but is preferably methyl.
- the polymer product may be treated with a solution of the oxidizing agent at any temperature from about 60 C. up to about 180 C. or higher for various periods of time. For example, the treatment may be effected for about 10 seconds to 15 minutes at about C.
- the permissible upper limits of the conditions of temperature, time, and concentration depend on the individual oxidizing agents and they are correlated to provide a mild oxidation which serves to effect cross-linking, but does not go appreciably further to form substantial amounts of sulfone and sulfonic acid groups.
- the upper limit of concentration depends on the individual agent and the temperature at which the oxidation is carried out.
- the heating stage in such event may be termed a baking or curing step and may be carried out at temperatures of 50 C. to 200 C. but, as discussed hereinbefore, the upper limit of temperature in this stage is dependent on the particular oxidant employed.
- the excess of such medium may be removed as by suction or air-squeegeeing and the oxidation which may or may not have been started while the polymer product is immersed in the medium containing the oxidizing agent may be pushed to completion by subsequently heating the polymer product at elevated temperatures from about 80 C. to 200 C. for a period of time ranging from about 5 minutes to about half an hour at the higher temperature to about 15 minutes to about an hour or two at the lower temperature.
- the cross-linkable units of the polymer may consist of alkoxymethylthiolalkyl acrylate, methacrylate, or itaconate units. These units are hydrolyzed to thiol groups in the same manner as the alkoxymethyl vinyl sulfide units hereinbefore described and mild oxidation as described above serves to form disul-fide linkages.
- ester units in the polymer such as acrylates, particularly methyl acrylate, and vinyl acetate to introduce acid or hydroxyl groups respectively.
- Acryl'onitrile polymers may likewise be hydrolyzed to introduce amide and acid units.
- Polymers comprising units of esters of acrylic or methacrylic acid or of other acids may be aminolyzed by reaction with an amine or a diamine such as diethanolamine or N,N-dimethylaminoethylamine for the purpose of introducing basic amine groups in the copolymer.
- the treatment may also involve alkylation of polymers containing amine groups to produce quaternary ammonium compounds.
- All of these treatments may be effected at temperatures of 50 C. up to 130 C. or even in some cases up to 200 C. so that the present process is of advantage in these treatments as it enables the treatment to be carried out at temperatures which may be higher than the apparent second order transition temperature of the fiber.
- release-agents such as silicone oils are not. necessary to' assure complete freedom from cementa tion.
- such oils may be used if desired.
- the chemical re-agent which serves to modify the fiber may be applied in liquid medium consisting entirely of the re-agent if such re-agent is liquid at the temperature of application or as a solution or dispersion in either aqueous or organic solvent media.
- Application may be effected by spraying, immersion, soaking, or by forcing the liquid treating media through the windings of the bobbin by means of an internal perforated core into which the liquid medium may be forced under pressure so that it permeates from the core through the entire body of the winding.
- the bobbin or plurality thereof may be mounted on such perforated core within an enclosed drum or chamber so that the liquid flow may be. alternately forced to proceed from the interior of the core through the winding or from the space in the chamber through the winding and out through the perforated core.
- the wound bobbin may be subjected to the heat treatment during the impregnation with the liquid medium and for this purpose, the liquid medium may itself be heated and/ or the vessel containing the bobbins may be heated externally by means of a steam jacket.
- the winding may be preheated by being subjected to a hot gas such as hot air or an inert gas such as hot nitrogen or carbon dioxide before it is impregnated.
- the heat treatment may be performed after the impregnation such as in a baking or curing operation.
- the impregnated bobbin may be removed from the impregnating medium, excess being removed by squeegeeing, vibrating, and then the bobbins are subjected to the heat treatment as in a baking or curing operation in an oven or under the influence of any other suitable heating equipment.
- the procedure involving impregnation and subsequent subjection to heat has the advantage of favoring completely uniform distribution of the impregnating liquid including the reagent before appreciable reaction is effected.
- Example 1 A yarn formed of a polymer of 70 parts of acrylonitrile, 10 parts of butoxyethyl acrylate, and 20 parts of methoxymethyl vinyl sulfide which has been stretched about 600% during its formation is wound on a bobbin under a tension of about 2 grams per denier.
- the bobbin is then treated by soaking in 4% aqueous phosphoric acid for one hour at 40 'C., and then treated with a solution of 5% iodine in ethanol at 40 C. for one hour.
- the yarn is withdrawn from the solution, excess iodine solution is removed, and the yarn is then cured by heating it on the bobbin at 150 C. for 40 minutes. It has a tensile strength of 3.0 grams. per denier and an extensibility at break of 28%.
- the temperature at which the yarn shows 5% shrinkage is 150 C. It. shrinks solution, and subsequent heating shows 5% shrinkageat C. and shrin-gs 75% on being heated
- Example 2 A yarn formed of a copolymer of 65 parts of acrylo nitrile, 15 parts of butoxyethyl acrylate, and 20 parts of methoxymethyl vinyl sulfide which had been stretched 600% during its initial formation is wound at a tension of about 1 /2 grams per denier into a compact bobbin on a perforated core.
- the wound bobbin is soaked in aqueous 4.9% phosphoric acid for 30 minutes at 40 C.
- The. yarn is then soaked for ten minutes in an aqueous solution containing 0.04% NaOH and 1% iodine, the pH of which is adjusted to 9.0 with N/2. H the temperature of this solution being 40 C.
- the yarn is then heated at 150 C. for one hour.
- the yarn which is now cross-linked in an oriented state, is then treated with 140 milliliters per gram of a mixture of 50 parts of N/ZO sodium hydroxide in water and 50 parts of ethanol at the refluxing temperature of the mixture for two days to hydrolyze some of its units to carboxylic groups.
- the resulting product is a carboxylic ion-exchange material in the form of a yarn, the filaments of which show orientation along the fiber axis and have a capacity for exchanging sodium of 3.2 milliequivalents per gram.
- Example 3 (a)- A yarn comprising fibers formed of a copolymer of 70% acrylonitrile, 25% ethyl acrylate, and 5% ureidopentyl vinyl ether, which has been stretched about 250% during its formation, is wound on a bobbin at a tension of about 1 gram per denier and the bobbin is soaked in toluene-2,4-diisocyanate at 25 C. for two minutes and heated at 70 C. for 40 hours. The cured yarn is then hydrolyzed with a solution of sodium hydroxide in water and ethanol in the manner described in Example 2. The product has a capacity for exchanging sodium of about 3 milliequivalents per gram.
- a cation-exchange fiber is obtained by subjecting a yarn comprising fibers formed of 65% of acrylonitrile, 25% of methyl acrylate, and 10% of hydroxypentyl vinyl ether, wound in the form of a bobbin under a tension of about 1.5 grams per denier, to the same treatment as just described.
- Example 4 A yarn comprising filaments formed of a copolymer of 45% ethyl acrylate, 35% acrylonitrile, and 20% glycidyl methacrylate, which has been stretched about 150% during formation, is wound into a bobbin under a tension of about 1.5 grams per denier. The bobbin is then, soaked in an aqueous 20% solution of hexamethylenediamine for hours at 25 C. The soaked yarn is removed from the solution and allowed to dry in the air to eliminate excess surface moisture and is then heated at 80 C. for one hour, followed by subjection to C. for one hour. It is then washed in 5% aqueous acetic acid solution at 25 C., washed with water, and air-dried.
- the bobbin may then be treated by soaking in a 50:50 volume mixture of N/ 20 sodium hydroxide and ethanol at 60 C. for about two days. Yarn obtained in this fashion.
- Example 5 is forced and recirculated a solution comprising a 50:50
- a bobbin prepared in this fashion may then be impregnated with a mixture in 60:40 volume ratio of N/20 sodium hydroxide and ethanol for about 24 hours at 60 C.
- Yarn obtained in this fashion has .a cation-exchange capacity of about 2 to 2.5 milliequivalents per gram.
- Example 6 The procedure of Example (a) is repeated except that the p-xylylene dichloride solution is replaced with a solution of 10% of p-Xylylene dichoride and benzyl chloride in toluene.
- the resulting anion-exchange fibers can be converted into sulfate form by soaking the bobbin in 5% sulfuric acid.
- a process for chemically modifying a filamentous material formed of a thermoplastic linear addition polymer having an apparent second order transition temperature of 40 C. up to 200 C. which comprises the step of winding a yarn of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid medium comprising an agent for modifying the polymer by chemical reaction, and then heating the impregnated bobbin to a temperature which is above the apparent second order transition temperature of the polymer and is at least 50 C. in order to effect chemical modification of the polymer in the fiber.
- a process for chemically modifying a filamentous material formed of a thermoplastic linear addition polymer having an apparent second order transition temperature of 40 C. up to 200 C. and containing reactive groups which comprises the step of winding a yarn of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid medium comprising a polyfunctional reagent having groups which react with the reactive groups of the polymer, and then heating the impregnated bobbin to a temperature which is above the apparent second order transition temperature of the polymer and is at least 50 C. in order to effect cross-linking of the polymer in the fiber.
- a process for chemically modifying a filamentous material formed of a thermoplastic linear addition polymer having an apparent second order transition temperature of 40 C. up to 200 C. and containing reactive groups selected from the group consisting of carboxyl, hydroxyl, amido, amino, epoxy, isocyanato, and ureido groups which comprises the step of winding a yarn of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid medium comprising a polyfunctional reagent having groups which react with the reactive groups of the polymer, and then heating the impregnated bobbin to a temperature which is above the apparent second order transition temperature of the polymer and is at least 50 C. in order to effect cross-linking of the polymer in the fiber.
- a process for chemically modifying a filamentous material formed of a thermoplastic linear addition polymer having an apparent second order transition temperature of 40 C. up to 200 C. and containing reactive ureido groups which comprises the step of winding a yarn of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid medium containing an organic polyisocyanate, and then heating the impregnated bobbin to a temperature which is above the apparent second order transition temperature of the polymer and is at least 50 C. in order to effect cross-linking of the polymer in the fiber.
- a process for chemically modifying a filamentous material formed of a thermoplastic linear addition polymer having an apparent second order transition temperature of 40 C. up to 200 C. and containing reactive hy droxyl groups which comprises the step of winding a yam of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid medium containing an organic polyisocyanate, and then heating the impregnated bobbin to a temperature which is above the apparent second order transition temperature of the polymer and is at least 50 C. in order to effect cross-linking of the polymer in the fiber.
- a process for chemically modifying a filamentous material formed of a thermoplastic linear addition polymer having an apparent second order transition temperature of 40 C. up to 200 C. and containing reactive glycidyl groups which comprises the step of winding 21 yarn of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid medium containing a polyamine, and then heating the impregnated bobbin to a temperature which is above the apparent second order transition temperature of the polymer and is at least 50 C. in order to effect cross-linking of the polymer in the fiber.
- a process for chemically modifying a filamentous material formed of a thermoplastic linear addition polymer having an apparent second order transition temperature of 40 C. up to 200 C. and containing reactive amino groups which comprises the step of winding 21 yarn of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid medium containing an organic dihalide, and then heating the impregnated bobbin to a temperature which is above the apparent second order transition temperature of the polymer and is at least 50 C. in order to effect cross-linking of the polymer in the fiber.
- a process for chemically modifying a filamentous material formed of a thermoplastic linear addition polymer having an apparent second order transition temperature of 40 C. up to 200 C. and containing hydrolyzable alkoxymethylthio groups which comprises the step of winding a yarn of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid medium comprising an acid to hydrolyze the alkoxymethylthio groups to thiol groups, impregnating the bobbin with a solution of iodine and then heating the iodine-impregnated bobbin to form disulfide cross-linkages between the linear polymers in the fiber.
- a process for chemically modifying a filamentous material formed of a thermoplastic linear addition polymer of at least one monomer selected from the group consisting of the nitrile, amide, and ester derivatives of an acid selected from the group consisting of acrylic acid and methacrylic acid, having an apparent second order transition temperature of 40 C. up to 200 C. which comprises the step of winding a yarn of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid alkaline medium, and heating the impregnated bobbin to hydrolyze the acid derivative to introduce carboxylate salt groups into the polymer.
- a process for chemically modifying a filamentous material formed of a thermoplastic linear addition polymer of at least one monomer selected from the group consisting of the nitrile, amide, and ester derivatives of an acid selected from the group consisting of acrylic acid and methacrylic acid, having an apparent second order transition temperature of 40 C. up to 200 C. which comprises the step of winding a yarn of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid medium containing a diamine having a tertiary nitrogen atom'and a nitrogen atom having at least one hydrogen atom attached thereto, and heating the impregnated bobbin to aminolyze the acid derivative to introduce amino groups into the polymer.
- a process according to claim 10 comprising the additional steps of impregnating the bobbin of fiber containing aminolyzed polymer with a liquid medium containing a quaternizing material and heating the impregnated bobbin to effect quaternization of tertiary amine groups in the polymer.
- a process according to claim 10 comprising the additional steps of impregnating the bobbin of fiber containing aminolyzed polymer with a liquid medium containing a difunctional quaternizing material and heating the impregnated bobbin to eflect quaternization of tertiary amine groups in the polymer and thereby cross-linking the polymer, then impregnating the bobbin with a liquid alkaline medium and heating the impregnated bobbin to hydrolyze the acid derivative to introduce carboxylate salt groups into the polymer.
- a process for chemically modifying a filamentous material formed of a cross-linked addition polymer of at least one monomer selected from the group consisting of the ni-trile, amide, and ester derivatives of an acid selected from the group consisting of acrylic acid and methacrylic acid which comprises the step of winding a yarn of such filamentous material into a compact bobbin, impregnating the bobbin with a liquid alkaline medium and heating the impregnated bobbin to hydrolyze the acid derivative to introduce carboxylate salt groups into the polymer.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL262160D NL262160A (cs) | 1960-03-09 | ||
BE601127D BE601127A (cs) | 1960-03-09 | ||
US13731A US3094718A (en) | 1960-03-09 | 1960-03-09 | Process of treating filaments and yarns of thermoplastic addition polymers |
FR855105A FR1283529A (fr) | 1960-03-09 | 1961-03-09 | Modification chimique de filaments et fils de polymères thermoplastiques d'addition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13731A US3094718A (en) | 1960-03-09 | 1960-03-09 | Process of treating filaments and yarns of thermoplastic addition polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
US3094718A true US3094718A (en) | 1963-06-25 |
Family
ID=21761448
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13731A Expired - Lifetime US3094718A (en) | 1960-03-09 | 1960-03-09 | Process of treating filaments and yarns of thermoplastic addition polymers |
Country Status (3)
Country | Link |
---|---|
US (1) | US3094718A (cs) |
BE (1) | BE601127A (cs) |
NL (1) | NL262160A (cs) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2521176A1 (fr) * | 1982-02-05 | 1983-08-12 | Sheldon Maurice Atlas | Tissu de bonneterie antistatique, resistant a l'abrasion et confortable |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2090862A (en) * | 1932-05-09 | 1937-08-24 | North American Rayon Corp | Manufacture and after treatment of artificial filaments, yarns, etc. |
US2093140A (en) * | 1932-03-02 | 1937-09-14 | Ig Farbenindustrie Ag | Manufacture of artificial silk |
US2325060A (en) * | 1942-02-25 | 1943-07-27 | Du Pont | Nonshrinking yarn |
US2786732A (en) * | 1949-08-20 | 1957-03-26 | Inventa Ag | Process for raising the melting point of poly-e-caprolactam filaments, threads, and yarns by treatment with gaseous formaldehyde and products produced thereby |
US2926062A (en) * | 1956-03-05 | 1960-02-23 | Gagliardi Res Corp | Water repellent compositions, products and processes for making same |
US3022926A (en) * | 1953-11-27 | 1962-02-27 | Proctor & Schwartz Inc | Method of heat setting, dyeing and optionally scouring boarded synthetic thermoplastic textiles with superat-mospheric steam |
-
0
- NL NL262160D patent/NL262160A/xx unknown
- BE BE601127D patent/BE601127A/xx unknown
-
1960
- 1960-03-09 US US13731A patent/US3094718A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2093140A (en) * | 1932-03-02 | 1937-09-14 | Ig Farbenindustrie Ag | Manufacture of artificial silk |
US2090862A (en) * | 1932-05-09 | 1937-08-24 | North American Rayon Corp | Manufacture and after treatment of artificial filaments, yarns, etc. |
US2325060A (en) * | 1942-02-25 | 1943-07-27 | Du Pont | Nonshrinking yarn |
US2786732A (en) * | 1949-08-20 | 1957-03-26 | Inventa Ag | Process for raising the melting point of poly-e-caprolactam filaments, threads, and yarns by treatment with gaseous formaldehyde and products produced thereby |
US3022926A (en) * | 1953-11-27 | 1962-02-27 | Proctor & Schwartz Inc | Method of heat setting, dyeing and optionally scouring boarded synthetic thermoplastic textiles with superat-mospheric steam |
US2926062A (en) * | 1956-03-05 | 1960-02-23 | Gagliardi Res Corp | Water repellent compositions, products and processes for making same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2521176A1 (fr) * | 1982-02-05 | 1983-08-12 | Sheldon Maurice Atlas | Tissu de bonneterie antistatique, resistant a l'abrasion et confortable |
Also Published As
Publication number | Publication date |
---|---|
NL262160A (cs) | |
BE601127A (cs) |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2933460A (en) | Ion-exchange fibers, films and the like from sulfur containing alkoxymethyl monomers | |
US3841832A (en) | Process for treating cellulosic material with formaldehyde in liquid phase and sulfur dioxide | |
US2403464A (en) | Hydrolyzed vinyl ester interpolymer fibers | |
US2895786A (en) | Process for making filaments from polyvinyl alcohol polyamide mixture and product | |
US2902391A (en) | Process for improving the properties of regenerated cellulose fibrous material wherein said material is treated while still in the gel state | |
JPS6315380B2 (cs) | ||
US3055729A (en) | Process for producing ion-exchange fibers, films, and the like | |
US5520705A (en) | Surface treated aramid fibers and a process for making them | |
US2333914A (en) | Isocyanate treatment of polyamides | |
US2350188A (en) | Textile treatment | |
US3094718A (en) | Process of treating filaments and yarns of thermoplastic addition polymers | |
DE1934349A1 (de) | Verfahren zum Beschichten von Endlos-Glasfaeden | |
US3498740A (en) | Imparting permanent dimensional stability and finish stability to fabrics containing keratinous fibers | |
US3233026A (en) | Method of producing anion-exchange fibers, films, and the like | |
US2846337A (en) | Magnesium chloride catalyst for modified urea resins | |
DE1085334B (de) | Verfahren zur Vernetzung von Polyvinylalkohol | |
US4689159A (en) | Textile processing agent and treatment of textile with the same | |
USRE30860E (en) | Process for treating cellulosic material with formaldehyde in liquid phase and sulfur dioxide | |
US3127732A (en) | Method for producing bulked, highly stretchable textured cotton yarns | |
US5352483A (en) | Preadhered melt spun spin-drawn polyester filaments | |
US2893892A (en) | Method for the coating of glass threads and tissues with artificial resin | |
US2890978A (en) | Paper of high dry strength and low wet strength | |
US3140265A (en) | Fibrous textile and industrial fabrics | |
US2636804A (en) | Process of treating polyvinyl alcohol fibers | |
US3837799A (en) | Process for creaseproofing cellulosic fiber-containing fabric using formaldehyde vapor and a solid and a solid catalyst |