US3337652A - Modification of stereoregular polyolefins - Google Patents
Modification of stereoregular polyolefins Download PDFInfo
- Publication number
- US3337652A US3337652A US406631A US40663164A US3337652A US 3337652 A US3337652 A US 3337652A US 406631 A US406631 A US 406631A US 40663164 A US40663164 A US 40663164A US 3337652 A US3337652 A US 3337652A
- Authority
- US
- United States
- Prior art keywords
- vinyl
- polyolefin
- weight
- pyrrolidone
- phosphoric 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
- 229920000098 polyolefin Polymers 0.000 title claims description 66
- 230000004048 modification Effects 0.000 title description 4
- 238000012986 modification Methods 0.000 title description 4
- -1 POLYPROPYLENE Polymers 0.000 claims description 26
- 229920001577 copolymer Polymers 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 239000011885 synergistic combination Substances 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 13
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical class CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 7
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 150000005215 alkyl ethers Chemical class 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- LPNSCOVIJFIXTJ-UHFFFAOYSA-N 2-methylidenebutanamide Chemical compound CCC(=C)C(N)=O LPNSCOVIJFIXTJ-UHFFFAOYSA-N 0.000 claims description 5
- DGPVNNMFVYYVDF-UHFFFAOYSA-N 1-prop-2-enoylpyrrolidin-2-one Chemical compound C=CC(=O)N1CCCC1=O DGPVNNMFVYYVDF-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 229920000306 polymethylpentene Polymers 0.000 claims description 4
- 239000011116 polymethylpentene Substances 0.000 claims description 4
- ZMALNMQOXQXZRO-UHFFFAOYSA-N 4-ethenylmorpholin-3-one Chemical compound C=CN1CCOCC1=O ZMALNMQOXQXZRO-UHFFFAOYSA-N 0.000 claims description 3
- ZAEHYVZEBONAIX-UHFFFAOYSA-N 1-(3-methylbuta-1,3-dienyl)pyrrolidin-2-one Chemical compound CC(=C)C=CN1CCCC1=O ZAEHYVZEBONAIX-UHFFFAOYSA-N 0.000 claims description 2
- HXFNRRNDWNSKFM-UHFFFAOYSA-N 3-ethenyl-5-methyl-1,3-oxazolidin-2-one Chemical compound CC1CN(C=C)C(=O)O1 HXFNRRNDWNSKFM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002193 fatty amides Chemical class 0.000 claims description 2
- UBPXWZDJZFZKGH-UHFFFAOYSA-N 1-ethenyl-3-methylpyrrolidin-2-one Chemical compound CC1CCN(C=C)C1=O UBPXWZDJZFZKGH-UHFFFAOYSA-N 0.000 claims 1
- XHULUQRDNLRXPF-UHFFFAOYSA-N 3-ethenyl-1,3-oxazolidin-2-id-4-one Chemical compound C(=C)N1[CH-]OCC1=O XHULUQRDNLRXPF-UHFFFAOYSA-N 0.000 claims 1
- VUEZBQJWLDBIDE-UHFFFAOYSA-N 3-ethenyl-1,3-oxazolidin-2-one Chemical compound C=CN1CCOC1=O VUEZBQJWLDBIDE-UHFFFAOYSA-N 0.000 claims 1
- YSFGBPCBPNVLOK-UHFFFAOYSA-N 6-hydroxy-2-methylhex-2-enamide Chemical compound NC(=O)C(C)=CCCCO YSFGBPCBPNVLOK-UHFFFAOYSA-N 0.000 claims 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 claims 1
- 239000003607 modifier Substances 0.000 description 51
- 239000000975 dye Substances 0.000 description 29
- 239000000835 fiber Substances 0.000 description 27
- 238000007792 addition Methods 0.000 description 21
- 239000000654 additive Substances 0.000 description 18
- 230000006872 improvement Effects 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000004043 dyeing Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 8
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical group CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 3
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical class O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- UNBOSJFEZZJZLR-UHFFFAOYSA-N 4-(4-nitrophenylazo)aniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 UNBOSJFEZZJZLR-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- FRXGWNKDEMTFPL-UHFFFAOYSA-N dioctadecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCCCC FRXGWNKDEMTFPL-UHFFFAOYSA-N 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 229940085632 distearyl ether Drugs 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 150000002194 fatty esters Chemical class 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical class CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- DRXCNVFYHXCBFE-UHFFFAOYSA-N 1-dodecoxypropan-2-ol Chemical compound CCCCCCCCCCCCOCC(C)O DRXCNVFYHXCBFE-UHFFFAOYSA-N 0.000 description 1
- ZQCIPRGNRQXXSK-UHFFFAOYSA-N 1-octadecoxypropan-2-ol Chemical compound CCCCCCCCCCCCCCCCCCOCC(C)O ZQCIPRGNRQXXSK-UHFFFAOYSA-N 0.000 description 1
- XZBACIYYJPQCJG-UHFFFAOYSA-N 2,3-didodecoxypropan-1-ol Chemical compound CCCCCCCCCCCCOCC(CO)OCCCCCCCCCCCC XZBACIYYJPQCJG-UHFFFAOYSA-N 0.000 description 1
- MSDLTIIVMVDTLX-UHFFFAOYSA-N 2,3-dihexoxypropan-1-ol Chemical compound CCCCCCOCC(CO)OCCCCCC MSDLTIIVMVDTLX-UHFFFAOYSA-N 0.000 description 1
- QEHCYTDFERPPPU-UHFFFAOYSA-N 2,3-dioctadecoxypropan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCOCC(CO)OCCCCCCCCCCCCCCCCCC QEHCYTDFERPPPU-UHFFFAOYSA-N 0.000 description 1
- FKOKUHFZNIUSLW-UHFFFAOYSA-N 2-Hydroxypropyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(C)O FKOKUHFZNIUSLW-UHFFFAOYSA-N 0.000 description 1
- ICIDSZQHPUZUHC-UHFFFAOYSA-N 2-octadecoxyethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCO ICIDSZQHPUZUHC-UHFFFAOYSA-N 0.000 description 1
- BKKDPCPRVWPIEN-UHFFFAOYSA-N 3-ethenyl-4-methyl-1,3-oxazolidin-2-one Chemical compound CC1COC(=O)N1C=C BKKDPCPRVWPIEN-UHFFFAOYSA-N 0.000 description 1
- WRNODTYYEUSETK-UHFFFAOYSA-N 3-prop-2-enyl-1,3-oxazolidin-2-one Chemical compound C=CCN1CCOC1=O WRNODTYYEUSETK-UHFFFAOYSA-N 0.000 description 1
- IKDHIMYPOLRLJB-UHFFFAOYSA-N 4-hydroxybutyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCO IKDHIMYPOLRLJB-UHFFFAOYSA-N 0.000 description 1
- KRGOMVGRWXRUTK-UHFFFAOYSA-N 4-octadecoxybutan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCOCCCCO KRGOMVGRWXRUTK-UHFFFAOYSA-N 0.000 description 1
- UKYSQGFHAINBIH-UHFFFAOYSA-N 6-octoxyhexan-1-ol Chemical compound CCCCCCCCOCCCCCCO UKYSQGFHAINBIH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KTRZMOZGJIMFQI-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].C(CCCCCCCCCCCCCCCCC)[N+](C)(CCO)CCO.C(CCCCCCCCCCCCCCCCC)[N+](CCO)(CCO)C Chemical group S(=O)(=O)([O-])[O-].C(CCCCCCCCCCCCCCCCC)[N+](C)(CCO)CCO.C(CCCCCCCCCCCCCCCCC)[N+](CCO)(CCO)C KTRZMOZGJIMFQI-UHFFFAOYSA-L 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical compound CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- SUZSZZWHCFLFSP-UHFFFAOYSA-M bis(2-hydroxyethyl)-methyl-octadecylazanium;chloride Chemical group [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(CCO)CCO SUZSZZWHCFLFSP-UHFFFAOYSA-M 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 150000002195 fatty ethers Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- UHUSDOQQWJGJQS-UHFFFAOYSA-N glycerol 1,2-dioctadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCCCCCCCCCCC UHUSDOQQWJGJQS-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WPEOOEIAIFABQP-UHFFFAOYSA-N hexanedioic acid;hexane-1,6-diol Chemical compound OCCCCCCO.OC(=O)CCCCC(O)=O WPEOOEIAIFABQP-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229920001480 hydrophilic copolymer Polymers 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NQNOMXXYKHWVKR-UHFFFAOYSA-N methylazanium;sulfate Chemical compound NC.NC.OS(O)(=O)=O NQNOMXXYKHWVKR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VSEAAEQOQBMPQF-UHFFFAOYSA-N morpholin-3-one Chemical class O=C1COCCN1 VSEAAEQOQBMPQF-UHFFFAOYSA-N 0.000 description 1
- XMMDVXFQGOEOKH-UHFFFAOYSA-N n'-dodecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCNCCCN XMMDVXFQGOEOKH-UHFFFAOYSA-N 0.000 description 1
- DXYUWQFEDOQSQY-UHFFFAOYSA-N n'-octadecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCCCCNCCCN DXYUWQFEDOQSQY-UHFFFAOYSA-N 0.000 description 1
- NNKSAZWMTWKXLD-UHFFFAOYSA-N n-methyloctadecan-1-amine;hydrochloride Chemical group [Cl-].CCCCCCCCCCCCCCCCCC[NH2+]C NNKSAZWMTWKXLD-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940093625 propylene glycol monostearate Drugs 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- KRIXEEBVZRZHOS-UHFFFAOYSA-N tetradecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCOP(O)(O)=O KRIXEEBVZRZHOS-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
Definitions
- polyethylene is vastly unsuitable for the production of textile fibers due to the relatively poor properties imparted to the product.
- staple polyethylene fiber will not hold a crimp and this is necessary for textile processing.
- it is useless to make a textured or stretch yarn from continuous filament polyethylene yarn because the characteristics imparted to the yarn are not maintained during weaving, dyeing, or ordinary use.
- the material from which a fabric is made must be thermally stable before it may be subjected to ordinary use. It must not have a relatively low melting point, and the final fabric must not have a high degree of heat sensitivity, nor relatively soft mechanical properties at elevated temperatures.
- These secondary polar modifiers are generally low molecular weight additives or possess melting points somewhat lower than the polyolefin itself. These secondary additives associate themselves with the primary hydrophilic polymeric modifier in such a way as to give synergistic combinations that are fusible at temperatures not exceeding the temperature of processing of the polyolefin (150 C. to 350 C.) and have improved processability and dyeability.
- the use of the secondary polar additives improves brightness and clarity of the final film or luster and brightness of the final fiber.
- the whiteness of the fiber is also improved because a smaller amount of the primary polymeric modifier, which is responsible for the off-white color, is utilized.
- An economic advantage is also associated with the use of the present composition for a smaller amount of the more expensive primary polymeric modifier is utilized in the composition while still maintaining or improving the affinity of the composition for dyes.
- stereoregular polyolefin structures with increased affinity for dyes comprising a matrix of a stereoregular polyolefin taken from the group consisting of (a) polypropylene, (b) polymethylpentene, and (o) polymethylbutene, said matrix having dispersed therein between 2 and 20% of a synergistic combination consisting of:
- modifying copolymer which is hydrophilic, non-soluble in the polyolefin, and fusible at a temperature between C. and 350 C.
- said modifying copolymer being selected from the group consisting of:
- alkyl esters of polyhydroxy compounds (a) alkyl esters of polyhydroxy compounds, (b) alkyl esters of polyglycols, 60 to 4000 M, (c) alkyl ethers of polyglycols, 60 to 4000 M, (d) alkyl ethers of polyhydroxy compounds, (e) alkoxylated alkyl amines,
- said synergistic combination being fusible at a temperature of processing of the polyolefin (150 to 350 C.) and forming a complex in said polyolefin.
- stereoregular polyolefins which may be used within the concept of this invention include isotactic and syndiotactic polyolefins. These materials are usually made by utilizing stereo-specific catalysts which give polymers which are substantially linear and which develop a high degree of crystallinity.
- a preferred class of my primary polymeric modifiers consists of copolymers derived from oxygen containing N-alkenyl heterocyclic monomers, particularly alkenyl substituted lactams, oxazolidone, oxazolidinone and morpholinone monomers.
- This class of polymers is highly desirable because it has little or no basicity and has very high levels of affinity for a Wide range of dyes.
- My preferred primary modifiers are neutral or only very slightly basic and yet in polyolefins, surprisingly, have higher dyability with anionic (acid) dyes than the much more basic polymeric modifiers.
- the alkenyl substituted nitrogen is part of an internal amide group and is essentially neutral. Additional ring and substituted oxygen containing groups are more acidic than the substituted amide nitrogen and further reduce basicity.
- the secondary polar additives which may be used with the primary modifier to give synergistic combinations include the following:
- Alkyl esters of polyhydroxy compounds such as:
- Example I prepared discs of polyolefin in the following manner utilizing as modifier N-vinyl-S-methyl-2-oxazo1idinone in a balanced weight fraction copolymer with vinyl acetate (VOOM/Va) (Devlex A515, Dow Chemical Co.) alone and in combination with (GMS) g1ycerol monostearate.
- VOOM/Va vinyl acetate
- GMS g1ycerol monostearate
- the mixtures were then air dried (to remove some solvent) and then heated in a drying oven at 80 C. until all of the solvent had been removed.
- Each of the dried mixtures was prepared in the form of a disc in the following manner:
- the powder of each sample was spread uniformly in a circular shouldered Pyrex glass dish with an inside diameter of 4 inches.
- the dishes were then covered by an inner nesting circular shouldered Pyrex glass dish with a bottom outer separation rib projecting downwardly about 0.05 inch.
- the assembly weighted with a preheated 5 pound weight was then placed in an oven at 250 C. for 6 to minutes. Then the weight was removed and the assembly was placed in a refrigerator at about 4 C. to cool.
- the assembly dishes were then separated to give a fuzed disc.
- AMRColour Index Acid Red 182, AR-Colour Index, Acid Red 127, DO-Colour Index, Disperse Orange 3, and DLVLatyl Violet 2R, Disperse Dye.
- the dye baths were each heated over an hour to a temperature of about 95 C. and the temperature was"
- an improvement in dyeability is achieved, although accompanied by a 20% reduction in the amount of copolymer utilized in the composition if a selected lower melting additive is substituted in part for the copolymer.
- higher levels of dispersion and dyeability may be achieved with higher levels of addition. This is surprising because when the primary polymeric modifiers are utilized alone, one obtains poor dispersibility with higher levels of addition.
- Example 2 In this example, tests similar to those of Example 1 were performed except that, in this case, the modifier containing polyolefin was extruded into fiber, drawn and then dyed using conventional equipment and processes.
- the formulation was melt mixed in a continuous screw extruder, forced through a 60 mil die at 260 C. and collected at ambient temperature on a reel as a 30 denier filament.
- the filament was then heat stretched 300% to give a strong, oriented 10 denier fiber.
- Fiber skeins Were then scoured with detergent at 140 F., and dyed at the boil for one hour at 2-0/ 1 bath to fiber ratio.
- the synergistic combination which was utilized as the modifier, consisted of a copolymer, 50% vinyl methyloxazolidinone with 50% vinyl acetate (VOOM/Va), in combination with (GMS)-glycerol monostearate.
- Percent VOOM/Va 4 9.
- Percent GMS 1 1. Dispersibility in Polyolefin Excellent Good/excellent.
- Example 3 dispersion and depth of coloration. The results of these tests are tabulated below:
- the modifier containing polyolefin was extruded into fiber, drawn, and then dyed using conventional equipment and processes.
- the synergistic combination which was utilized as the modifier, consisted of a copolymer, 70% vinyl pyrrolidone with vinyl acetate (VP/Va), in combination with Dyeability with dyes Dispersibillty Secondary Additive in Polyolefin (b) a DLV, DO AMR, AR
- ammonium chloride Tertiigry stearyl amine with 15 moles ethylene Excellent Dark Do.
- the dispersibility was only fair while the depth of coloration lies in the medium range.
- the dispersability was good to excellent and the depth of coloration was increased, in some cases, from medium to medium/dark and dark. This improvement, in all cases, is the direct result of the synergistic combination in the olefinic composition as taught by the present concept.
- Example 5 I prepared discs using as modifiers the copolymers enumerated below, both alone, and in combination with selected secondary additives. The discs were dyed following the procedure heretofore described and the finished discs were judged subjectively In accordance with the procedure set forth in Example for uniformity of dispersion and depth of color.
- my modifiers with polyolefins are readily available. They may be combined during formation of the polymeric modifier or during actual polymerization of the polyolefin, with or without melting. They may be added to freshly polymerized polyolefin, which is still in solution in a suitable solvent, in the powdered form, or as a solution in a compatible solvent, or merely as a dispersion. They may be added to the polyolefin during precipitation, washing, neutralizing or compounding of the freshly prepared polyolefin prior to drying.
- modifiers may also be melt mixed during processing or blending of the polymer prior to use in extension of fiber, film, coating or plastic. It may also be added as a liquid or powder to finely ground or micronized polyolefin polymers and then melt dispersed in situ during hot dip or spray coating or during spreading and heat coating operation. They may be incorporated in polyolefin solutions or emulsion and then applied to surfaces with or without heating.
- the level of additionto the polyolefin of the synergistic combination heretofore described should be between 2 and 20% of the weight of the overall composition. If less than 2% is utilized, significant improvement will not be achieved in dyeability. If an amount greater than 20% is added to the polyolefin, many of the physical properties of the final product will be adversely aifected. These include loss of strength and a lower resistance to repeated flexing.
- the synergistic combination it is desirable to use a minimum amount of secondary lower molecular weight additive to minimize any adverse effects on the properties of the fibers.
- An addition of the secondary additive above the limit stated (50%) may be in excess of that required to associate and complex with the primary modifier which makes up 50% to by weight of the synergistic combination. As a result, the excess secondary additive may sweat out of the polyolefin and interfere with processing.
- the addition of the secondary additive not go below 5% by weight because below this level very little improvement is achieved in dyeability.
- the primary polymeric modifier of the combination should comprise at least 25% by weight of an oxygen containing N-heterocycle monomeric unit in combination with not more than 75% of an ethylenically unsaturated monomeric unit having no basic groups. If the latter unit is present in an amount over 75 you obtain very low levels of dyeability. It is therefore necessary to use very excessive amounts of modifier to achieve desired results.
- the ethylenically unsaturated unit is present between 50 to 75 by weight, higher levels of addition are required.
- the melting point of the overall composition may be reduced to such an extent that the modifier, particularly at higher levels of addition, may give some problems 111 processing.
- hydrophilic polymeric primary modifiers as part of my synergistic combination which may be soluble in either water or an oxygenated solvent but which are not soluble in the polyolefin.
- modifiers which are fusible and can be dispersed in the polyolefin.
- My hydrophilic primary polymeric modifiers must be fusible with the polyolefin. This is necessary for the formation of a continuous network of modifier throughout the polyolefin in order to permit dye penetration and efiicient coordination of the dye and modifier throughout the film or fiber.
- the synergistic combination of this invention may be used to increase opacity and the afiinity of the polyolefin for finishes. They may also be used to improve the printability of the polyolefin, increase the adhesion of the polyolefin to other materials, or to reduce the overall static propensity of the final product. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced th erwise than as specifically described.
- a polymeric composition having improved aflinity for dyes consisting essentially of:
- a matrix of stereoregular polyolefin taken from the group consisting of: polypropylene, polymethylpentene, and polymethylbutene;
- said matrix having dispersed therein between 2 and 20 percent by weight of a synergistic combination consisting of:
- modifying copolymer which is hydrophilic, non-soluble in the polyolefin, and fusible at a temperature between 150 12 C. and 350 C.
- said modifying copolymer being selected from the group consisting of:
- N-vinyl p-yrrolidone/ 10% ethylene said percent being by weight
- composition of claim 1 wherein:
- said copolymer consists of 50% by weight N-vinyl methyloxazolidinone in combination with 50% by Weight of vinyl acetate, and said lower molecular weight organic substance consists of fatty esters of polyhydroxy compounds.
- composition of claim 1 wherein:
- said copolymer consists of 30 to 70% by Weight of N-vinyl pyrrolidone in combination with 30 to 70% vinyl acetate, and said lower molecular weight organic substance consists of alkoxylated fatty amines.
- composition of claim 1 wherein:
- said copolymer consists of 60% by weight of N-vinyl morpholinone in combination .with 40% by weight of methyl acrylate, and said lower molecular weight organic substance consists of fatty esters of polyglycols.
- composition of claim 1 wherein: References Cited said copolymer consists of 70% by weight of N-vinyl UNITED STATES PATENTS pyrrolidone in combination with 30% by weight of ethyl acrylate, and said lower molecular weight 3,153,680 10/1964 Guisfiniani et 260 897 organic substance consists of fatty ethers of poly- 5 FOREIGN PATENTS glycols. l
- composition of claim 1 wherein: 83416O 5/1960 Great Bntam' said copolymer consists of 60% by weight of N-acrylyl pyrrolidone in combination with 40% by weight MURRAY TILLMAN Pnmary Exammer' ethyl acrylamide, and said lower molecular Weight 10 D. J. BREZNER, Assistant Examiner. organic substance consists of alkyl phosphoric acid.
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Description
United States Patent M 3,337,652 MODIFICATION OF STEREOREGULAR POLYOLEFINS Jack J. Press, 12-18 E. Laurelton Parkway, Teaneck, NJ. 07666 No Drawing. Filed Oct. 26, 1964, Ser. No. 406,631 6 Claims. (Cl. 260-895) I particularly, this invention relates to polymeric compositions having improved afiinity for dyes, said compositions containing a major amount of stereoregular polyolefins.
It is known that polyethylene is vastly unsuitable for the production of textile fibers due to the relatively poor properties imparted to the product. For one thing, staple polyethylene fiber will not hold a crimp and this is necessary for textile processing. For another, it is useless to make a textured or stretch yarn from continuous filament polyethylene yarn because the characteristics imparted to the yarn are not maintained during weaving, dyeing, or ordinary use. Further, the material from which a fabric is made must be thermally stable before it may be subjected to ordinary use. It must not have a relatively low melting point, and the final fabric must not have a high degree of heat sensitivity, nor relatively soft mechanical properties at elevated temperatures. However, the thermal properties of a polyethylene fabric are such that it is impossible to subject it to ordinary ironing without physically damagingthe fabric and it has been found to shrink in the conventional dryer. As is apparent from the foregoing, polyethylene cannot be utilized in the manufacture of everyday fabrics for ordinary use.
In recent times, it has been found that certain linearcrystalline hydrocarbon polymers containing stereoregular macromolecules and having melting points between 150 and 300 C. can be used for the production of textile fibers without the inherent diificulties encountered with the use of polyethylene polymers for this purpose. Aside from melting point differences, polypropylene with a tertiary carbon and a methyl side chain, crystallizes differently and has a much higher resilience and elasticity. These properties are esesntial in generally useful textile fiber. Further, polymers of olefinic hydrocarbons containing stereoregular macromolecules, such as polypropylene, polymethylpentene, and polymethylbutene, offer considerable advantages in the production of fibers, particularly because of their good mechanical properties and light weight. However, such polmyers have not been satisfactory because of their poor afiinity for dyes, this poor afiinity being due to the particular chemical nature of such polyolefinic hydrocarbons.
Many processes have been proposed in order to improve the aflinity of such polyolefinic hydrocarbons for dyes, such as the addition of soluble solid substances to the molten polyolefin before spinning. The addition of basic substances facilitates dyeing with acid dyes, whereas the addition of acid substances favors dyeing with basic dyes. However, such processes have not been completely satisfactory because soluble modifiers interfere with crystallization, impair strength and thermal stability, and are not sufficiently available in the amorphous regions where dyeing takes place.
It has also been proposed to increase the afiinity of dyes for polyolefin fibers by grafting monomers onto the fibers after subjecting the fibers to a preliminary peroxida- Patented Aug. 22, 1967 tion or to high energy radiation. When such processes are applied to the polyolefin after it is in filamentary form the surface properties of the grafted fibers are considerably modified and the dye receptivity is improved. However, when such processes are applied to highly crystalline filaments, any grafting onto the preformed fibers takes place only at the surface. Therefore, subsequent dyeing is limited to the surface portion of the fiber and the dye does not penetrate inside the fiber.
In my copending application titled Modification of Stereoregular Polyolefins With Hydrophilic Copolymers, Ser. No. 400,612, filed Sept. 30, 1964, I teach that the affinity of polyolefins for dyes may be enhanced through the use of selected hydrophilic, nonsoluble copolymers consisting of oxygen containing N-heterocyclic monomeric units in combination with neutral ethylenically unsaturated monomeric units. The level of addition ranges from 2 to 20% by weight based on the polyolefin.
Now, I have discovered that the affinity of polyolefins for dyes may be further improved, over and above the improvement achieved with the above polymeric materials, if the modifier incorporated in the polyolefin is one of a specified class of copolymers in combination with selected class of secondary polar additives. Surprisingly, I have found that even at low levels of addition, I obtain synergistic improvements in dyeability by replacing between 5% and 50%, preferably only up to 25%, of the above primary hydrophilic copolymeric modifiers with selected liquid, wax, or polymeric secondary polar modifiers having negligible dyeability by themselves.
These secondary polar modifiers are generally low molecular weight additives or possess melting points somewhat lower than the polyolefin itself. These secondary additives associate themselves with the primary hydrophilic polymeric modifier in such a way as to give synergistic combinations that are fusible at temperatures not exceeding the temperature of processing of the polyolefin (150 C. to 350 C.) and have improved processability and dyeability.
As an added advantage, the use of the secondary polar additives improves brightness and clarity of the final film or luster and brightness of the final fiber. The whiteness of the fiber is also improved because a smaller amount of the primary polymeric modifier, which is responsible for the off-white color, is utilized. There is also an improvement in the ease and uniformity of dispersion of the composition. There is less blockage of filters and spinerette holes by the composition and this tends towards an improvement in processability. An economic advantage is also associated with the use of the present composition for a smaller amount of the more expensive primary polymeric modifier is utilized in the composition while still maintaining or improving the affinity of the composition for dyes.
It is therefore an object of this invention to provide polymeric compositions having improved affinity for dyes devoid of difficulties of the prior art.
Included in this invention are stereoregular polyolefin structures with increased affinity for dyes comprising a matrix of a stereoregular polyolefin taken from the group consisting of (a) polypropylene, (b) polymethylpentene, and (o) polymethylbutene, said matrix having dispersed therein between 2 and 20% of a synergistic combination consisting of:
(l) 50 to of a modifying copolymer which is hydrophilic, non-soluble in the polyolefin, and fusible at a temperature between C. and 350 C., said modifying copolymer being selected from the group consisting of:
(a) 30 to 70% N-vinyl pyrro1idone/30 to 70% vinyl acetate,
(b) 60% N-vinyl pyrrolidone/40% vinyl methyl ether,
(c) 80% N-vinyl pyrrolidone/20% styrene,
(d) 70% N-vinyl pyrrolidone/30% ethyl acrylate,
(e) 70% N-isoprenyl pyrrolidone/30% ethylene oxide,
(f) 60% N-acrylyl pyrrolidone/40% ethyl acrylamide,
all said percentages being percent by weight; and
(2) 5 to 50% of a lower molecular weight organic substance having at least one alkyl group with 6 to 30 carbons, said substance selected from the group consisting of:
(a) alkyl esters of polyhydroxy compounds, (b) alkyl esters of polyglycols, 60 to 4000 M, (c) alkyl ethers of polyglycols, 60 to 4000 M, (d) alkyl ethers of polyhydroxy compounds, (e) alkoxylated alkyl amines,
(f) di (2ethylhexyl)phosphoric acid,
(g) stearyl phosphoric acid,
(h) salts of dodecylbenzene sulfonic acid,
(i) salts of naphthalene sulfonic acid,
(j) N-lauryl trimethylene diamine, and
(k) salts of di (2-ethylhexyl) phosphoric acid,
said synergistic combination being fusible at a temperature of processing of the polyolefin (150 to 350 C.) and forming a complex in said polyolefin.
The stereoregular polyolefins which may be used within the concept of this invention include isotactic and syndiotactic polyolefins. These materials are usually made by utilizing stereo-specific catalysts which give polymers which are substantially linear and which develop a high degree of crystallinity.
A preferred class of my primary polymeric modifiers consists of copolymers derived from oxygen containing N-alkenyl heterocyclic monomers, particularly alkenyl substituted lactams, oxazolidone, oxazolidinone and morpholinone monomers. This class of polymers is highly desirable because it has little or no basicity and has very high levels of affinity for a Wide range of dyes. My preferred primary modifiers are neutral or only very slightly basic and yet in polyolefins, surprisingly, have higher dyability with anionic (acid) dyes than the much more basic polymeric modifiers. In these monomers and polymers, the alkenyl substituted nitrogen is part of an internal amide group and is essentially neutral. Additional ring and substituted oxygen containing groups are more acidic than the substituted amide nitrogen and further reduce basicity.
The secondary polar additives which may be used with the primary modifier to give synergistic combinations include the following:
(1) Alkyl esters of polyhydroxy compounds such as:
(21) glycerol monostearate, (b) glycerol distearate, (c) glycerol tristearate, (d) glycerol mono/dilaurate, (e) sorbitan monostearate, and (f) sorbitan dilaurate. (2) Alkyl esters of polyglycols (M 60 to 4000) such as:
(a) ethylene glycol monostearate, (b) polyethylene glycol 200 monostearate, (c) polyethylene glycol 200 distearate,
(d) polyethylene glycol 4000 distearate, (e) propylene glycol monostearate, (f) polypropylene glycol 600 monooctate, (g) butylene glycol monostearate, (h) polybutylene glycol 800 monostearate, (i) hexylene glycol monooctate, (j) hexylene glycol adipate, and (k) poly(hexylene glycol adipate) 800 to 5000 M. (3) Alkyl ethers of polyglycols (60 to 4000 M) such as:
(a) ethylene glycol monostearyl ether, (b) ethylene glycol monolauryl ether, (c) polyethylene glycol 200 monostearyl ether, (01) polyethylene glycol 200 monolauryl ether, (e) polyethylene glycol 200 distearyl ether, (f) polyethylene glycol 200 monononylphenol ether, (g) polyethylene glycol 4000 monostearyl ether, (h) polyethylene glycol 4000 distearyl ether, (i) propylene glycol monostearyl ether, (j) propylene glycol monolauryl ether, (k) polypropylene glycol 600 monolauryl ether, (1) butylene glycol monostearyl ether, (m) hexylene glycol monooctyl ether. (4) Alkyl ethers of polyhydroxy compounds such as:
(a) glycerol monostearyl ether, (b) glycerol distearyl ether, (0) glycerol dilauryl ether, (d) glycerol dihexyl ether, (e) sorbitan monostearyl ether, and (f) sorbitan dioctyl ether. (5) Alkyloxylated amines such as:
(a) tertiary stearyl amine with '15 moles ethylene oxide, (b) tertiary stearyl di (hydroxyethyl) amine, (c) tertiary stearyl di (hydroxypropyl) amine, (d) tertiary stearyl di (hydroxybutyl) amine, (e) tertiary lauryl di (hydroxypropyl) amine, (f) tertiary lauryl amine with 15 moles of ethylene oxide, (g) tertiary stearyl amine with 15 moles of propylene oxide, (h) quaternary stearyl di (hydroxyethyl) methyl ammonium sulfate, (i) quaternary stearyl di (hydroxyethyl) methyl ammonium chloride, and (j) quaternary stearyl methyl ammonium chloride with 15 moles of ethylene oxide. (6) Alkyl phosphoric acids and salts such as:
(a) di (Z-ethylhexyl) phosphoric acid, (b) sodium salt of di (2-ethylhexyl) phosphoric acid, (c) potassium salt of di (2-ethylhexy1) phosphoric acid, (d) isopropyl amine salt of di (2-ethylhexyl) phosphoric acid, (e) triethanolamine salt of di (2-ethylhexyl) phosphoric acid, (f) monostearyl phosphoric acid, (g) potassium salt of monostearyl phosphoric acid, (h) distearyl phosphoric acid, (i) sodium salt of distearyl phosphoric acid, (j) monolauryl phosphoric acid, (k) lauryl ethyl phosphoric acid, and (l) dioctyl phosphoric acid. (7) Miscellaneous compounds such as:
(a) N-lauryl trimethylene amine, (b) N-stearyl trimethylene diamine, (c) perfluorononylic acid, (d) dihydrogenated tallow-methyl amine, (e) stearic acid, (f) alkylene (2 to 4 carbon) oxide derivatives of alkyl (6 to 30 carbons) amide, (g) polyalkylene glycols having 2 to 4 carbons and 4 to 50 alkylene oxide groups. (8) Alkyl and aryl sulfonic acids and salts such as:
(a) dodecylbenzene sulfonic acid,
(b) sodium salt of dodecylbenzene sulfonic acid,
(c) potassium salt of dodecylbcnzene sulfonic acid,
(d) isopropyl amine salt of dodecylbenzene sulfonic acid,
(e) trialkanolamine salt of dodecylbenzene sulfonic acid,
(f) lauryl sulfonic acid,
maintained for 2 hours. The dye samples were then rinsed, given a minute 95 C. launder in the dye pot at a 20 to 1 bath to sample ratio with a 5 gram per gallon Tide detergent solution. The samples were then rinsed, dried, and judged for depth and uniformity of shades. The results of such test are set forth in the table below:
All percentages are by weight.
(g) sodium salt of lauryl sulfonic acid,
(h) naphthalene sulfonic acid,
(i) sodium salt of naphthalene sulfonic acid,
(j) potassium salt of naphthalene sulfonic acid, and
(k) formaldehyde condensate of naphthalene sulfonic acid.
The following examples set forth typical synergistic combinations of primary and secondary modifiers falling within the concept of this invention. Each is followed by results quite clearly illustrating the synergism en countered when each combination is introduced into the stereoregular polyolefin.
Example I I prepared discs of polyolefin in the following manner utilizing as modifier N-vinyl-S-methyl-2-oxazo1idinone in a balanced weight fraction copolymer with vinyl acetate (VOOM/Va) (Devlex A515, Dow Chemical Co.) alone and in combination with (GMS) g1ycerol monostearate.
Various percent additions, as indicated in the table which follows, were each uniformly mixed, as solutions or as finely divided solid, with separate 5 gram samples of a finely powdered (SO -200 mesh) commercial, unin hibited isotactic polypropylene (molecular weight about 350,000, melting point about 170 C., melt index of 3, and isotacticity of 95%).
The mixtures were then air dried (to remove some solvent) and then heated in a drying oven at 80 C. until all of the solvent had been removed.
Each of the dried mixtures was prepared in the form of a disc in the following manner: The powder of each sample Was spread uniformly in a circular shouldered Pyrex glass dish with an inside diameter of 4 inches. The dishes were then covered by an inner nesting circular shouldered Pyrex glass dish with a bottom outer separation rib projecting downwardly about 0.05 inch. The assembly weighted with a preheated 5 pound weight was then placed in an oven at 250 C. for 6 to minutes. Then the weight was removed and the assembly was placed in a refrigerator at about 4 C. to cool. The assembly dishes were then separated to give a fuzed disc.
A portion of each of the fusion discs after water rinsing were individually placed in a separate dye pot together with times its weight of distilled Water and from 0.5 to 2% of the dye on the weight of the sample.
The following dyes were utilized in separate baths, viz.
AMRColour Index, Acid Red 182, AR-Colour Index, Acid Red 127, DO-Colour Index, Disperse Orange 3, and DLVLatyl Violet 2R, Disperse Dye.
The dye baths were each heated over an hour to a temperature of about 95 C. and the temperature was" As indicated, an improvement in dyeability is achieved, although accompanied by a 20% reduction in the amount of copolymer utilized in the composition if a selected lower melting additive is substituted in part for the copolymer. As an added advantage, higher levels of dispersion and dyeability may be achieved with higher levels of addition. This is surprising because when the primary polymeric modifiers are utilized alone, one obtains poor dispersibility with higher levels of addition.
Example 2 In this example, tests similar to those of Example 1 were performed except that, in this case, the modifier containing polyolefin was extruded into fiber, drawn and then dyed using conventional equipment and processes.
The formulation was melt mixed in a continuous screw extruder, forced through a 60 mil die at 260 C. and collected at ambient temperature on a reel as a 30 denier filament.
The filament was then heat stretched 300% to give a strong, oriented 10 denier fiber. Fiber skeins Were then scoured with detergent at 140 F., and dyed at the boil for one hour at 2-0/ 1 bath to fiber ratio.
The fiber, as spun, was judged subjectively for uniformity of dispersion of the modifiers in the polyolefin and the dyeings were judged for level of dyeability (depth of shade) with the following dyes:
DLV-Latyl Violet 2R, Disperse Dye, DO-Colour Index, Disperse Orange 3, AMR-Colour Index, Acid Red 182, AR-Colour Index, Acid Red 127.
The synergistic combination, which was utilized as the modifier, consisted of a copolymer, 50% vinyl methyloxazolidinone with 50% vinyl acetate (VOOM/Va), in combination with (GMS)-glycerol monostearate.
TABLE* Percent VOOM/Va; 4 9. Percent GMS 1 1. Dispersibility in Polyolefin Excellent Good/excellent.
Dyeability with:
(a) DLV,DO Medium/dark--. Dark.
(b) MAR,AR Medium Medium/dark.
All percentages being by weight.
As indicated above, one obtains improvement in dyeability even when the combination is reduced to fiber form.
Example 3 dispersion and depth of coloration. The results of these tests are tabulated below:
2, the modifier containing polyolefin was extruded into fiber, drawn, and then dyed using conventional equipment and processes.
The synergistic combination, which was utilized as the modifier, consisted of a copolymer, 70% vinyl pyrrolidone with vinyl acetate (VP/Va), in combination with Dyeability with dyes Dispersibillty Secondary Additive in Polyolefin (b) a DLV, DO AMR, AR
Blank Fair Polyethylene glycol 200 nonylphenol. Good/excellent. Ethylene glycol monostearate Excellent Polyethylene glycol 200 distearate .do Do. Dihydrogenated tallow methyl amine Good Medium/dark. Lauryl di (hydroxy propyl) amine Good/excellent. Medium. Tertiary lauryl amine with 15 moles of ethyl- Excellent Medium/dark.
ene oxide. Quaternary hydrogenated tallow di (hy- ...do do D0.
droxymethyl) methyl ammonium sulfate. Stearyl di (hydroxy ethyl) amine. Good/excellent.. do Medium. Quaternary stearyl di (hydroxyethyl) methyl -do Medium/dark... Medium/dark.
ammonium chloride. Tertiigry stearyl amine with 15 moles ethylene Excellent Dark Do.
ox e. Di (2'ethylhexyl) phosphoric acid. "do... do Medium. Stearic acid do do D0.
Note that, in all cases, the affinity of the polyolefin composition for dyes was increased by addition of a (TSA)tertiary stearyl amine with 15 moles ethylene All percentages being by weight.
selected secondary additive. In the case of the blank, the dispersibility was only fair while the depth of coloration lies in the medium range. With the addition of the selected secondary additive, the dispersability was good to excellent and the depth of coloration was increased, in some cases, from medium to medium/dark and dark. This improvement, in all cases, is the direct result of the synergistic combination in the olefinic composition as taught by the present concept.
Example 4 sition.
Example 5 In accordance with Example I, I prepared discs using as modifiers the copolymers enumerated below, both alone, and in combination with selected secondary additives. The discs were dyed following the procedure heretofore described and the finished discs were judged subjectively In accordance with the procedure set forth in Example for uniformity of dispersion and depth of color.
Dyeability with dyes Copolymer Percent Percent Secondary Additive Percent* Dispersibility Ratio Addition Addition in Polyolefin (a) DLV, DO (b) AMR, AR
(a) N-vinyl pyrrolidone- /40 4 Light/medium.. Light.
vinyl methyl ether. (13).... do 60/40 4 Ethylene glycol 1 Excellent Medium/dark Medium.
monostearate. (c) N-ginyl pyrrolidone- 80/20 4 Light/mediunn, Light.
5 yrene. (d) -do 80/20 4 Di(2 ethylhexyl) 1 Good Medium/dark Medium.
phosphoric acid. (e)- N-vinylpyrrolidone- 70130 4 Medium- Light.
ethyl acrylate. (t) d0 /30 4 Tertiary stearyl 1 Excellent Dark. Medium/dark.
amine with 15 moles of ethylene oxide. (g) N-isoprenyl pyrroli- 70/30 4 Medium Light.
done-ethylene oxide. (h) d0 70/30 4 Ethylene glycol 1 Excellent Dark. Medium/dark.
distearate. (i) N-acrylyl pyrroli- 60/40 4 Medium Light.
done ethyl acrylamide.
' Dyeability with dyes Gopolymer Percent? Percent* Secondary Additive Percent? Dispersibility Ratio Addition Addition in Polyolefin (a) DLV, DO (1)) AMR, AR
(j) .d 60/40 4 Dihydrogenated l Good/exeellent Dark Medium.
tallow-methyl amine. (k) N-vinyl oxazolidone- 60/40 4 Medium Light.
aerylonitrile. (l) v do 60/40 4 Stearyl di-(hydroxy 1 Good/excellent. Dark Medium.
ethyl) amine. (m) N-vinyl methyl 70/30 7 4 Light/medium. Light.
oxazolidinonean na a ami e. (n) "333m 70/30 4 Darlg Medium/dark. (0),--- N-vinyl morpho- 60/40 4 Medlum Light.
linerl ile-melthtyl me ac a e. v (p) .do 60/40 4 Tertiary stearyl 1 Good/excellent" Medium/dark--. Medium.
amine with moles ethylene oxide. I (q) N-vinyl l pyrrolidone- 90/10 4 Medium Light/medium. eth one I (r) "iii; 90/10 4 Tertiary stearyl 1 Good Medium/dark- Medium.
amine with 15 moles ethylene oxide.
*All percentages being by weight.
Note that the affinity of the polyolefin for dyes is increased, when one of the above selected secondary additives are utilized, in conjunction with the copolymers listed, to modify the composition of the polyolefin. This being an improvement, in all cases, over the use of the copolymer alone for the same purpose.
Many alternate methods of combining my modifiers with polyolefins are readily available. They may be combined during formation of the polymeric modifier or during actual polymerization of the polyolefin, with or without melting. They may be added to freshly polymerized polyolefin, which is still in solution in a suitable solvent, in the powdered form, or as a solution in a compatible solvent, or merely as a dispersion. They may be added to the polyolefin during precipitation, washing, neutralizing or compounding of the freshly prepared polyolefin prior to drying. This may be accomplished by adding the modifier as a powder or as a solution which is a non-solvent for the The modifiers may also be melt mixed during processing or blending of the polymer prior to use in extension of fiber, film, coating or plastic. It may also be added as a liquid or powder to finely ground or micronized polyolefin polymers and then melt dispersed in situ during hot dip or spray coating or during spreading and heat coating operation. They may be incorporated in polyolefin solutions or emulsion and then applied to surfaces with or without heating.
In may copending application, I show the use of selected hydrophilic polymers to improve the dyeability of the stereoregular, high melting polyolefin. The level of addition of these primary modifiers should be between 2 and of the weight of the overall composition including polyolefin. As shown and substantiated herein by the results which follow each of the examples, the utility of these primary modifiers may be vastly improved by replacing from 5 to 50%, preferably not more than of the primary modifier by a secondary modifier, heretofore listed, which has limited utility by itself.
The synergistic effects of the combinations, as taught, on the polyolefin includes vastly improved dyeability. However, the listed secondary modifiers also enhance the compatibility of the primary polymeric modifier in the polyolefin. These advantages are also accompanied by improvements in processing of the overall combination and, surprisingly, many infusable primary modifiers are rendered fusible and may be utilized within the concept of this invention to improve the dyeability of a polyolefin structure as heretofore taught.
The level of additionto the polyolefin of the synergistic combination heretofore described should be between 2 and 20% of the weight of the overall composition. If less than 2% is utilized, significant improvement will not be achieved in dyeability. If an amount greater than 20% is added to the polyolefin, many of the physical properties of the final product will be adversely aifected. These include loss of strength and a lower resistance to repeated flexing.
As to the synergistic combination, it is desirable to use a minimum amount of secondary lower molecular weight additive to minimize any adverse effects on the properties of the fibers. An addition of the secondary additive above the limit stated (50%) may be in excess of that required to associate and complex with the primary modifier which makes up 50% to by weight of the synergistic combination. As a result, the excess secondary additive may sweat out of the polyolefin and interfere with processing.
I prefer however to use not more than 25% by weight of the secondary polar additive, since even between 25 and 50% there might be excessive reduction in the melting point of the combination and this would result in difficulties in processing, particularly drying.
It is also preferred that the addition of the secondary additive not go below 5% by weight because below this level very little improvement is achieved in dyeability.
The primary polymeric modifier of the combination should comprise at least 25% by weight of an oxygen containing N-heterocycle monomeric unit in combination with not more than 75% of an ethylenically unsaturated monomeric unit having no basic groups. If the latter unit is present in an amount over 75 you obtain very low levels of dyeability. It is therefore necessary to use very excessive amounts of modifier to achieve desired results.
If the ethylenically unsaturated unit is present between 50 to 75 by weight, higher levels of addition are required. The melting point of the overall composition may be reduced to such an extent that the modifier, particularly at higher levels of addition, may give some problems 111 processing.
However, if the latter monomeric units are present below 50% by weight of the overall primary modifier, lower levels of addition can be used to improve dyeability without processing problems resulting from an excessive reduction in melting point. This represents the optimum from a commercial point of view.
Under present concept, I prefer hydrophilic polymeric primary modifiers as part of my synergistic combination which may be soluble in either water or an oxygenated solvent but which are not soluble in the polyolefin. I do prefer modifiers which are fusible and can be dispersed in the polyolefin.
Prior experience with comparatively less hydrophobic fiber forming polymers, such as polyacrylonitrile polymers and polyamides, have shown that the use of hydro philic, water soluble or dispersible, modifiers is impractical. Mainly, because excessive amount of the modifier are leached out in scouring and dyeing processes. Surprisingly, I have found that my hydrophilic polymeric modifiers, when melt dispersed in the more hydrophobic polyolefin, have good dispersion stability and are not susceptible to leachage.
I have found that at comparatively low levels of addition, my synergistic combination, as taught, confers good dyea bility on the polyolefin Without the necessity for costly and sometimes impractical post treatments.
My hydrophilic primary polymeric modifiers must be fusible with the polyolefin. This is necessary for the formation of a continuous network of modifier throughout the polyolefin in order to permit dye penetration and efiicient coordination of the dye and modifier throughout the film or fiber.
The use of a non-fusible cross-linked modifier, which results in poor dispersion, is ineffectual. The required modifier network in such a case cannot be formed and the discrete, separate particles are surrounded by unmodified areas within the polyolefin matrix. As as result, dyeing is limited to the fiber surface and the dye cannot penetrate into the interior of the fiber where it is most desired.
It is generally recognized that dyeing takes place almost entirely in the more open and readily accessible amorphous areas. When a soluble modifier is utilized, it is usually spread throughout the amorphous and crystalline areas of the polyolefin. As a result, the modifier in the crystalline areas is not available for improvement in dyeability. It also interferes with crystallization and adversely affects strength and thermal stability. However, my synergistic combination is not sufficiently compatible to be a part of the more uniform and denser crystalline areas. It appears to concentrate in the more amorphous areas where it is necessary for dyeability. It has also been found that an increase in molecular weight of my modifiers, further reduces compatibility with stereoregular polyolefins and promotes concentration of the modifier in the more amorphous regions where it may improve the dyeability of the polyolefinic matrix.
Obviously, many modifications and variations of the present invention are possible in the light of the above teaching. For instance, the synergistic combination of this invention may be used to increase opacity and the afiinity of the polyolefin for finishes. They may also be used to improve the printability of the polyolefin, increase the adhesion of the polyolefin to other materials, or to reduce the overall static propensity of the final product. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced th erwise than as specifically described.
I claim:
1. A polymeric composition having improved aflinity for dyes consisting essentially of:
a matrix of stereoregular polyolefin taken from the group consisting of: polypropylene, polymethylpentene, and polymethylbutene;
said matrix having dispersed therein between 2 and 20 percent by weight of a synergistic combination consisting of:
(1) 50 to 95% by weight of a modifying copolymer which is hydrophilic, non-soluble in the polyolefin, and fusible at a temperature between 150 12 C. and 350 C., said modifying copolymer being selected from the group consisting of:
(a) 30 to 70% N-vinyl pyrrolidone/ 30 to 70% vinyl acetate, (b) 60% N-vinyl pyrrolidone/40% vinyl methyl ether, (c) N-vinyl pyrrolidone/20% styrene, (d) 70% N-vinyl pyrrolidone/ 30% ethyl acrylate, (e) 70% N-isoprenyl pyrrolidone/ 30% ethylene oxide,
(f) 60% N-acrylyl pyrrolidone/ 40% ethyl acrylamide,
(g) 50% N-vinyl methylpyrrolidone/50% vinyl methyl ether, (h) 60% N-vinyl oxazolidone/ 40 acrylonitrile, (i) 70% N-vinyl oxazolidinone/ 30% hydroxypropyl methacrylamide,
(j) 50% N-vinyl- 5 -methyl-2-oxazolidinone/ 5 0% vinyl acetate,
(k) 60% N-vinyl morpholinone/ 40% methyl acrylate, and
(1) N-vinyl p-yrrolidone/ 10% ethylene, said percent being by weight, and
(2) 5 to 50% by weight of a lower molecular Weight polar organic substance having at least one alkyl group with 6 to 30 carbons, said substance selected from the group consisting of:
(a) alkyl esters of polyhydroxy compounds,
(b) alkylene amines,
(0) fatty amides,
(d) alkyl ethers of polyhydroxy compounds,
(e) alkoxylated amines,
(f) di (Z-ethylhexyl) phosphoric acid,
(g) stearyl ester of phosphoric acid,
(h) salts of dodecylbenzene sulfonic acid,
(i) salts of naphthalene sulfonic acid,
(j) salts of di (2-ethylhexyl) phosphoric acid; said synergistic combination being fusible with said polyolefin at processing temperatures up to 350 C.
2. The composition of claim 1 wherein:
said copolymer consists of 50% by weight N-vinyl methyloxazolidinone in combination with 50% by Weight of vinyl acetate, and said lower molecular weight organic substance consists of fatty esters of polyhydroxy compounds.
3. The composition of claim 1 wherein:
said copolymer consists of 30 to 70% by Weight of N-vinyl pyrrolidone in combination with 30 to 70% vinyl acetate, and said lower molecular weight organic substance consists of alkoxylated fatty amines.
4. The composition of claim 1 wherein:
said copolymer consists of 60% by weight of N-vinyl morpholinone in combination .with 40% by weight of methyl acrylate, and said lower molecular weight organic substance consists of fatty esters of polyglycols.
5. The composition of claim 1 wherein: References Cited said copolymer consists of 70% by weight of N-vinyl UNITED STATES PATENTS pyrrolidone in combination with 30% by weight of ethyl acrylate, and said lower molecular weight 3,153,680 10/1964 Guisfiniani et 260 897 organic substance consists of fatty ethers of poly- 5 FOREIGN PATENTS glycols. l
6. The composition of claim 1 wherein: 83416O 5/1960 Great Bntam' said copolymer consists of 60% by weight of N-acrylyl pyrrolidone in combination with 40% by weight MURRAY TILLMAN Pnmary Exammer' ethyl acrylamide, and said lower molecular Weight 10 D. J. BREZNER, Assistant Examiner. organic substance consists of alkyl phosphoric acid.
Claims (1)
1. A POLYMERIC COMPOSITION HAVING IMPROVED AFFINITY FOR DYES CONSISTING ESSENTIALLY OF: A MATRIX OF STEROREGULAR POLYOLEFIN TAKEN FROM THE GROUP CONSISTING OF: POLYPROPYLENE, POLYMETHYLPENTENE, AND POLYMETHYLBUTENE; SAID MATRIX HAVING DISPERSED THEREIN BETWEEN 2 AND 20 PERCENT BY WEIGHT OF A SYNERGISTIC COMBINATION CONSISTING OF: (1) 50 TO 95% BY WEIGHT OF A MODIFYING COPOLYMER WHICH IS HYDROPHILIC, NON-SOLUBLE IN THE POLYOLEFIN, AND FUSIBLE AT A TEMPERATURE BETWEEN 150* C. AND 350*C., SAID MODIFYING COPOLYMER BEING SELECTED FROM THE GROUP CONSISTING OF: (A) 30 TO 70% N-VINYL PYRROLIDONE/ 30 TO 70% VINYL ACETATE, (B) 60% N-VINYL PYRROLIDONE/40% VINYL METHYL ETHER, (C) 80% N-VINYL PYRROLIDONE/20% STYRENE, (D) 70% N-VINYL PYRROLIDONE/30% ETHYL ACRYLATE, (E) 70% N-ISOPRENYL PYRROLIDONE/ 30% ETHYLENE OXIDE, (F) 60% N-ACRYLYL PYRROLIDONE/ 40% ETHYL ACRYLAMIDE, (G) 50% N-VINYL METHYLPYRROLIDONE/50% VINYL METHYL ETHER, (H) 60% N-VINYL OXAZOLIDONE/ 40% ACRYLONITRILE, (I) 73% N-VINYL OXAZOLIDINONE/ 30% HYDROXYPROPYL METHACRYLAMIDE, (J) 50% N-VINYL - 5 - METHYL-2-OXAZOLIDINONE/50% VINYL ACETATE, (K) 60% N-VINYL MORPHOLINONE/ 40% METHYL ACRYLATE, AND (1) 90% N-VINYL PYRROLIDONE/10% ETHYLENE, SAID PERCENT BEING BY WEIGHT, AND (2) 5 TO 50% BY WEIGHT OF A LOWER MOLECULAR WEIGHT POLAR ORGANIC SUBSTANCE HAVING AT LEAST ONE ALKYL GROUP WITH 6 TO 30 CARBONS, SAID SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF: (A) ALKYL ESTERS OF POLYHYDROXY COMPOUNDS, (B) ALKYLENE AMINES, (C) FATTY AMIDES, (D) ALKYL ETHERS OF POLYHYDROXY COMPOUNDS, (E) ALKOXYLATED AMINES, (F) DI (2-ETHYLHEXYL) PHOSPHORIC ACID, (G) STEARYL ESTER OF PHOSPHORIC ACID, (H) SALTS OF DODECYLBENZENE SULFONIC ACID, (I) SALTS OF NAPHTHALENE SULFONIC ACID, (J) SALTS OF DI (2-ETHYLHEXYL) PHOSPHORIC ACID; SAID SYNERGISTIC COMBINATION BEIN FUSIBLE WITH SAID POLYOLEFIN AT PROCESSING TEMPERATURES UP TO 350*C.
Priority Applications (2)
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US406631A US3337652A (en) | 1964-10-26 | 1964-10-26 | Modification of stereoregular polyolefins |
US502719A US3425969A (en) | 1961-04-04 | 1965-10-22 | Process of preferentially modifying stereoregular polyhydrocarbons to improve dyeability |
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US406631A US3337652A (en) | 1964-10-26 | 1964-10-26 | Modification of stereoregular polyolefins |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3468864A (en) * | 1965-10-18 | 1969-09-23 | Continental Oil Co | Oil soluble alkaryl sulfonate lithium and polyvalent metal salts in polyolefin fibers and films |
US3530201A (en) * | 1966-12-06 | 1970-09-22 | Uniroyal Inc | Dyeable polyolefins containing thermoplastic nitrogen containing polymers and polyethylene oxide |
US3652198A (en) * | 1968-09-13 | 1972-03-28 | Uniroyal Inc | Mixture of filaments capable of being dyed to a multicolor pattern with anionic disperse dyes |
US4133844A (en) * | 1977-07-22 | 1979-01-09 | E. I. Du Pont De Nemours And Company | Product and process |
US5714258A (en) * | 1992-07-02 | 1998-02-03 | Hoechest Celanese Corporation | Fiber having improved properties, compositions for producing such fibers, and process for improving properties of fibers |
WO2022210543A1 (en) * | 2021-03-29 | 2022-10-06 | Tdk株式会社 | Copolymer, piezoelectric material, piezoelectric film, and piezoelectric element |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB834160A (en) * | 1957-04-10 | 1960-05-04 | Gen Aniline & Film Corp | Pigment composition |
US3153680A (en) * | 1959-08-03 | 1964-10-20 | Montedison Spa | Poly-alpha-olefin compositions having improved dye affinity |
-
1964
- 1964-10-26 US US406631A patent/US3337652A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB834160A (en) * | 1957-04-10 | 1960-05-04 | Gen Aniline & Film Corp | Pigment composition |
US3153680A (en) * | 1959-08-03 | 1964-10-20 | Montedison Spa | Poly-alpha-olefin compositions having improved dye affinity |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3468864A (en) * | 1965-10-18 | 1969-09-23 | Continental Oil Co | Oil soluble alkaryl sulfonate lithium and polyvalent metal salts in polyolefin fibers and films |
US3530201A (en) * | 1966-12-06 | 1970-09-22 | Uniroyal Inc | Dyeable polyolefins containing thermoplastic nitrogen containing polymers and polyethylene oxide |
US3652198A (en) * | 1968-09-13 | 1972-03-28 | Uniroyal Inc | Mixture of filaments capable of being dyed to a multicolor pattern with anionic disperse dyes |
US4133844A (en) * | 1977-07-22 | 1979-01-09 | E. I. Du Pont De Nemours And Company | Product and process |
US5714258A (en) * | 1992-07-02 | 1998-02-03 | Hoechest Celanese Corporation | Fiber having improved properties, compositions for producing such fibers, and process for improving properties of fibers |
WO2022210543A1 (en) * | 2021-03-29 | 2022-10-06 | Tdk株式会社 | Copolymer, piezoelectric material, piezoelectric film, and piezoelectric element |
CN115413283A (en) * | 2021-03-29 | 2022-11-29 | Tdk株式会社 | Copolymer, piezoelectric material, piezoelectric film, and piezoelectric element |
CN115413283B (en) * | 2021-03-29 | 2024-05-07 | Tdk株式会社 | Copolymer, piezoelectric material, piezoelectric film, and piezoelectric element |
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