US3112241A - Process of imparting oil-repellency to solid materials, and materials thus produced - Google Patents
Process of imparting oil-repellency to solid materials, and materials thus produced Download PDFInfo
- Publication number
- US3112241A US3112241A US53884A US5388460A US3112241A US 3112241 A US3112241 A US 3112241A US 53884 A US53884 A US 53884A US 5388460 A US5388460 A US 5388460A US 3112241 A US3112241 A US 3112241A
- Authority
- US
- United States
- Prior art keywords
- paper
- oil
- pulp
- phosphate
- repellency
- 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
- 238000000034 method Methods 0.000 title claims description 30
- 239000000463 material Substances 0.000 title claims description 20
- 239000011343 solid material Substances 0.000 title description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 55
- 239000010452 phosphate Substances 0.000 claims description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000005871 repellent Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229920001131 Pulp (paper) Polymers 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000123 paper Substances 0.000 description 62
- 235000021317 phosphate Nutrition 0.000 description 54
- 239000003795 chemical substances by application Substances 0.000 description 33
- 239000000835 fiber Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 24
- 235000019198 oils Nutrition 0.000 description 24
- 238000011282 treatment Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- 230000035515 penetration Effects 0.000 description 18
- 239000004744 fabric Substances 0.000 description 17
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- -1 cationic ions Chemical class 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229920006317 cationic polymer Polymers 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000002655 kraft paper Substances 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 7
- 239000000312 peanut oil Substances 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 235000019483 Peanut oil Nutrition 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000010985 leather Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000009877 rendering Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 5
- 239000002657 fibrous material Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003389 potentiating effect Effects 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229910052571 earthenware Inorganic materials 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229940059904 light mineral oil Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BARVGPTVPZLMIU-UHFFFAOYSA-N 2-(diethylamino)ethanol Chemical compound [CH2]CN(CC)CCO BARVGPTVPZLMIU-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- SWKPGMVENNYLFK-UHFFFAOYSA-N 2-(dipropylamino)ethanol Chemical compound CCCN(CCC)CCO SWKPGMVENNYLFK-UHFFFAOYSA-N 0.000 description 1
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 1
- UJCCSVVTAYOWLL-UHFFFAOYSA-N 2-[bis(2-methylpropyl)amino]ethanol Chemical compound CC(C)CN(CCO)CC(C)C UJCCSVVTAYOWLL-UHFFFAOYSA-N 0.000 description 1
- KHYKXDSWXWVQTA-UHFFFAOYSA-N 4-(diethylamino)butan-1-ol Chemical compound CCN(CC)CCCCO KHYKXDSWXWVQTA-UHFFFAOYSA-N 0.000 description 1
- LVHDNIMNOMRZMF-UHFFFAOYSA-N 4-penten-1-yl acetate Chemical compound CC(=O)OCCCC=C LVHDNIMNOMRZMF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 101100520660 Drosophila melanogaster Poc1 gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 101100520662 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PBA1 gene Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- NKVXTZGCOMJXCH-UHFFFAOYSA-N acetic acid;2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(O)=O.CCN(CC)CCOC(=O)C(C)=C NKVXTZGCOMJXCH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-O morpholinium Chemical compound [H+].C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-O 0.000 description 1
- ADABARLJFURQEM-UHFFFAOYSA-N n-(1-methylpyridin-1-ium-2-yl)octadecanamide;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC(=O)NC1=CC=CC=[N+]1C ADABARLJFURQEM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/466—Halogenated compounds, e.g. perfluor-compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/004—Surface-active compounds containing F
- C11D1/006—Surface-active compounds containing fluorine and phosphorus
-
- 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
- D06M13/244—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 sulfur or phosphorus
- D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; 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
- D06M13/244—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 sulfur or phosphorus
- D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
- D06M13/298—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing halogen atoms
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/10—Phosphorus-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/11—Halides
Definitions
- polyfluoroalkyl phosphate linear cationic polymer Pulp slurry i Screen of paper machine Paper drier and finisher
- solid material hereinabove I mean water-insoluble materials customarily employed in the manufacture of articles of utility, for instance textile fabric, textile yarns, leather, paper, plastic sheeting, wood, ceramic clays, as well as manufactured articles prepared therefrom such as articles of apparel, wall paper, paper bags, cardboard boxes, porous earthenware, etc.
- oil repellency for the purpose of definiteness, I shall refer hereinafter to the quality of repelling, under the standard tests herein discussed, a light mineral oil such as a commercial liquid hydrocarbon or a vegetable oil such as peanut oil.
- the materials treated according to this invention are found to possess repellency to oils, greases and fats generally, regardless of their origin (as for instance, mineral, vegetable or animal kingdom) or their consistency.
- a special further object of this invention is to modify the mode of application of certain types of oil-repellency agents whereby to intensify their quality of exhausting from an aqueous treatment bath onto the solid material being treated.
- a particular further object, which is in effect a corollary of the last mentioned object, is to provide a method for rendering paper oil-repellent which can be applied to the paper pulp prior to sheet formation, whereby a more uniform, more effective and more economical impregnation may be achieved.
- Another corollary object is to provide as a novel article oil-repellent paper in which the oil-repellent factor is distributed essentially uniformly throughout the volume of the paper instead of being restricted to the surface or superficial layers thereof.
- Oii-repellency in articles such as wearing apparel, cardboard boxes, paper bags or wrapping paper is a relatively young and not fully developed art.
- the demand for such articles is perhaps old enough.
- the advantages of having for instance grease-repellent overalls for mechanics, wallpaper that does not stain easily, oilrepellent paper bags for bakery goods, or-on the contrarycontainers which will keep the contents safe against contamination with greasy soil from the outside, are so obvious as not to require much elaboration. Hitherto, however, the solution to this problem has not been entirely satisfactory from the economical viewpoint.
- Some of the oil-repellency agents hitherto used or suggested are complicated and costly chemicals. Others can be applied only from an organic solvent. Still others are relatively inefiicient and require application of large quantities thereof with respect to the Weight of the fiber or solid material being treated therewith.
- m is an integer from 3 to 12
- n is an integer from 6 to 12
- y is a number of average value from 1.0 to 2.5
- Z is a member of the group consisting of hydrogen and water-solubilizing cationic ions.
- the mixtures can be practicably separated, and where the intended use justifies the added cost of separation, the compounds wherein y equals 2 constitute the preferred agents.
- the compounds defined have also the quality of versatility, being applicable to a wide variety of textile fibers, including cotton, viscose, cellulose acetate, wool, silk, nylon, acrylic fiber and polyester fiber. They are also 3 applicable to leather, paper, wood and unglazed earthenware.
- a concentrated aqueous bath is generally employed.
- the fabric is impregnated with the treatment bath and then squeezed until there remains a definite amount of the aqueous liquors in proportion to the weight of the fiber.
- the fiber may be squeezed to a 100% pickup. In such event, the fiber picks up an equal weight of the treatment bath, and when the padded fiber is dried, there remains inside it (or on it) a percentage weight of the treating agent equal to its original concentration in the treatment bath.
- the fabric generally extracts the treating agent from the bath, until the latter becomes essentially exhausted.
- the quantity of agent absorbed by the fiber (provided a sufficient quantity of fiber has been used) is then essentially the entire quantity of agent that had been added to the bath.
- the quantity of agent therefore, is independent of the quan- 4 tity of water picked up by the fiber (with or without squeezing). In such cases, the quantity of agent initially added to the bath is calculated in advance O.W.F., that is, on the weight of the dry fiber.
- exhaust treatments are more economical than padding treatments; they permit the use of dilute aqueous baths and are often adapted for use in fields where padding procedures are inapplicable.
- oil-repellency agent be now added in a quantity corresponding to a few percent by Weight of the paper pulp, it is obvious that its concentration in the aqueous mass will be exceedingly low. So unless the fiber has the quality of drawing the agent out of solution, it is clear that the desired percentage deposit on the fiber cannot practicably be achieved.
- dialkylarnino alcohols coming into consideration for this purpose include 2(dimethylamino)ethanol, 2 (diethylamino)ethanol, 2-(dipropylamino)ethanol, 2- (N methyl N-cyclohexylamino)ethanol, 2-morpholinoethanol, 2 (diisobutylamino)ethanol, S-(diethylamino) propanol and 4-(diethylamino)butanol.
- the esters are prepared according to the method set forth in U.S.P.
- esters may also be converted to acid salts with acids such as acetic, formic or hydrochloric, and polymerized or copolym; erized by known procedure. (See for instance U.S.P. 2,138.762.)
- Preferred cationic compounds of this group are the polymers derived from the dimethyl sulfate quaternization product or from the acetic acid addition salt of 2-dimethylamino-ethyl methacrylate and Z-diethylamino-ethyl methacrylate.
- Item 17 Mono(Z-perfluorohexyl-ethyl) ester of phosphoric acid
- Item .27 bis(l l-perfluoroheptyl-l-undecyl) ester of phosphoric acid
- Phosphates of polyiluoroalcohols having the structure F(CF (CH OH where r is greater than 2 are prepared hy similar procedure, from l-iodopolyfiuoroalkanes Item Item Item and higher omega-alkenyl acetates such as 4-pentenyl acetate, IO-undecenyl acetate and the like.
- Oil-Repellency P erccnt by Percent by Rating Volume Volume Iloptane N ujol No resistance to Nujol; i.e. penetration within 3 minutes
- acceptable ratings are 70 and above, although beneficial effect to oil staining is sometimes obtained with ratings as low as 50.
- Example 1 Four parts of dry bleached Kraft pulp are agitated vigorously in a vessel containing 300 parts of Water, and 4 parts of an aqueous 1% solution of polymerized 2-(diethylamino)ethyl methacrylate acetic acid salt are added (1% of the polymer on the dry weight of the pulp). Agitation is continued for five minutes (or more), and then 20 parts of an aqueous 1% solution of a mixture of monoand bis(1H,1HJH-dodecafluoroheptyl) phosphate, morpholine salt, having a y-value of about 1.5, are added.
- Example 2 Example 3 Stock: Unbleached kraft pulp.
- Cationic polymer Polymer of dimethyl-sulfate-quaternized Z-diethylaminoethyl methacrylate. Quantity: 0.3% O.W.F.
- Polyfiuoroalkyl phosphate Ammonium bis(lH,lH,9l-I- hexadecafluorononyl) phosphate. Quantity: 0.3% O.W.F.
- Oil usedpeanut oil Penetration time-treated sample30 minutes.
- Example 4 Bleached sulfite pulp beaten to a freeness of 480.
- Cationic polymer Same as in Example 3. Quantity:
- Polyfluoroalkyl phosphate A mixture of monoand bis- 1H,lH-pentadecafluorooctyl) phosphate containing 77.3% of the mono phosphate ester; 0.3% O.W.F. Oil penetration test:
- Oil used--coconut oil Penetration timetreated sample-5 minutes. Controlwithin a few seconds.
- Example 5 Stock: Unbleached kraft pulp. Cationic polymer: Same as in Example 3; 0.5% O.W.F. Polyiluoroalkyl phosphate: A mixture of monoand his (1H,1H,2H,2H-heptafluoropentyl) phosphate containing 20% of the mono ester; 5% O.W.F. Oil penetration test:
- Oil usedpeanut oil Penetration timetreated paper-30 minutes.
- Oil usedpeanut oil Penetration time-treated Control-immediately.
- Cationic polymer A .polyethyleneimine of M.W. between 30,000 and 40,000, quaternized with dimethyl sulfate. (A commercial product.) Quantity: 2.5% O.W.F.
- Oil used-peanut oil Penetration timetreated paper30 minutes. Controlimmediately.
- Example 8 [omitting the cationic agent]
- Four parts of dry bleached kraft pulp are agitated vigorously in a vessel containing 300 parts of water, and 8 parts of an aqueous 1% solution of ammonium bis (Z-perfluoroheptyl- -ethyl) phosphate (2% O.W.F.) are added.
- the aqueous pulp is conveyed to the screen of a paper making machine, and the process of forming a paper sheet is proceeded with and finished in ordinary manner.
- Test B using peanut oil, it takes about 30 minutes for the first observable penetration compared with essentially immediate penetration for an untreated control.
- Example 9 100 parts of cotton fabric are dipped into an aqueous bath containing 1000 or more parts of water and 1 part by weight (i.e. 1% O.W.F.) of a polymer obtained from the dimethyl-sulfate quaternary salt of Z-diethylaminoethyl methacrylate. After agitating for 5 minutes or more, the fabric is removed, squeezed and reimrnersed in a bath containing 1000 parts or more of water and 1 part (i.e. 1.0% OWE.) of ammonium bis(1H,1H,9H-hexadecafiuorononyl) phosphate. After agitating in said bath for 5 minutes or more, the fabric is removed, squeezed and air-dried.
- aqueous bath containing 1000 or more parts of water and 1 part by weight (i.e. 1% O.W.F.) of a polymer obtained from the dimethyl-sulfate quaternary salt of Z-diethylamin
- Example 0 Six pounds of unbleached kraft stock was beaten to a Canadian Standard freeness of 450' and the pulp transferred to the machine chest of an 8%2-inch laboratory Fourdrin-ier paper machine. The concentration of fibers in the pulp in the chest was about 0.6%. A solution of 13.6 g. of ammonium bis(lH,lH,9H hexadecafiuorononyl) phosphate, [H CF 2 CH OJ P'( 0) ONH in about /2 gallon of water was added over a period of about 15 minutes to the pulp in the chest with agitation. The paper machine was then started and run at about 11 feet per minute to produce a sheet of 50 pounds (24" x 36" x 500) basis weight.
- Paper so produced exhibited greater than 30 minutes holdout :to peanut oil.
- a sheet run under similar conditions but containing no additives was found to have essentially no holdout to peanut oil.
- Example 11 1000 pounds of bleached k-raft furnish was beaten to a vfreeness of 600. 0.25 oz. of a blue direct azo dye was added to tint or whiten the paper. The charge was dropped to the beater chest. The pulp consistency was about 3.5% and the pH 7.5. 15 lbs. of a 30% solution of polymerized dimethyl-sulfate-quaternized Z-diethylaminoethyl methacrylate were mixed with 50 gallons of water and the resultant solution was added over a 40- minute period to the pulp in the beater chest. The pulp pH was then 5.8. The stock was transferred to the beater chest through a jordan. 6 lbs.
- ammonium bis(1H,1H,9H-hexadecafluoro-nonyl) phosphate were dissolved in 6 lbs. of acetone, diluted to 50 gallons with water, and the solution was added to the pulp in the beater chest over a 20-minute period. The pulp was again jordaned, diluted to machine consistency in the fan pump and fed to a l08-inch Fourdrinier machine.
- the agents have been added in the form of 1% aqueous solutions, solutions of other concentrations may, obviously, be employed.
- preparation of the aqueous solution may be facilitated by first dissolving the agent in an organic solvent, such as acetone, methanol, or ethanol, followed by dilution with water, or a solution of the free acid phosphate in an organic solvent as aforenoted may be diluted with an aqueous amine or ammonia solution.
- an organic solvent such as acetone, methanol, or ethanol
- the quantities of materials added may vary from 0.05 to 3% O.W.'F. for the cationic polymer and from 0.05 to 10% O.W.F. for the phosphate.
- the optimum amount will depend upon such factors as the nature of the pulp, the particular nitrogen-containing polymeric material selected, the composition of the phosphate, and the degree of oil-repellency desired. As a rule, a given combination of agents in specified amounts produces a greater effect on unbleached kraft pulp than on bleached kralft or bleached sulfite pulp.
- the ammonium salts or amine-addition products are more elfective than the free phosphoric acid, and the wF-compounds (Formula I) are more potent than the wH-compounds (Formula ll).
- the bis-fluoroalkyl phosphates are enormous more effective than the mono compounds, and where mixtures are unavoidable, it is preferred to use such mixtures wherein the bis-fluoroalkyl compounds predominate (i.e. y has an average value greater than 1.5).
- Fully alkylated phosphates i.e.
- the wF-compounds may be generically referred to as (perfiuoroalkyl-alkyl) phosphates. It follows from the aforegoing discussion that the most potent compounds for the purposes or" this invention, and therefore the most desirable from the practical viewpoint, are the bis(perlluoroalkyl-alkyl)ammonium phosphates.
- the wF-compounds possess the added advantage that they also impart water-repellence to the treated articles.
- the order of treatment of the solid material with the two principal agents of this invention is immaterial, provided care is taken to eliminate or minimize contact between the two agents except when either of them is in contact with the solid material being treated.
- the cationic agent may be applied first and after a little time, to allow for complete exhaustion of said agent onto the material being treated (say, an aqueous paper pulp), the polyfluoroalkyl phosphate may be applied.
- the reverse sequence may be applied, with a suitable time interval to allow for maximum exhaustion of the phosphate compound onto the fiber.
- the materials may be .fed simultaneously from separate pipes into the vessel or pipe containing the pulp, provided vigorous agitation (or turbulent flow in the case of a pipe) is applied to insure rapid contact of either agent with the pulp, thus minimizing the frequency and time of contact beiween the two agents when not in contact with the pu p.
- the process of this invention may be applied to many types and grades of pulp. These include unbleached kraft pulp, unbleached sulfite pulp, bleached draft pulp, bleached sulfite pulp, alpha pulp or rag stock from cotton fibers, such pulps being used alone or in mutual admixture, or again in admixture with ground-wood pulps.
- the novel paper thus produced itself has several important valuable qualities and advantages.
- the paper may possess a high degree of oil-repellency, its appearance, feel, porosity and other physical qualities are not changed, and the paper may, further-more, be given customary finishing treatments such as sizing, coating and the like, to improve the surface for printing or to provide water repellency.
- customary finishing treatments such as sizing, coating and the like, to improve the surface for printing or to provide water repellency.
- the paper is creased it does not produce a break in the oil-repellent film, as is the case with surface-treated paper.
- Oil-repellent paper which has been produced from treated pulp according to this invention has been found to be excellently adapted for further treatment with tarry or waxy coatings, giving consistently a superior product in respect to adhesion of the coating, opacity of the paper and economy of the process compared to other papers which have not been made oil-repellent at all or papers which have been made oil-repellent by surface treatment of the paper sheet.
- said water-soluble linear polymer containing cationic nitrogen atoms is a member selected from the group consisting of cationic urea-formaldehyde resins, cationic melamine-formaldehyde resins, quaternary salts and acid salts of polymerized ethyleneimine, cationic starches and quaternary salts and acid salts of polymerized dialkylaminoalkyl acrylates and methacrylates.
- water-soluble linear polymer is the acetic acid salt of polymerized 2- diethylaminoethyl methacrylate.
- water-soluble linear polymer is the dimethyl-sulfate quaternization product of polymerized Z-diethylaminoethyl methacrylate.
- a process of producing an oil-repellent paper which comprises treating an aqueous paper pulp, in the stage prior to sheet formation, with an aqueous solution of a polyfiuoroalkyl phosphate containing from 3 to 12 CF groups per molecule whereby to exhaust onto said pulp from 0.05 to 3% of its weight of said polyfiuoroalkyl compounds, further treat-ing said aqueous pulp with an aqueous solution of a water-soluble linear polymer containing cationic N-atoms whereby to exhaust onto said pulp from 0.05 to 10% of its weight of said polymer, and forming paper sheet material from the pulp so treated.
- polyfiuoro-alkyl phosphate selected is a mixed product in which the dominant component is a compound whose y-value is 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Paper (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
United States Patent This invention relates to novel processes for rendering solid materials oil-repeilent and to the novel materials thus produced.
Water soln. of
Water soln. of
polyfluoroalkyl phosphate linear cationic polymer Pulp slurry i Screen of paper machine Paper drier and finisher By solid material hereinabove I mean water-insoluble materials customarily employed in the manufacture of articles of utility, for instance textile fabric, textile yarns, leather, paper, plastic sheeting, wood, ceramic clays, as well as manufactured articles prepared therefrom such as articles of apparel, wall paper, paper bags, cardboard boxes, porous earthenware, etc. By oil repellency, for the purpose of definiteness, I shall refer hereinafter to the quality of repelling, under the standard tests herein discussed, a light mineral oil such as a commercial liquid hydrocarbon or a vegetable oil such as peanut oil. But as a general proposition the materials treated according to this invention are found to possess repellency to oils, greases and fats generally, regardless of their origin (as for instance, mineral, vegetable or animal kingdom) or their consistency.
it "is a primary object of this invention to provide a novel means of imparting oil-repellency to water-insoluble solid materials which is applicable to said material from an aqueous treating bath. Another object is to provide a novel means as aforesaid which is applicable from aqueous baths by ordinary means such as padding, dipping, impregnation, spraying, etc.
A special further object of this invention is to modify the mode of application of certain types of oil-repellency agents whereby to intensify their quality of exhausting from an aqueous treatment bath onto the solid material being treated. A particular further object, which is in effect a corollary of the last mentioned object, is to provide a method for rendering paper oil-repellent which can be applied to the paper pulp prior to sheet formation, whereby a more uniform, more effective and more economical impregnation may be achieved. Another corollary object is to provide as a novel article oil-repellent paper in which the oil-repellent factor is distributed essentially uniformly throughout the volume of the paper instead of being restricted to the surface or superficial layers thereof. Other objects and achievements of this invention will become apparent as the description proceeds.
Oii-repellency in articles such as wearing apparel, cardboard boxes, paper bags or wrapping paper is a relatively young and not fully developed art. The demand for such articles is perhaps old enough. The advantages of having for instance grease-repellent overalls for mechanics, wallpaper that does not stain easily, oilrepellent paper bags for bakery goods, or-on the contrarycontainers which will keep the contents safe against contamination with greasy soil from the outside, are so obvious as not to require much elaboration. Hitherto, however, the solution to this problem has not been entirely satisfactory from the economical viewpoint. Some of the oil-repellency agents hitherto used or suggested are complicated and costly chemicals. Others can be applied only from an organic solvent. Still others are relatively inefiicient and require application of large quantities thereof with respect to the Weight of the fiber or solid material being treated therewith.
In the copending application of Werner V Cohen, filed on the same date herewith, it is taught that highly effective oil-repellency effects can be produced on solid materials such as above indicated by applying to the same an aqueous solution of a polyfluoroalkyl phosphate of the group defined by the general formulas:
wherein m is an integer from 3 to 12, n is an integer from 6 to 12, y is a number of average value from 1.0 to 2.5, and Z is a member of the group consisting of hydrogen and water-solubilizing cationic ions. The treated material is then dried, whereby to form in intimate contact therewith an evenly distributed deposit of said polyfiuoroalkyl phosphate.
As examples of water-solubilizing cations in the definition of Z above, are mentioned in said copending application the alkali-metals (Na, K, Li), ammonium, diethanolammonium, triethanolammonium, morpholinium, and the like.
Compounds falling within the above general formulas are disclosed in U.S.P. 2,597,702 and 2,559,749, which assign to them the special property of being excellent dispersing agents. But their quality as oii-repellency agents has apparently not been recognized heretofore.
According to said application, however, it has been found that the above defined polyfiuoroalkyl phosphates not only possess the desirable quality of imparting oilrepellency to solid bodies, but some of them are highly potent in this respect. Tins is particularly true of compounds of the above formulas wherein y is 2. And inasmuch as the synthesis of these phosphates naturally re sults in a mixture of phosphates of different degrees of esterification, it is taught in said application that mixtures of bisand rnono-polyfluoroalkyl phosphates in which the his compounds predominate constitute the most desirable agents for practical use. Expressed in different words, they are mixtures of compounds falling within one or the other of the above formulas and wherein y has an average value from 1.0 to 2.5 with a preferred range of 1.5 to 2.0.
Furthermore, the mixtures can be practicably separated, and where the intended use justifies the added cost of separation, the compounds wherein y equals 2 constitute the preferred agents.
The above compounds possess also other valuable properties for the purpose intended. For instance, their watersolubility adapts them for application from a purely aqueous bath or, if desired, from an aqueous bath containing acetone, alcohol, or any other water-miscible, volatile adjuvant.
The compounds defined have also the quality of versatility, being applicable to a wide variety of textile fibers, including cotton, viscose, cellulose acetate, wool, silk, nylon, acrylic fiber and polyester fiber. They are also 3 applicable to leather, paper, wood and unglazed earthenware.
Now, according to my present invention, I have firstly augmented the list of phosphates available for producing oil-repellency, by the discovery that polyfluoroalkyl compounds wherein the perfluoroalkyl radical is separated from the P-atom by more than one CH group are equal- 1y potent and effective for the above purpose. This is rather surprising when it is considered that in the analogous case of water-repellency agents wherein stearamidomethyl pyridinium chloride was at one time the most popular practical agent on the market for said purpose, it was learned that analogous compounds in which the stearamido radical was separated from the nitrogen atom of the pyridinium radical by a link of 2 or more CH groups (eg ethylene) were totally ineffective. Accordingly, the compounds which this invention adds to the teachings of said copending application of Werner V. Cohen are compounds of the general formula wherein m, y and Z have the same significance as in Formulas I and II above, while r is an integer from 2 to 16. Many of these are novel compounds, and are claimed in the copending application of Neal 0. Brace and myself, Ser. No. 158,128, filed December 8, 1961.
Secondly, I have found that the polyfluoroalkyl phosphates hereinabove discussed (including Formulas I, II and III) possess in themselves the quality of exhaustion from an aqueous bath onto textile fiber, leather or paper. This is a very valuable practical quality, and enables for instance the treatment of paper stock in the pulp stage, prior to sheet formation, as will be more fully explained below.
Furthermore, according to a further feature of this invention, I have found that the exhausting qualities of any of the compounds hereinabove discussed for fibrous materials such as textile yarn or fabric, paper or leather can be immensely increased (or that the quality of exhaustibility can be essentially created where it did not exist before) by further treating said fibrous materials with an aqueous bath comprising a water-soluble linear polymer containing cationic N-atoms, said polymer being present in sufficient quantity to desposit thereof on said fibrous material a quantity corresponding to from 0.05 to by weight. Said further treatment may be done prior to treatment with said polyfiuoroalkyl phosphates, after such treatment, or simultaneously therewith, provided in the last case that very rapid contact of both agents with the fiber is assured.
To shed more light on this subject, treatments of textile fibers with aqueous baths generally proceed under two major categories: Padding and exhaustion.
In padding, a concentrated aqueous bath is generally employed. The fabric is impregnated with the treatment bath and then squeezed until there remains a definite amount of the aqueous liquors in proportion to the weight of the fiber. For instance, the fiber may be squeezed to a 100% pickup. In such event, the fiber picks up an equal weight of the treatment bath, and when the padded fiber is dried, there remains inside it (or on it) a percentage weight of the treating agent equal to its original concentration in the treatment bath.
If, on the other hand, the fiber does have affinity for the treating agent, as is more commonly the case in dyeing cellulosic fiber or wool with compounds which are true dyes (as distinguished from pigments), the fabric generally extracts the treating agent from the bath, until the latter becomes essentially exhausted. The quantity of agent absorbed by the fiber (provided a sufficient quantity of fiber has been used) is then essentially the entire quantity of agent that had been added to the bath. The quantity of agent, therefore, is independent of the quan- 4 tity of water picked up by the fiber (with or without squeezing). In such cases, the quantity of agent initially added to the bath is calculated in advance O.W.F., that is, on the weight of the dry fiber.
It will be readily seen that exhaust treatments are more economical than padding treatments; they permit the use of dilute aqueous baths and are often adapted for use in fields where padding procedures are inapplicable.
A practical illustration on this point is the problem of rendering paper oil-repellent. Hitherto, this problem has invariably been solved by applying the chosen oil-repellency agent to the finished paper sheet by spraying, dipping or transfer from a moistened roll. Although treatment of the pulp prior to sheet formation has several obvious advantages (for instance, uniform distribution of the agent throughout the mass of the paper sheet as opposed to superficial saturation), it has not been practicably possible heretofore to apply the agent at this stage, because the paper pulp as prepared in ordinary paper-making machines is generally obtained in the form of a highly dilute aqueous suspension, of at most a few percent by weight. If the oil-repellency agent be now added in a quantity corresponding to a few percent by Weight of the paper pulp, it is obvious that its concentration in the aqueous mass will be exceedingly low. So unless the fiber has the quality of drawing the agent out of solution, it is clear that the desired percentage deposit on the fiber cannot practicably be achieved.
According to my present invention, however, further treatment of the fiber with cationic polymers as above set forth endows it somehow with the quality of drawing polyfiuoroalkyl oil-repellency compounds out of aqueous solution, and treatment of paper in the pulp stage becomes a highly practical matter.
As examples of commercially available cationic polymeric materials suitable for the aforesaid pretreatment may be mentioned:
(a) The polymers or copolymers of quaternary or acid salts of esters of a dialkylamino alcohol and acrylic acid or methacrylic acid.
Specific dialkylarnino alcohols coming into consideration for this purpose include 2(dimethylamino)ethanol, 2 (diethylamino)ethanol, 2-(dipropylamino)ethanol, 2- (N methyl N-cyclohexylamino)ethanol, 2-morpholinoethanol, 2 (diisobutylamino)ethanol, S-(diethylamino) propanol and 4-(diethylamino)butanol. The esters are prepared according to the method set forth in U.S.P. 2,138,763, then quaternized, for example, in an aqueous solution of dimethyl sulfate, and the resulting quaternary ammonium salt is polymerized, or two or more of them are copolymerized, by known procedure. The esters may also be converted to acid salts with acids such as acetic, formic or hydrochloric, and polymerized or copolym; erized by known procedure. (See for instance U.S.P. 2,138.762.)
Preferred cationic compounds of this group are the polymers derived from the dimethyl sulfate quaternization product or from the acetic acid addition salt of 2-dimethylamino-ethyl methacrylate and Z-diethylamino-ethyl methacrylate.
(b) Water-soluble urea resins which possess cationic N-atoms, for instance one prepared from urea, formaldehyde, tetraethylenepentamine, and hydrochloric acid as described by Suen, in Polymer Processes, edited by Schildknecht (Intersciencc, 1956), page 343.
(c) Melamine-formaldehyde resins which possess cationic N-atoms, for instance the acid colloid prepared from formaldehyde, melamine, and hydrochloric acid as described by Suen, loc. cit., at pages 315, 344.
(d) The quaternized or acid salts of polymerized ethyleneimine, for instance those having a molecular weight of 30,000 to 40,000.
(e) Cationically modified nitrogen-containing starches, certain representatives of which occur in commerce.
Returning now to the polyfluoroalkyl phosphates dcfined by the general Formulas I, H and "III hereinabove, the following table indicates, by formula, a number of practical illustrations thereof in the free acid state:
The nomenclature of these compounds is rather com plicated, but is typified by the following samples:
1: 1H, lH,7H-dodecafiuoroheptyl phosphate 9: lH,lH,tridecafluoroheptyl phosphate tlem l2: bis(=1H,lH-pentacosafluorotridecyl) phosphate Item 26: bis(12 through l4-heptafiuorotetradecyl) phosphate They can also be named as typified by the following samples:
Item 17: Mono(Z-perfluorohexyl-ethyl) ester of phosphoric acid Item .27: bis(l l-perfluoroheptyl-l-undecyl) ester of phosphoric acid Some of the compounds in the above table which are not named in U.S.P. 2,559,749 and 2,597,702 may be prepared hy methods analogous to those indicated in said pat ents. This is true of all the compounds of Formulas I and H above. Of the compounds of Formula III above, those which are new may he prepared by procedures analogous to the one set forth hereinbelow for a typical member of this group:
One mole of vinyl acetate and about 1.05 moles of l-iodopentadecafiuoroheptane are heated together at to C. in the presence Olf 2,2-azodiisobutyronitrile for seven hours. The excess of l-iodopentadecafiuoroheptane is then distilled off under a vacuum, and 550 parts (by Weight) of the residual liquid, which is essentially 1H,2H,2H-l-iodopentadecafiuorononyl acetate, are reacted in 1200 parts of ethanol with 200 parts of zinc dust and 200 parts of concentrated HCl. The reaction mass is cooled and drowned in water, and the oily layer is drawn off.
The oily product is then treated with a 10% ethanol solution of potassium hydroxide, then drowned in water and extracted with chloroform. The extract is dried over anhydrous magnesium sulfate, and the chloroform is stripped off, leaving behind 2-perfiuoroheptyl-ethanol, which is a colorless liquid, of B.P. 84 C. at 10 rnin. pressure. It has a refractive index (11 of 1.3164. When this alcohol is reacted in molar proportions with POCl in benzene in the presence of pyridine, it yields a dichlorophosphate which upon hydrolysis with pyridine and water yields the compound of Formula 19 above. If two moles of the alcohol are reacted with one mole of POC1 and hydrolyzed, the his compound of Formula 20 is obtained.
Phosphates of polyiluoroalcohols having the structure F(CF (CH OH where r is greater than 2 are prepared hy similar procedure, from l-iodopolyfiuoroalkanes Item Item Item and higher omega-alkenyl acetates such as 4-pentenyl acetate, IO-undecenyl acetate and the like.
Without limiting this invention, the following examples are given to illustrate my preferred mode of operation. Parts mentioned are by Weight. The oil-repellency tests referred to in these examples are of two types, depending on whether the material tested has been prepared by surface treatment or it is paper made by treating the pulp. The tonmer test is known in the art, and its essential features are as follows:
A. TESTING OF SURFACE-TREATED, SHEET MATERIAL This test is based on the different penetrating properties of mineral oil (Nujol) and n-heptane. Mixtures of these two hydrocarbon liquids, which are miscible in all proportions, show penetrating properties proportional to the amount of n-heptane in the mixture.
To measure oil repellency of a treated fabric, 8" x 8" swatches of the fabric are placed on a table and a drop of one of several test-mixtures of the above hydrocarbons is gently placed onto each fabric surface. After 1 minute, the fabrics are inspected to determine the mixture of highest heptane percentage which did not wet the fabric under the drop. According to said highest heptane percentage, the fabric is assigned a rating as set forth in the following table:
Oil-Repellency P erccnt by Percent by Rating Volume Volume Iloptane N ujol (No resistance to Nujol; i.e. penetration within 3 minutes) Usually, acceptable ratings are 70 and above, although beneficial effect to oil staining is sometimes obtained with ratings as low as 50.
B. TESTING OF PAPER MADE FROM TREATED PULP This test is effected by cementing to the surface of a sheet of the paper to be tested and to a sheet of untreated control paper, four metal cylinders, one inch in diameter and one-half inch high. The sheets of paper are supported on glass so that the under surface can be observed. To each metal cylinder is then added about 1 ml. of oil, and the time until the first trace of oil penetration can be seen on the under surface on the paper is observed. A comparison of the average times for penetration by the oil of the treated and untreated papers indicates the order of magnitude of the oil repellency that has been attained.
Example 1 Four parts of dry bleached Kraft pulp are agitated vigorously in a vessel containing 300 parts of Water, and 4 parts of an aqueous 1% solution of polymerized 2-(diethylamino)ethyl methacrylate acetic acid salt are added (1% of the polymer on the dry weight of the pulp). Agitation is continued for five minutes (or more), and then 20 parts of an aqueous 1% solution of a mixture of monoand bis(1H,1HJH-dodecafluoroheptyl) phosphate, morpholine salt, having a y-value of about 1.5, are added. (This quantity calculates to 5% O.W.F.) After additional stirring for five minutes or more, the aqueous pulp is conveyed to the screen of a paper making machine, and the process of forming a paper sheet is proceeded with and finished in ordinary manner.
In an actual procedure as above described, carried out on laboratory-size paper making equipment, a sheet of 8 paper was formed which under Test B above described, using peanut oil, required 5 minutes for the first observable penetration of the oil to the underside of the paper. In another sheet of paper made on the same equipment but without the addition of the aforementioned agents.
to the pulp, the penetration by peanut oil was essentially instantaneous.
In other experiments carried out according to the above procedure in laboratory-size equipment, the adjuvants and quantities were varied as in the examples below, with the results there indicated.
Example 2 Example 3 Stock: Unbleached kraft pulp.
Cationic polymer: Polymer of dimethyl-sulfate-quaternized Z-diethylaminoethyl methacrylate. Quantity: 0.3% O.W.F.
Polyfiuoroalkyl phosphate: Ammonium bis(lH,lH,9l-I- hexadecafluorononyl) phosphate. Quantity: 0.3% O.W.F.
Oil penetration test:
Oil usedpeanut oil. Penetration time-treated sample30 minutes.
Control-almost immediately.
Example 4 Stock: Bleached sulfite pulp beaten to a freeness of 480. Cationic polymer: Same as in Example 3. Quantity:
0.2 part of a 1% solution (i.e. 0.05% O.W.F.). Polyfluoroalkyl phosphate: A mixture of monoand bis- 1H,lH-pentadecafluorooctyl) phosphate containing 77.3% of the mono phosphate ester; 0.3% O.W.F. Oil penetration test:
Oil used--coconut oil. Penetration timetreated sample-5 minutes. Controlwithin a few seconds.
Example 5 Stock: Unbleached kraft pulp. Cationic polymer: Same as in Example 3; 0.5% O.W.F. Polyiluoroalkyl phosphate: A mixture of monoand his (1H,1H,2H,2H-heptafluoropentyl) phosphate containing 20% of the mono ester; 5% O.W.F. Oil penetration test:
Oil usedpeanut oil. Penetration timetreated paper-30 minutes.
trolirnmediately.
Con-
Example 6 Stock: Unbleached kraft pulp. Cationic polymer: Same as in Example 3; 0.5% O.W.F. Polyfluoroalkyl phosphate: Ammonium salt of a mixture of monoand bis(l2 through 18 pentadecafluorooctadecyl) phosphate. Quantity: 1.6 parts of a 1% acetone solution (=0.4% O.W.F.). Oil penetration test:
Oil usedpeanut oil. Penetration time-treated Control-immediately.
sample-30 minutes.
9*. Example 7 Stock: Unbleached ltraft pulp.
Cationic polymer: A .polyethyleneimine of M.W. between 30,000 and 40,000, quaternized with dimethyl sulfate. (A commercial product.) Quantity: 2.5% O.W.F.
Polyfiuoroalkyl phosphate: Same as in Example 3; 0.4%
O.W.F.
Oil penetration test:
Oil used-peanut oil. Penetration timetreated paper30 minutes. Controlimmediately.
Example 8 [omitting the cationic agent] Four parts of dry bleached kraft pulp are agitated vigorously in a vessel containing 300 parts of water, and 8 parts of an aqueous 1% solution of ammonium bis (Z-perfluoroheptyl- -ethyl) phosphate (2% O.W.F.) are added. After stirring for 5 minutes or more, the aqueous pulp is conveyed to the screen of a paper making machine, and the process of forming a paper sheet is proceeded with and finished in ordinary manner. When the resulting paper is subjected to Test B, using peanut oil, it takes about 30 minutes for the first observable penetration compared with essentially immediate penetration for an untreated control.
Example 9 100 parts of cotton fabric are dipped into an aqueous bath containing 1000 or more parts of water and 1 part by weight (i.e. 1% O.W.F.) of a polymer obtained from the dimethyl-sulfate quaternary salt of Z-diethylaminoethyl methacrylate. After agitating for 5 minutes or more, the fabric is removed, squeezed and reimrnersed in a bath containing 1000 parts or more of water and 1 part (i.e. 1.0% OWE.) of ammonium bis(1H,1H,9H-hexadecafiuorononyl) phosphate. After agitating in said bath for 5 minutes or more, the fabric is removed, squeezed and air-dried.
The above procedure is applicable likewise to other fabrics, such as Wool, nylon, polyester fabric, acrylic fabric, to the corresponding materials in the form of yarn, as well as to leather.
In a series of actual experiments according to the above procedure followed by oil-repellency Test A hereinabove described, the following results were obtained.
Oil-repellency Material rating Cotton (sateen) 70 Wool (worsted) 70 Nylon 70-80 Acrylic fiber 80 Polyester fiber 80 Cellulose triacetate fiber 80 Retanned suede leather 50 in another series of experiments following the same procedure as above except for omitting the first dip (i.e. eliminating the treatment with the cationic polymer), the oil-repelleney rating obtained was 50 on all fabrics. When, however, the same set of experiments is repeated except for increasing the concentration of the polyfluoroalkyl phosphate to 2% O.W.F., ratings as high at 80 are obtained.
Example 0 Six pounds of unbleached kraft stock was beaten to a Canadian Standard freeness of 450' and the pulp transferred to the machine chest of an 8%2-inch laboratory Fourdrin-ier paper machine. The concentration of fibers in the pulp in the chest was about 0.6%. A solution of 13.6 g. of ammonium bis(lH,lH,9H hexadecafiuorononyl) phosphate, [H CF 2 CH OJ P'( 0) ONH in about /2 gallon of water was added over a period of about 15 minutes to the pulp in the chest with agitation. The paper machine was then started and run at about 11 feet per minute to produce a sheet of 50 pounds (24" x 36" x 500) basis weight. After a steady state condition of machine operation had been reached, a 1.5% solution of poly[2-(diethylmethylammonio)ethyl methacrylate methosulfate] was metered continuously to the machine headbox by a metering pump at a rate to give 0.5% of the polymeric material based on the dry weight of the pulp. This solution was added at a point where turbulence insured an even distribution of the polymer throughout the polyfiuoroal'kyl phosphate-treated pulp. The paper was produced by the usual operation of the Fourdrinier machine, except that the sheet was not calendered.
Paper so produced exhibited greater than 30 minutes holdout :to peanut oil. A sheet run under similar conditions but containing no additives was found to have essentially no holdout to peanut oil.
Example 11 1000 pounds of bleached k-raft furnish was beaten to a vfreeness of 600. 0.25 oz. of a blue direct azo dye was added to tint or whiten the paper. The charge was dropped to the beater chest. The pulp consistency was about 3.5% and the pH 7.5. 15 lbs. of a 30% solution of polymerized dimethyl-sulfate-quaternized Z-diethylaminoethyl methacrylate were mixed with 50 gallons of water and the resultant solution was added over a 40- minute period to the pulp in the beater chest. The pulp pH was then 5.8. The stock was transferred to the beater chest through a jordan. 6 lbs. of ammonium bis(1H,1H,9H-hexadecafluoro-nonyl) phosphate were dissolved in 6 lbs. of acetone, diluted to 50 gallons with water, and the solution was added to the pulp in the beater chest over a 20-minute period. The pulp was again jordaned, diluted to machine consistency in the fan pump and fed to a l08-inch Fourdrinier machine.
The paper-making process was then completed in the usual manner. When subjected to Test B, using a light mineral oil, this paper required about 30 minutes for the first observable penetration to the underside. I
It will be understood that the details of the above examples may be varied widely without departing from the spirit of this invention.
Thus, while in most of the above examples the agents have been added in the form of 1% aqueous solutions, solutions of other concentrations may, obviously, be employed. Moreover, in the case of the polyifiuoroalkyl phosphates, preparation of the aqueous solution may be facilitated by first dissolving the agent in an organic solvent, such as acetone, methanol, or ethanol, followed by dilution with water, or a solution of the free acid phosphate in an organic solvent as aforenoted may be diluted with an aqueous amine or ammonia solution.
The quantities of materials added may vary from 0.05 to 3% O.W.'F. for the cationic polymer and from 0.05 to 10% O.W.F. for the phosphate. The optimum amount will depend upon such factors as the nature of the pulp, the particular nitrogen-containing polymeric material selected, the composition of the phosphate, and the degree of oil-repellency desired. As a rule, a given combination of agents in specified amounts produces a greater effect on unbleached kraft pulp than on bleached kralft or bleached sulfite pulp.
'In the phosphates, the ammonium salts or amine-addition products are more elfective than the free phosphoric acid, and the wF-compounds (Formula I) are more potent than the wH-compounds (Formula ll). Moreover, with either kind, the bis-fluoroalkyl phosphates are immensely more effective than the mono compounds, and where mixtures are unavoidable, it is preferred to use such mixtures wherein the bis-fluoroalkyl compounds predominate (i.e. y has an average value greater than 1.5). Fully alkylated phosphates (i.e. y=3) are inoperable, but where a mixture is readily available, they constitute an inert, but harmless diluent to the active biscompounds. Therefore, mixtures of polyi'luoroalkyl phosphates having a y-value greater than 2, say up to y=2.5, are tolerable. Altogether then, compounds wherein y=2 are preferred, but mixtures having an average y value between 1.0 and 2.5 can be used.
The wF-compounds (Formula I) may be generically referred to as (perfiuoroalkyl-alkyl) phosphates. It follows from the aforegoing discussion that the most potent compounds for the purposes or" this invention, and therefore the most desirable from the practical viewpoint, are the bis(perlluoroalkyl-alkyl)ammonium phosphates.
Incidentally, the wF-compounds possess the added advantage that they also impart water-repellence to the treated articles. Thus, while production of oil-repellent solid articles has been stressed throughout the above discussion as being the primary object of this invention, the porcess and means herein described, when wF polyfiuoroalkyl phosphates are employed, produce both oilrepellency and water-repellency on the article treated therewith, be it textile fiber, paper or any other Waterinsoluble, solid material.
The order of treatment of the solid material with the two principal agents of this invention (i.e. polyfluoroalkyl phosphate and cationic resinous material) is immaterial, provided care is taken to eliminate or minimize contact between the two agents except when either of them is in contact with the solid material being treated. This implies that the cationic agent may be applied first and after a little time, to allow for complete exhaustion of said agent onto the material being treated (say, an aqueous paper pulp), the polyfluoroalkyl phosphate may be applied. Or the reverse sequence may be applied, with a suitable time interval to allow for maximum exhaustion of the phosphate compound onto the fiber. Or again, the materials may be .fed simultaneously from separate pipes into the vessel or pipe containing the pulp, provided vigorous agitation (or turbulent flow in the case of a pipe) is applied to insure rapid contact of either agent with the pulp, thus minimizing the frequency and time of contact beiween the two agents when not in contact with the pu p.
The process of this invention may be applied to many types and grades of pulp. These include unbleached kraft pulp, unbleached sulfite pulp, bleached draft pulp, bleached sulfite pulp, alpha pulp or rag stock from cotton fibers, such pulps being used alone or in mutual admixture, or again in admixture with ground-wood pulps.
The advantages of my invention will now be readily apparent. Firstly, new fields of utility and a new degree of potency are opened up for the polyfluoroalkyl phosphates when used as oil-repellency agents. Thus, the 'polyfluoroalkyl phosphates can now be made to exhaust onto fibrous material from dilute baths, and when so applied they are about times as powerful, insofar as oil-repellency elfects are concerned, as some other present-day commercial polyfluoro compounds. Secondly, the last mentioned quality in turn opens up the commercial feasibility of producing oil-repellent paper by treating the paper stock in the aqueous pulp stage. From this in turn flows a new commercial product, namely paper that is permeated uniformly throughout its mass with the oil-repellent agent.
The novel paper thus produced itself has several important valuable qualities and advantages. Thus, while the paper may possess a high degree of oil-repellency, its appearance, feel, porosity and other physical qualities are not changed, and the paper may, further-more, be given customary finishing treatments such as sizing, coating and the like, to improve the surface for printing or to provide water repellency. When the paper is creased it does not produce a break in the oil-repellent film, as is the case with surface-treated paper.
Furthermore, in certain processes of coating paper with waxy, or tarry coatings, as for instance in producing typewriter carbon paper, asphalt-laminated seed bags or water-proof containers in general, it has been found in the art advantageous to give the paper first an oil-repellency treatment, to prevent said coatings from penetrating deeply into the paper stock, with the result that both economy in the consumption of the coating material is achieved and the paper is prevented from becoming transparent. This remedy, however, often results in a tarry or waxy coating of weak adhesion; that is, it may readily flake off when the paper is flexed. Oil-repellent paper, however, which has been produced from treated pulp according to this invention has been found to be excellently adapted for further treatment with tarry or waxy coatings, giving consistently a superior product in respect to adhesion of the coating, opacity of the paper and economy of the process compared to other papers which have not been made oil-repellent at all or papers which have been made oil-repellent by surface treatment of the paper sheet.
I claim as my invention:
1. The process of rendering a water-insoluble solid material oil repellent which comprises treating said material with an aqueous bath containing a water-soluble polyfluoroalkyl phosphate in quantity sufiicient to deposit thereof on said solid material from 0.05 to 3% by weight, and with an aqueous bath comprising a water-soluble linear polymer containing cationic N-atoms, said polymer being present in sufficient quantity to deposit thereof on said solid material a quantity corresponding to from 0.05 to 10% by weight, said treatments being effected in optional time relation to each other but under conditions Whereby to minimize contact between said linear polymer and said phosphate except when either of them is in contact with the fiber, and removing excess moisture from the thus treated solid material.
2. A process as in claim 1, wherein said water-soluble linear polymer containing cationic nitrogen atoms is a member selected from the group consisting of cationic urea-formaldehyde resins, cationic melamine-formaldehyde resins, quaternary salts and acid salts of polymerized ethyleneimine, cationic starches and quaternary salts and acid salts of polymerized dialkylaminoalkyl acrylates and methacrylates.
3. A process as in claim 1, wherein said water-soluble linear polymer is the acetic acid salt of polymerized 2- diethylaminoethyl methacrylate.
4. A process as in claim 1, wherein said water-soluble linear polymer is the dimethyl-sulfate quaternization product of polymerized Z-diethylaminoethyl methacrylate.
5. A process of producing an oil-repellent paper, which comprises treating an aqueous paper pulp, in the stage prior to sheet formation, with an aqueous solution of a polyfiuoroalkyl phosphate containing from 3 to 12 CF groups per molecule whereby to exhaust onto said pulp from 0.05 to 3% of its weight of said polyfiuoroalkyl compounds, further treat-ing said aqueous pulp with an aqueous solution of a water-soluble linear polymer containing cationic N-atoms whereby to exhaust onto said pulp from 0.05 to 10% of its weight of said polymer, and forming paper sheet material from the pulp so treated. Y
6. The process of rendering a water-insoluble solid material oil repellent which comprises treating said material with an aqueous bath containing a water-soluble polyfiuoroalkyl phosphate of the formula wherein r is an integer from 2 to 16, m is an integer from 3 to 12, y is a number of average value from 1.0 to 2.5, and Z is a member of the group consisting of hydrogen and water-solubilizing cationic ions, and drying the maerial whereby to form in intimate contact therewith an 13 evenly distributed deposit of said polyfiuoroalkyl phosphate.
7. A process as in claim 6, wherein the polyfiuoro-alkyl phosphate selected is a mixed product in which the dominant component is a compound whose y-value is 2.
8. As an article of manufacture, paper uniformly permeated throughout its body with a polyfluoroalkyl phosphate, said phosphate rendering said paper oil-repellent.
References Cited in the file of this patent UNITED STATES PATENTS Benning May 20, 1952 Mich-eels Nov. 17, 1959 Hessburg et a1 Jan. 12, "1960 Brovm Oct. 11, 1960 Pattilloch et a1. Oct. 25, 1960
Claims (1)
- 5. A PROCESS OF PRODUCING AN OIL-REPELLENT PAPER, WHICH COMPRISES TREATING AN AQUEOUS PAPER PULP, IN THE STAGE PRIOR TO SHEET FORMATION, WITH AN AQUEOUS SOLUTION OF A POLYFLUOROALKYL PHOSPHATE CONTAINING FROM 3 TO 12 CH2 GROUPS PER MOLECULE WHEREBY TO EXHAUST ONTO SAID PULP FROM 0.05 TO 3% OF ITS WEIGHT OF SAID POLYFLUOROALKYL COMPOUNDS, FURTHER TREATING SAID AQUEOUS PULP WITH AN AQUEOUS SOLUTION OF A WATER-SOLUBLE LNEAR POLYMER CONTAINING CATIONIC N-ATOMS WHEREBY TO EXHAUST ONTO SAID PULP FROM 0.05 TO 12% OF ITS WEIGHT OF SAID POLYMER, AND FORMING PAPER SHEET MATERIAL FROM THE PULP SO TREATED.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US53884A US3112241A (en) | 1960-09-06 | 1960-09-06 | Process of imparting oil-repellency to solid materials, and materials thus produced |
US53885A US3096207A (en) | 1960-09-06 | 1960-09-06 | Process of imparting oil-repellency to solid materials |
FI1530/61A FI40279B (en) | 1960-09-06 | 1961-08-30 | |
DEP27822A DE1260059B (en) | 1960-09-06 | 1961-09-05 | Oil-repellent rendering of solid, water-insoluble substances |
GB31993/61A GB939902A (en) | 1960-09-06 | 1961-09-06 | Process for imparting oil-repellency to solid materials and materials thus produced |
FR872469A FR1305612A (en) | 1960-09-06 | 1961-09-06 | Process for imparting oil repellency properties to solids and materials thus obtained |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US53884A US3112241A (en) | 1960-09-06 | 1960-09-06 | Process of imparting oil-repellency to solid materials, and materials thus produced |
US53885A US3096207A (en) | 1960-09-06 | 1960-09-06 | Process of imparting oil-repellency to solid materials |
Publications (1)
Publication Number | Publication Date |
---|---|
US3112241A true US3112241A (en) | 1963-11-26 |
Family
ID=26732342
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US53884A Expired - Lifetime US3112241A (en) | 1960-09-06 | 1960-09-06 | Process of imparting oil-repellency to solid materials, and materials thus produced |
US53885A Expired - Lifetime US3096207A (en) | 1960-09-06 | 1960-09-06 | Process of imparting oil-repellency to solid materials |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US53885A Expired - Lifetime US3096207A (en) | 1960-09-06 | 1960-09-06 | Process of imparting oil-repellency to solid materials |
Country Status (5)
Country | Link |
---|---|
US (2) | US3112241A (en) |
DE (1) | DE1260059B (en) |
FI (1) | FI40279B (en) |
FR (1) | FR1305612A (en) |
GB (1) | GB939902A (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3468697A (en) * | 1966-03-02 | 1969-09-23 | Colgate Palmolive Co | Method of treating textile articles which are usually laundered |
JPS4969909A (en) * | 1972-11-11 | 1974-07-06 | ||
US3953283A (en) * | 1972-10-05 | 1976-04-27 | Continental Can Company, Inc. | Paperboard having improved oil resistance |
US4064067A (en) * | 1976-04-26 | 1977-12-20 | E. I. Du Pont De Nemours And Company | Fluorosurfactant leveling agent |
US4118235A (en) * | 1975-09-18 | 1978-10-03 | Daikin Kogyo Co., Ltd. | Mold release agent |
US4380565A (en) * | 1982-01-08 | 1983-04-19 | Champion International Corporation | Color preservation of wax-coated paperboard |
US5120364A (en) * | 1990-10-10 | 1992-06-09 | Ciba-Geigy Corporation | Heteroatom containing perfluoroalkyl terminated neopentyl sulfates and salts thereof |
EP0683267A2 (en) | 1994-05-18 | 1995-11-22 | Minnesota Mining And Manufacturing Company | Fluorine-containing phosphates, and their use in papermaking |
EP0687533A1 (en) * | 1994-06-14 | 1995-12-20 | AUSIMONT S.p.A. | Process for surface treatment of cellulosic, metallic, vitreous materials, or cements, marbles, granites and the like |
US5525261A (en) * | 1994-10-18 | 1996-06-11 | Henkel Corporation | Anti-static composition and method of making the same |
US7943567B2 (en) | 2004-01-30 | 2011-05-17 | E.I. Du Pont De Nemours And Company | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
US20110257423A1 (en) * | 2008-01-22 | 2011-10-20 | Dupont Performance Elastomers Llc | Process for producing fluoroelastomers |
US20110303620A1 (en) * | 2010-06-10 | 2011-12-15 | Di Gao | Superoleophobic and Superhydrophilic Fabric Filters for Rapid Water-Oil Separation |
US8318656B2 (en) | 2007-07-03 | 2012-11-27 | E. I. Du Pont De Nemours And Company | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
US20130210976A1 (en) * | 2012-02-13 | 2013-08-15 | E. I. Du Pont De Nemours And Company | Fluorinated phosphates as surface active agents |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3188340A (en) * | 1961-12-08 | 1965-06-08 | Du Pont | Polyfluoro alkanamidoalkyl phosphates |
US3431140A (en) * | 1964-09-29 | 1969-03-04 | American Cyanamid Co | Oil and water repellent textiles |
US3318240A (en) * | 1966-02-21 | 1967-05-09 | Beveridge Paper Company | Matrix mat for plastic printing plate |
US3754979A (en) * | 1970-05-01 | 1973-08-28 | Du Pont | Line resolution in screen printing |
US4145303A (en) * | 1971-03-08 | 1979-03-20 | Minnesota Mining And Manufacturing Company | Cleaning and treating compositions |
US4097297A (en) * | 1975-08-07 | 1978-06-27 | E. I. Du Pont De Nemours And Company | Barrier coatings |
US4313978A (en) * | 1978-12-20 | 1982-02-02 | Minnesota Mining And Manufacturing Company | Antistatic compositions and treatment |
JPS63267792A (en) * | 1987-04-22 | 1988-11-04 | Daikin Ind Ltd | Production of phosphoric acid ester salt of dialkyl substituted with fluoroalkyl-containing groups |
EP0462063A1 (en) * | 1990-06-13 | 1991-12-18 | Ciba-Geigy Ag | Fluorinated paper sizes |
JP3030863B2 (en) * | 1990-12-25 | 2000-04-10 | ダイキン工業株式会社 | Leather modifying agent, leather modifying method and modified tanned leather |
DE69332402T2 (en) * | 1992-01-27 | 2003-06-26 | Daikin Ind Ltd | USE OF A TREATMENT AGAINST FIBER PRODUCTS, METHOD FOR TREATING FIBER PRODUCTS AND THE FIBER PRODUCTS TREATED BY THIS |
US6191389B1 (en) * | 2000-03-31 | 2001-02-20 | General Electric Company | Grease resistant oven grille |
KR20070001117A (en) * | 2004-01-30 | 2007-01-03 | 그레이트 레이크스 케미칼 코퍼레이션 | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
JP2007528917A (en) * | 2004-01-30 | 2007-10-18 | グレート・レークス・ケミカル・コーポレーション | Manufacturing method and system, composition, surfactant, monomer unit, metal complex, phosphate ester, glycol, aqueous film-forming foam, and foam stabilizer |
MXPA06008620A (en) * | 2004-01-30 | 2007-03-21 | Great Lakes Chemical Corp | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers. |
US20090137773A1 (en) * | 2005-07-28 | 2009-05-28 | Andrew Jackson | Production Processes and Systems, Compositions, Surfactants, Monomer Units, Metal Complexes, Phosphate Esters, Glycols, Aqueous Film Forming Foams, and Foam Stabilizers |
US20070027349A1 (en) * | 2005-07-28 | 2007-02-01 | Stephan Brandstadter | Halogenated Compositions |
WO2008019111A2 (en) * | 2006-08-03 | 2008-02-14 | Great Lakes Chemical Corporation | Telomer compositions and production processes |
CA3167784A1 (en) | 2018-01-26 | 2019-08-01 | Ecolab Usa Inc. | Solidifying liquid anionic surfactants |
CN111655829A (en) | 2018-01-26 | 2020-09-11 | 埃科莱布美国股份有限公司 | Curing liquid amine oxide, betaine and/or sulfobetaine surfactants with binders and optional carriers |
AU2019210740B2 (en) | 2018-01-26 | 2022-02-17 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2597702A (en) * | 1950-06-29 | 1952-05-20 | Du Pont | Fluoroalkylphosphoric compounds |
US2913427A (en) * | 1957-06-25 | 1959-11-17 | Stamford Chemical Company | Water repellent composition and article coated therewith |
US2920979A (en) * | 1956-01-13 | 1960-01-12 | Minnesota Mining & Mfg | Paper sized with fluorocarbon agents on one side and coated on the opposite side with thermoplastic materials |
US2955958A (en) * | 1956-03-05 | 1960-10-11 | Nathan J Brown | Process of treating woven textile fabric with a vinyl chloride polymer |
US2957796A (en) * | 1957-05-01 | 1960-10-25 | Michigan Res Lab Inc | Grease-proof paper |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2917409A (en) * | 1958-12-31 | 1959-12-15 | Du Pont | Fluorine compounds, process of preparing said compounds, and process of rendering textile oil repellent |
-
1960
- 1960-09-06 US US53884A patent/US3112241A/en not_active Expired - Lifetime
- 1960-09-06 US US53885A patent/US3096207A/en not_active Expired - Lifetime
-
1961
- 1961-08-30 FI FI1530/61A patent/FI40279B/fi active
- 1961-09-05 DE DEP27822A patent/DE1260059B/en active Pending
- 1961-09-06 FR FR872469A patent/FR1305612A/en not_active Expired
- 1961-09-06 GB GB31993/61A patent/GB939902A/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2597702A (en) * | 1950-06-29 | 1952-05-20 | Du Pont | Fluoroalkylphosphoric compounds |
US2920979A (en) * | 1956-01-13 | 1960-01-12 | Minnesota Mining & Mfg | Paper sized with fluorocarbon agents on one side and coated on the opposite side with thermoplastic materials |
US2955958A (en) * | 1956-03-05 | 1960-10-11 | Nathan J Brown | Process of treating woven textile fabric with a vinyl chloride polymer |
US2957796A (en) * | 1957-05-01 | 1960-10-25 | Michigan Res Lab Inc | Grease-proof paper |
US2913427A (en) * | 1957-06-25 | 1959-11-17 | Stamford Chemical Company | Water repellent composition and article coated therewith |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3468697A (en) * | 1966-03-02 | 1969-09-23 | Colgate Palmolive Co | Method of treating textile articles which are usually laundered |
US3953283A (en) * | 1972-10-05 | 1976-04-27 | Continental Can Company, Inc. | Paperboard having improved oil resistance |
JPS4969909A (en) * | 1972-11-11 | 1974-07-06 | ||
JPS5545680B2 (en) * | 1972-11-11 | 1980-11-19 | ||
US4118235A (en) * | 1975-09-18 | 1978-10-03 | Daikin Kogyo Co., Ltd. | Mold release agent |
US4308063A (en) * | 1975-09-18 | 1981-12-29 | Daikin Kogyo Co., Ltd. | Mold release agent |
US4064067A (en) * | 1976-04-26 | 1977-12-20 | E. I. Du Pont De Nemours And Company | Fluorosurfactant leveling agent |
US4380565A (en) * | 1982-01-08 | 1983-04-19 | Champion International Corporation | Color preservation of wax-coated paperboard |
US5120364A (en) * | 1990-10-10 | 1992-06-09 | Ciba-Geigy Corporation | Heteroatom containing perfluoroalkyl terminated neopentyl sulfates and salts thereof |
US5714266A (en) * | 1994-05-18 | 1998-02-03 | Minnesota Mining And Manufacturing Company | Fluorine-containing phosphates |
EP0683267A2 (en) | 1994-05-18 | 1995-11-22 | Minnesota Mining And Manufacturing Company | Fluorine-containing phosphates, and their use in papermaking |
EP0687533A1 (en) * | 1994-06-14 | 1995-12-20 | AUSIMONT S.p.A. | Process for surface treatment of cellulosic, metallic, vitreous materials, or cements, marbles, granites and the like |
US5691000A (en) * | 1994-06-14 | 1997-11-25 | Ausimont S.P.A. | Process for surface treatment of cellulosic, metallic, vitreous materials, or cements, marbles, granites and the like |
US5525261A (en) * | 1994-10-18 | 1996-06-11 | Henkel Corporation | Anti-static composition and method of making the same |
US7943567B2 (en) | 2004-01-30 | 2011-05-17 | E.I. Du Pont De Nemours And Company | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
US8318656B2 (en) | 2007-07-03 | 2012-11-27 | E. I. Du Pont De Nemours And Company | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
US20110257423A1 (en) * | 2008-01-22 | 2011-10-20 | Dupont Performance Elastomers Llc | Process for producing fluoroelastomers |
US20110303620A1 (en) * | 2010-06-10 | 2011-12-15 | Di Gao | Superoleophobic and Superhydrophilic Fabric Filters for Rapid Water-Oil Separation |
US8695810B2 (en) * | 2010-06-10 | 2014-04-15 | University of Pittsburgh—of the Commonwealth System of Higher Education | Superoleophobic and superhydrophilic fabric filters for rapid water-oil separation |
US20130210976A1 (en) * | 2012-02-13 | 2013-08-15 | E. I. Du Pont De Nemours And Company | Fluorinated phosphates as surface active agents |
Also Published As
Publication number | Publication date |
---|---|
FI40279B (en) | 1968-09-02 |
FR1305612A (en) | 1962-10-05 |
DE1260059B (en) | 1968-02-01 |
US3096207A (en) | 1963-07-02 |
GB939902A (en) | 1963-10-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3112241A (en) | Process of imparting oil-repellency to solid materials, and materials thus produced | |
US2416232A (en) | Coated organic material and method of making the same | |
US4136218A (en) | Process for the improvement of the water-absorbing capacity and the absorptivity of textile materials | |
US5100566A (en) | Fabric wrinkle reduction composition and method | |
US2468086A (en) | Process of rendering anionic coating materials adherent to anionic bases | |
US4230746A (en) | Foaming composition for textile finishing and coatings | |
US3183054A (en) | Aldehyde condensation products and their use in treating fibrous materials | |
US3220869A (en) | Process for improving textile fabrics | |
US2137465A (en) | Process of finishing textiles | |
US2899263A (en) | Eneurea | |
US2826514A (en) | Treatment of textile materials and composition therefor | |
US2804402A (en) | Treatment of cellulose containing textile materials and compositions therefor | |
US2426770A (en) | Textile finishing composition comprising a methoxymethyl melamine and an aliphatic alcohol having at least eight carbon atoms | |
US4198316A (en) | Foaming composition for textile finishing and coatings | |
US3519562A (en) | Textile lubricant | |
CA1145507A (en) | Concentrated aqueous solutions of sulfo group-containing fluorescent brighteners which are stable on storage | |
US3054698A (en) | Flame proofing of cellulosic materials | |
US2686121A (en) | Process of loading cellulosic fibers | |
US4208485A (en) | Foaming composition for textile finishing and coatings | |
GB2241515A (en) | Flame retardant composition | |
US3627556A (en) | Durable press finish for wool/cellulosic fabrics (melamine/dihydroxy-imidazolidinone resins) | |
US3983269A (en) | Durable press composition and process | |
US2718478A (en) | Antistatic treatment of fibrous materials | |
US2316057A (en) | Textile material | |
US3984367A (en) | Durable press composition and process |