US3342630A - Silicate and titanate orthoesters and soil-proofed textile materials - Google Patents
Silicate and titanate orthoesters and soil-proofed textile materials Download PDFInfo
- Publication number
- US3342630A US3342630A US30863963A US3342630A US 3342630 A US3342630 A US 3342630A US 30863963 A US30863963 A US 30863963A US 3342630 A US3342630 A US 3342630A
- Authority
- US
- United States
- Prior art keywords
- soil
- orthoesters
- oily
- oil
- titanate
- 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
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- 239000004753 textile Substances 0.000 title claims description 24
- -1 titanate orthoesters Chemical class 0.000 title claims description 21
- 239000000463 material Substances 0.000 title claims description 17
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title description 7
- 239000002689 soil Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 239000005871 repellent Substances 0.000 claims description 8
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 230000002940 repellent Effects 0.000 claims description 3
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 108010081348 HRT1 protein Hairy Proteins 0.000 claims 1
- 102100021881 Hairy/enhancer-of-split related with YRPW motif protein 1 Human genes 0.000 claims 1
- 239000004744 fabric Substances 0.000 description 20
- 239000007921 spray Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 238000009736 wetting Methods 0.000 description 16
- 239000003921 oil Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 11
- 150000002905 orthoesters Chemical class 0.000 description 11
- 229920000742 Cotton Polymers 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052605 nesosilicate Inorganic materials 0.000 description 3
- 150000004762 orthosilicates Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- GJYLSFCFHFUODO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-icosafluoroundecan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F GJYLSFCFHFUODO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 240000008415 Lactuca sativa Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940035423 ethyl ether Drugs 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000012045 salad Nutrition 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 244000056139 Brassica cretica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000020434 chocolate syrup Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000019673 concord grape juice Nutrition 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019674 grape juice Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229940097789 heavy mineral oil Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000020344 instant tea Nutrition 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Substances ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
- D06M13/507—Organic silicon compounds without carbon-silicon bond
-
- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2279—Coating or impregnation improves soil repellency, soil release, or anti- soil redeposition qualities of fabric
- Y10T442/2287—Fluorocarbon containing
Definitions
- the present invention relates to the preparation of silicate and titanate orthoesters of fluorinated alcohols and to soil-proofed textiles produced by treatment of textiles therewith.
- Oily, particulate-soil is best illustrated by the grime, i.e., finely divided dirt and oily exudations of the human skin, which accumulates from the environment on the collars and cuffs of mens shirts and face powder, makeup and the oily exudations of the human skin which accumulates on the neckbands of womens blouses.
- any test based upon comparison of finishes applied and used in daily life is doomed to failure because of the inability of the investigator to control (1) the manner in which the oily, particul-ate-soil is accumulated, (2) the amount of oily, particulate-soil accumulated, and (3) the composition of the oily, particulate-soil and, hence, the tenacity with which the oily, particulate-soil is held by the treated textile.
- the degree of soiling is determined with a Photovolt Reflectance Meter using a Tri Blue Filter. Six readings are taken on each unwashed specimen and reported as reflectance before washing. This is an evaluation of the effectiveness of the finish provided by the treating agent to repel oily, particulate-soil. Six readings are taken on each washed specimen. This is an evaluation of the effectiveness of the finish provided by the treating agent to release any accumulated oily, particulate-soil during laundering. The arithmetic average of each of the six readings is reported. The higher the reflectance the more efficient is the finishing agent in repelling and/or releasing the oily, particulate-soil.
- a spray rating number 70/0 indicates a spray rating of 70 while the 0 in the denominator indicates wetting to the under surface of the cloth at the wet areas.
- test specimens of a minimum size of 7" x 7 are conditioned at 70 F. and 65 percent relative humidity for a minimum of four hours before testing. 7
- test specimen fastened securely and wrinkle-free in a metal hoop having a diameter of six inches, is placed and centered six inches under a standard spray nozzle at an angle of 45 degrees to the horizontal.
- Two hundred and fifty milliliters of water at 80i2 F. is poured into the funnel attached above the spray nozzle.
- the spray lasts 25-30 seconds at the end of which time the hoop is taken by one edge and the opposite edge tapped smartly once against a solid object with the Wet side facing the solid; this procedure is repeated with the hoop reversed 180 degrees.
- Oil repellency te'st The Minnesota Mining and Manufacturing Company oil repellency test is based on the dilference of penetrating properties of two hydrocarbon liquids, heavy mineral oil (Nujol) and n-heptane. The Nujol-heptane proportions for each rating were selected by 3M to give oily stain resistance somewhat comparable to the water-borne stain resistance corresponding to each of the spray ratings of the AATCC Standard Test Method 22-1952 described hereinbefore.
- the standard oil-heptane mixtures are contained in small stoppered medicine dropper bottles. A drop of each mixture is placed on the fabric. The appearance of the test oil is observed through the drop. The occurrence of wetting or penetration is noted. The number corresponding to that mixture containing the highest percentage of heptane which does not penetrate or wet the fabric after three minutes is considered the oil repellency rating of the finish.
- the change in the optical refractivity of the drop is often an indication of wetting. In some cases wetting can be better determined by observing the other side of the fabric. In some cases of oil/heptane rating, the term 0+ has been used to indicate a modicum of resistance to wetting by oil.
- Three inch medicine droppers are used to draw the stains from their containers. A one cubic centimeter calibration is established, and marked on the exterior of each dropper. The stains are squeezed vertically downward from a height of two inches above the fabric.
- Duplicate sets of stains are applied in separate areas so that one half of the fabric can be washed.
- the wash is carried out with fifty grams of FAB, a cotton cycle, and a dummy load to total five pounds in a Norge Home Automatic Washer.
- finishing agents or soil-repellent agents of the present invention are silicate and titanate orthoesters of fluorinated aliphatic alcohols in which at least 70 percent of the hydrogens, other than the hydroxyl hydrogen, has been replaced with fluorine and in which the terminal carbon atom is attached to at least two, and preferably three, fluorine atoms.
- the orthoesters of the present invention have compositions corresponding to the formula where X is Si or Ti; R is an alkyl group having one to six carbon atoms; Q is the fluorinated alkyl group of any aliphatic alcohol having one to twenty-two carbon atoms and three to forty-five hydrogen atoms of which at least seventy percent has been replaced by fluorine and the terminal group is CHF and preferably CF n is zero to three; and m is four to one.
- orthosilicates and orthotitanates are produced in any suitable manner.
- the orthosilicates of C -perfiu0roalc0h0l were prepared as follows: One equivalent of ethylorthosilicate was reacted with four equivalents of C perfluoroalcohol lH,ll-I,11H eicosafluoro-l-undecanol [CHF (CF CH OH] in the presence of a catalytic small amount of sodium methoxide (1 gram). About one-third of the theoretical amount of ethanol to be produced in a complete ester interchange was collected leaving a residue which was predominantly a mixture of orthosilicates having up to four fluoroalkyl radicals per molecule.
- the orthotitanate of the C -perfluoroalcohol was prepared. That is to say, four equivalents of the C -perfluoroalcohol were dissolved in about 710 milliliters of xylene. The Xylene solution was heated and one equivalent of tetrabutyltitanate was added. The xylene-and liberated butyl alcohol were removed by vacuum distillation. A brownish solid soluble in cold methanol remained as a residue of the vacuum distillation.
- a mixture of C -perfluoroalkyl orthotitanates was prepared as follows: Four equivalents of C -perfluoroalcohol and one equivalent of tetrabutyltitanate were dissolved in ethyl ether. The solution was agitated for about thirty minutes and allowed to stand for about sixty hours. The ethylether was removed at atmospheric pressure. Five grams of distillate were removed at reduced pressure leaving a yellow residue which solidified to a tan-colored, waxy solid, soluble in isopropanol.
- the silicate and titanate orthoesters of the fluorinated alcohols are applied to the textile material or substrate either from solution in suitable solvents such as C to C aliphatic alcohols, acetone, toluene, hexane, and heptane or from emulsions using a surfactant such as triethanolaminelaurylsulfonate, sorbitol monostearate and other non-rewetting surfactants.
- suitable solvents such as C to C aliphatic alcohols, acetone, toluene, hexane, and heptane or from emulsions using a surfactant such as triethanolaminelaurylsulfonate, sorbitol monostearate and other non-rewetting surfactants.
- a surfactant such as triethanolaminelaurylsulfonate, sorbitol monostearate and other non-rewetting surfactants.
- the fabric for illustrative purposes 80 x 80 cotton is padded one dip, one nip through the solution or dispersion of the orthoester or esters preferably containing an alkaline catalyst such as sodium bicarbonate, potassium hydroxide and triethanolamine or an acid catalyst such as phosphoric acid, oxalic acid, and zinc chloride.
- an alkaline catalyst such as sodium bicarbonate, potassium hydroxide and triethanolamine
- an acid catalyst such as phosphoric acid, oxalic acid, and zinc chloride.
- the treated substrate is dried and heat treated at a temperature in the range of room temperature (circa 70 F.) and 350 F. for a period inversely as the temperature and for example about twenty-four hours at 70 F.
- novel silicate and titanate orthoesters of fluorinated alcohols (corresponding in composition to the generic formula (RO) (OQ) given hereinbefore) of the present invention are not to be confused with products previously described.
- RO generic formula
- US. Patent No. 2,709,174 there are described products conforming to the formula TiY (ORY) where Y is a halogen such as chlorine or bromine, R is an alkylene or rolefinyl group either substituted or unsubstituted and x has the value of 0 to 3.
- these products may be dissolved in solvents and subjected to partial hydrolysis, or they may be directly subjected to hydrolysis and the partial hydrolytic and condensation products used as protective coatings, adhesives, binders, textile-treating agents and the like, or they maybe mixed with other organo titanium derivatives and employed in any of the manners set forth.
- US. Patent No. 2,928,857 relates to organic compounds of silicon containing polyfluoroalkoxy groups derived from tetrafluoroethylene/ alcohol telomers.
- the polyfluoroalkoxy silanes described in U.S. Patent No. 2,928,857 have the following general formula:
- R is a monovalent hydrocarbon radical free from aliphatic unsaturation
- n is 4, 6, or 8
- x and y are positive integers from 13, inclusive, i.e., integers having a value of 1, 2, or 3, and the sum of x-l-y equals 4.
- the polyfluoroalkoxysilanes described in US. Fatent No. 2,928,857 in view of their high thermal stability and good lubricating qualities are of great value as lubricants especially for use at high temperatures.
- Those polyfluoroalkoxysilanes boiling above 200 C. described in US. 2,928,857 are useful components in liquid polishes for glass and painted surfaces and in easy rubbing, self-polishing waxes.
- the fluorinated carbinoxysilanes and polymers thereof are useful in the surface treatment of metals.
- the patentee states that he has found that a preliminary application of his (1,1-dihydroperfluorobutoxy) dichlorosilane to the aluminum surface provides ahighly effective bonding action between the metal and a subsequently applied coating of plastic fluorinated sealer material for aircraft sealers designed to leakproof the wing section fuel tanks of all-metal aircraft.
- the carbinoxysilane compounds described in US. Patent No. 2,993,925 have the generic formula:
- Rf is a fluorinated alkyl radical containing only carbon and fluorine atoms
- X is a member of the class consisting of halogen atoms and amino groups
- x is 1-4.
- R is a monovalent hydrocarbon radical
- X is a member selected from the class consisting of hydrogen and fluorine
- m is an integer equal to at least 2, e.g., from 2 to 16 or more
- n is an integer equal to at least 2, e.g., from 2 to 6 or more
- a is 0 or 1
- b is 2 or 3
- the sum of a+b is equal to 3.
- cyclic siloxanes useful in the preparation of copolymers of bistrifluoropropylsiloxane with other siloxanes such as trifluoropropylmethylsiloxane, diphenylsiloxane and the like are described.
- the patented cyclic siloxanes conform to the formula where n is an integer from 3 to 4 inclusive. It will be observed that in the patented cyclic siloxanes only the terminal carbon of the alkyl moiety is attached to fluorine atoms.
- CH CH CH CH only three of seven hydrogen atoms or only forty-three percent of the hydrogens of the alkyl group has been replaced by fluorine atoms where as in the orthoesters of the present invention at least 70 percent of the hydrogen atoms of the alkyl group of the aliphatic alcohol has been replaced by fluorine atoms.
- ester interchange catalyst Ti(OR) where R is a hydrocarbon radical and preferably is isopropyl or butyl is described.
- Waxy solids having a composition corresponding to the formula )n Q)m where R is an alkyl group having one to six carbon atoms, Q is the fluorinated alkyl group of an aliphatic alcohol having one to twenty-two carbon atoms and three to fortyfive hydrogen atoms of which at least percent has been replaced by fluorine and the terminal group is selected from CHF and CF n is 0 to 3; m is 4 to 1; and x is selected from the group consisting of Si and Ti.
- a compound as defined in claim 1 wherein the aliphatic alcohol is 1H,1H,11H-eicosa-fluoro 1 undecanol and X is Ti.
- Textile material having affixed thereto in soil repellent amount, a waxy solid as defined in claim 1, said textile material and waxy solid having been cured at a temperature in the range of room temperature to 350 F. for a period inversely as the temperature and about twenty-four hours at room temperature.
Description
United States Patent C) l 3,342,630 SILICATE AND TITANATE ORTHOESTERS AND SiHL-PROOFED TEXTILE MATERIALS Domeniclc Donald Gagliardi, East Greenwich, R.I., as-
signor to Colgate-Palmolive Company, New York,
N.Y., a corporation of Delaware No Drawing. Filed Sept. 13, 1963, Ser. No. 308,639
7 Claims. (Cl. 117-1395) The present invention relates to the preparation of silicate and titanate orthoesters of fluorinated alcohols and to soil-proofed textiles produced by treatment of textiles therewith.
Since the early years of the nineteenth century man has sought to impart water-repellency and more recently oil-repellency to textiles. However, few, if any, of these prior arts attempting to produce waterand oil-repellent textiles were soil-repellent. That is to say, the textiles sotreated while water-repellent and/or oil-repellent when contacted with oily, particulate-soil attracted rather than repelled such oily particulate-soil.
Oily, particulate-soil is best illustrated by the grime, i.e., finely divided dirt and oily exudations of the human skin, which accumulates from the environment on the collars and cuffs of mens shirts and face powder, makeup and the oily exudations of the human skin which accumulates on the neckbands of womens blouses.
Those skilled in the art will recognize that for the evaluation of the comparative effectiveness of treating agents to repel such oily, particulate-soil any test based upon comparison of finishes applied and used in daily life is doomed to failure because of the inability of the investigator to control (1) the manner in which the oily, particul-ate-soil is accumulated, (2) the amount of oily, particulate-soil accumulated, and (3) the composition of the oily, particulate-soil and, hence, the tenacity with which the oily, particulate-soil is held by the treated textile. Accordingly, it has been necessary to employ an investigating procedure in which the composition of the oily, particulate-soil is known and controlled, in which the amount of oily, particulate-soil accumulated on the test pieces is uniform, and the manner in which the oily, particulate-soil is accumulated is uniform. The following investigative procedure provides such uniformit Composition of oily, parZiculate-soil (American Cyanamid Synthetic Soil) The following dry ingredients are blended thoroughly, dried in a forced draft convection oven for eight hours at 50 C., then milled for twenty-five hours with ceramic balls and stored in a polyethylene bag:
1 R. T. Vanderbilt Peerless. 2 Davison Chemical Co.
3 Bandy and Smith Molacco. 4 C. K. Williams Co.
Depositin.-Fifteen to twenty 6" x 8" numbered specimens (usually 80 x 80 cotton), including at least one untreated control, are tumbled for thirty minutes with ten percent of the aforedescribed oily, particulatesoil based on the Weight of the fabric. The tumbling is carried out in a five liter capacity Five Minute Home Cleaner 3,342,630 Patented Sept. 19, 1967 ICC at 44 rpm. Six No. 8 Neoprene rubber stoppers are distributed among the specimens to increase mechanical action. At the end of the tumbling, the specimens are removed and each individually shaken up and down fifteen times to remove surface dirt.
Evaluati0n.-The so-soiled specimens are then cut into two pieces (to produce two 4" x 6" pieces). One half is washed with fifty grams of FAB in a cotton cycle with a five pound dummy load, hung to dry, and lightly ironed under a clean cotton cloth.
The degree of soiling is determined with a Photovolt Reflectance Meter using a Tri Blue Filter. Six readings are taken on each unwashed specimen and reported as reflectance before washing. This is an evaluation of the effectiveness of the finish provided by the treating agent to repel oily, particulate-soil. Six readings are taken on each washed specimen. This is an evaluation of the effectiveness of the finish provided by the treating agent to release any accumulated oily, particulate-soil during laundering. The arithmetic average of each of the six readings is reported. The higher the reflectance the more efficient is the finishing agent in repelling and/or releasing the oily, particulate-soil.
While for many finishing applications it is manifest that the effectiveness of a finishing agent to repel rather than attract and to shed rather than retain oily, particulatesoil is of primary importance, the effectiveness of a finishing agent to impart waterand/or ioil-repellency to a treated textile is of interest also. For the determination of the water-repellency imparted to a textile there is the AATCC Standard Test Method 22-1952 generally known as the Spray Test. For the determination of the oilrepellency conferred upon a textile there is the 3M Oil Repellency Test described in the publication of the Minnesota Mining and Manufacturing Company entitled 3M Textile Chemicals at Appendix A-Test Methods, Page 1.
Spray Test (Resistance to Wetting).-This test method is applicable to any textile fabric. It measures the resistance of fabrics to wetting by a water spray and the results depend primarily on the degree of hy-drophobicity inherent in the fibers and yarns and subsequent treatments applied to the fibers and yarns. Water is sprayed against the taut surface of a test specimen. Evaluation of the wetted pattern is readily brought about by comparing the wetted pattern with standard wetting pattern pictures. The ratings are numerical and have the following significances.
100No sticking or Wetting of the upper surface. 90Slight random sticking or wetting of the upper surface. -Wetting of the upper surface at the spray points. 70Partial wetting of the whole of the upper surface. 50-Complete wetting of the whole of the upper surface. OCom-plete wetting of the whole of the upper and the lower surfaces.
When measuring the spray rating, it is not unusual to encounter a test specimen with sufiicient hydrophobic properties to confine the area of wetting and yet permit wetting through. The following illustrates the report of such a condition.
Thus a spray rating number 70/0 indicates a spray rating of 70 while the 0 in the denominator indicates wetting to the under surface of the cloth at the wet areas.
The test specimens of a minimum size of 7" x 7 are conditioned at 70 F. and 65 percent relative humidity for a minimum of four hours before testing. 7
The test specimen, fastened securely and wrinkle-free in a metal hoop having a diameter of six inches, is placed and centered six inches under a standard spray nozzle at an angle of 45 degrees to the horizontal. Two hundred and fifty milliliters of water at 80i2 F. is poured into the funnel attached above the spray nozzle. The spray lasts 25-30 seconds at the end of which time the hoop is taken by one edge and the opposite edge tapped smartly once against a solid object with the Wet side facing the solid; this procedure is repeated with the hoop reversed 180 degrees.
Oil repellency te'st.The Minnesota Mining and Manufacturing Company oil repellency test is based on the dilference of penetrating properties of two hydrocarbon liquids, heavy mineral oil (Nujol) and n-heptane. The Nujol-heptane proportions for each rating were selected by 3M to give oily stain resistance somewhat comparable to the water-borne stain resistance corresponding to each of the spray ratings of the AATCC Standard Test Method 22-1952 described hereinbefore.
The standard oil-heptane mixtures are contained in small stoppered medicine dropper bottles. A drop of each mixture is placed on the fabric. The appearance of the test oil is observed through the drop. The occurrence of wetting or penetration is noted. The number corresponding to that mixture containing the highest percentage of heptane which does not penetrate or wet the fabric after three minutes is considered the oil repellency rating of the finish.
The change in the optical refractivity of the drop is often an indication of wetting. In some cases wetting can be better determined by observing the other side of the fabric. In some cases of oil/heptane rating, the term 0+ has been used to indicate a modicum of resistance to wetting by oil.
The numerical values of the Oil Repellency Rating and the significance thereof are tabulated in the following:
1 No holdout to Nujol.
Since resistance to soiling by water-borne and/ or oilborne stains is also of importance in the finishing of household furnishing such as rugs, sheets, curtains, draperies, wearing apparel and the like, a test for evaluating the capacity of treating agents such as the novel orthoesters of the present invention to confer resistance to staining by coffee, salad oil, tea, ketchup, grape juice, ink and similar waterand/or oil-borne stains encountered in the every day environment is desirable and has been developed.
Waterand/0r oil-repellency test.The fabrics are streatched lightly on 12 x 31" frames. All or part of the frame area is used depending on the amount of fabric available. The frames are supported at both ends with the fabric about eight inches above a black horizontal surface. The fabric is in contact with nothing but the frame.
Three inch medicine droppers are used to draw the stains from their containers. A one cubic centimeter calibration is established, and marked on the exterior of each dropper. The stains are squeezed vertically downward from a height of two inches above the fabric.
After five minutes the unabsorbed stain is wiped off the fabric with two sweeps of Kleenex and the stain rated.
Duplicate sets of stains are applied in separate areas so that one half of the fabric can be washed. The wash is carried out with fifty grams of FAB, a cotton cycle, and a dummy load to total five pounds in a Norge Home Automatic Washer.
The stains employed are as follows:
Water stains Instant Tea, Tetley a Salad Mustard (Ann Page) Sheaffers 232 Blue-Black Chocolate Syrup (Bosco) l rip Concord Grape Juice Oil stains Oleomargarine b Tomato Sauce Wesson Oil Gulf Supreme Motor Oil 20/20 Hand Lotion (Jergens) 8 cubic centimeters dry powder per 200 cubic centimeters of water (applied at F.).
b Melted and applied at 160 F.
Stain ratings The finishing agents or soil-repellent agents of the present invention are silicate and titanate orthoesters of fluorinated aliphatic alcohols in which at least 70 percent of the hydrogens, other than the hydroxyl hydrogen, has been replaced with fluorine and in which the terminal carbon atom is attached to at least two, and preferably three, fluorine atoms. In general, the orthoesters of the present invention have compositions corresponding to the formula where X is Si or Ti; R is an alkyl group having one to six carbon atoms; Q is the fluorinated alkyl group of any aliphatic alcohol having one to twenty-two carbon atoms and three to forty-five hydrogen atoms of which at least seventy percent has been replaced by fluorine and the terminal group is CHF and preferably CF n is zero to three; and m is four to one.
These orthosilicates and orthotitanates are produced in any suitable manner. Presently, it is preferred to prepare the orthoesters by ester interchange. Thus, the orthosilicates of C -perfiu0roalc0h0l were prepared as follows: One equivalent of ethylorthosilicate was reacted with four equivalents of C perfluoroalcohol lH,ll-I,11H eicosafluoro-l-undecanol [CHF (CF CH OH] in the presence of a catalytic small amount of sodium methoxide (1 gram). About one-third of the theoretical amount of ethanol to be produced in a complete ester interchange was collected leaving a residue which was predominantly a mixture of orthosilicates having up to four fluoroalkyl radicals per molecule.
In a similar manner the orthotitanate of the C -perfluoroalcohol was prepared. That is to say, four equivalents of the C -perfluoroalcohol were dissolved in about 710 milliliters of xylene. The Xylene solution was heated and one equivalent of tetrabutyltitanate was added. The xylene-and liberated butyl alcohol were removed by vacuum distillation. A brownish solid soluble in cold methanol remained as a residue of the vacuum distillation.
A mixture of C -perfluoroalkyl orthotitanates was prepared as follows: Four equivalents of C -perfluoroalcohol and one equivalent of tetrabutyltitanate were dissolved in ethyl ether. The solution was agitated for about thirty minutes and allowed to stand for about sixty hours. The ethylether was removed at atmospheric pressure. Five grams of distillate were removed at reduced pressure leaving a yellow residue which solidified to a tan-colored, waxy solid, soluble in isopropanol.
The silicate and titanate orthoesters of the fluorinated alcohols are applied to the textile material or substrate either from solution in suitable solvents such as C to C aliphatic alcohols, acetone, toluene, hexane, and heptane or from emulsions using a surfactant such as triethanolaminelaurylsulfonate, sorbitol monostearate and other non-rewetting surfactants. The orthoester or esters of a fluorinated alcohol or a mixture of orthoesters of fluorinated alcohols is applied to the substrate in any suitable manner. For example, the fabric for illustrative purposes 80 x 80 cotton is padded one dip, one nip through the solution or dispersion of the orthoester or esters preferably containing an alkaline catalyst such as sodium bicarbonate, potassium hydroxide and triethanolamine or an acid catalyst such as phosphoric acid, oxalic acid, and zinc chloride. After impregnation with the solution or dis persion of the orthoester or esters the treated substrate is dried and heat treated at a temperature in the range of room temperature (circa 70 F.) and 350 F. for a period inversely as the temperature and for example about twenty-four hours at 70 F.
Cotton padded as described hereinbefore with the reaction product of tetrabutyl orthoester of titanium and C trihydrofluoroalkyl alcohol 1H,1H,11H-eicosafluoro- 1-undecanol [CHF (CF CHOH] in a 1:4 mol ratio had the repellencies indicated by the numerical values tabulated hereinafter.
Percent solids in bath 3 Cured at room temperature Repellency:
Spray 50/0 Oil 70 Reflectance:
B 37 A 68 Cured at 300 F. for 5 mins.-
Repellency:
Spray 5 O/ Oil 0 Reflectance:
It will be observed that the foregoing results are exemplary of results obtained without the use of either an alkaline catalyst or an acid catalyst. When a catalyst is to be used, the catalyst is incorporated in the padding bath in concentrations of about 0.5 to about 1.0 percent by weight based upon the weight of the treating solution.
The novel silicate and titanate orthoesters of fluorinated alcohols (corresponding in composition to the generic formula (RO) (OQ) given hereinbefore) of the present invention are not to be confused with products previously described. For example, in US. Patent No. 2,709,174 there are described products conforming to the formula TiY (ORY) where Y is a halogen such as chlorine or bromine, R is an alkylene or rolefinyl group either substituted or unsubstituted and x has the value of 0 to 3. As the patentees state these products may be dissolved in solvents and subjected to partial hydrolysis, or they may be directly subjected to hydrolysis and the partial hydrolytic and condensation products used as protective coatings, adhesives, binders, textile-treating agents and the like, or they maybe mixed with other organo titanium derivatives and employed in any of the manners set forth.
In US. Patent No. 2,892,859, the use of products corresponding to the formula (XR O),,Si(R) wherein n represents an integer 2 or 3, X represents a lower perfluoroalkyl group having one to eight carbon atoms, R 0 represents lower alkenoxy group having one to five car bon atoms, and R represents alkyl as snufler agents and lubricant additives. It will be observed that while the novel orthoesters of the present invention are waxy solids the products described in US. No. 2,892,859 are liquids 6 at room temperature, having boiling points from about centigrade to about 200 centigrade.
The disclosure of US. Patent No. 2,928,857 relates to organic compounds of silicon containing polyfluoroalkoxy groups derived from tetrafluoroethylene/ alcohol telomers. The polyfluoroalkoxy silanes described in U.S. Patent No. 2,928,857 have the following general formula:
wherein R is a monovalent hydrocarbon radical free from aliphatic unsaturation, n is 4, 6, or 8, x and y are positive integers from 13, inclusive, i.e., integers having a value of 1, 2, or 3, and the sum of x-l-y equals 4. The polyfluoroalkoxysilanes described in US. Fatent No. 2,928,857 in view of their high thermal stability and good lubricating qualities are of great value as lubricants especially for use at high temperatures. Those polyfluoroalkoxysilanes boiling above 200 C. described in US. 2,928,857, are useful components in liquid polishes for glass and painted surfaces and in easy rubbing, self-polishing waxes.
The fluorinated carbinoxysilanes and polymers thereof are useful in the surface treatment of metals. Thus, the patentee states that he has found that a preliminary application of his (1,1-dihydroperfluorobutoxy) dichlorosilane to the aluminum surface provides ahighly effective bonding action between the metal and a subsequently applied coating of plastic fluorinated sealer material for aircraft sealers designed to leakproof the wing section fuel tanks of all-metal aircraft. The carbinoxysilane compounds described in US. Patent No. 2,993,925 have the generic formula:
where Rf is a fluorinated alkyl radical containing only carbon and fluorine atoms, X is a member of the class consisting of halogen atoms and amino groups, and x is 1-4.
The silanes described in US. Patent No. 3,038,000 have the formula:
where R is a monovalent hydrocarbon radical, X is a member selected from the class consisting of hydrogen and fluorine, m is an integer equal to at least 2, e.g., from 2 to 16 or more, n is an integer equal to at least 2, e.g., from 2 to 6 or more, a is 0 or 1, b is 2 or 3, and the sum of a+b is equal to 3.
The carboperfluorooxyalkylsiloxane fluids prepared in Examples 2 through 5 of the US. Patent No. 3,038,000 have structures conforming to the formulae:
HF C (CF CH OOC (CH SiO (EX. 2) HF C CF CH OOC (CH SiO (EX. 3) F C(CF CH OOC(CH SiO (EX. 5)
These prior art siloxanes were dissolved in xylene mixed with a curing catalyst, padded onto cotton cloth and cured six minutes at C. The treated cloth was then subjected to spray rating tests similar to those described in the 1945 yearbook of the American Association of Textile Chemists and Colorists, Vol. XX, pages 229-233. It is to be observed that in these tests the cotton was padded from a solution made by adding two parts of silicone fluid to 100 parts by weight of xylene and 0.1 part of a 28 percent tin octoate solution in xylene was added to the mixture. The spray ratings of each material of the examples is given in the patent as follows- Spray Rating It will be observed that the oil repellency of the patented silicone fluid was not determined. It will also be observed that the particulate soil repellency was not determined. It will further be observed that the silicones of US. Patent No. 3,038,000 are fluids whereas the orthoesters f the present invention are waxy solids. Finally, it will be observed that the patented silicone fluid was padded on the cloth in the presence of the catalyst tin octoate whereas the mixture of orthotitanates of perfluoro-C alcohol were padded on the cotton in the absence of added or known catalyst.
In US. Patent No. 3,070,617 cyclic siloxanes useful in the preparation of copolymers of bistrifluoropropylsiloxane with other siloxanes such as trifluoropropylmethylsiloxane, diphenylsiloxane and the like are described. The patented cyclic siloxanes conform to the formula where n is an integer from 3 to 4 inclusive. It will be observed that in the patented cyclic siloxanes only the terminal carbon of the alkyl moiety is attached to fluorine atoms. In other words, CH CH CH only three of seven hydrogen atoms or only forty-three percent of the hydrogens of the alkyl group has been replaced by fluorine atoms where as in the orthoesters of the present invention at least 70 percent of the hydrogen atoms of the alkyl group of the aliphatic alcohol has been replaced by fluorine atoms.
Although the presently preferred method of preparing silicate and titanate orthoesters of fluorinated alcohols is through the classical method of ester interchange, applicant does not claim as his invention the ester interchange catalyst per se. In contrast in US. Patent No. 2,820,806 the ester interchange catalyst Ti(OR) where R is a hydrocarbon radical and preferably is isopropyl or butyl is described.
Those skilled in the art will recognize that, with the exception of the description of the use of the fluorinecontaining materials conforming to the generic formula (US. Patent No. 3,038,000) for imparting water repellency to cotton cloth, none of the fluorine-containing materials described in the US. patents discussed hereinbefore are concerned with imparting water and/ or oil repellency to textile materials. Furthermore, there is no suggestion in any of the patents discussed hereinbefore that any of the fluorine-containing materials described in these US. patents impart to or confer on textile materials treated therewith with the capability to repel oily, particulate soil as do the silicate and titanate orthoesters of fluorinated alcohols of the present invention.
What is claimed is: 1. Waxy solids having a composition corresponding to the formula )n Q)m where R is an alkyl group having one to six carbon atoms, Q is the fluorinated alkyl group of an aliphatic alcohol having one to twenty-two carbon atoms and three to fortyfive hydrogen atoms of which at least percent has been replaced by fluorine and the terminal group is selected from CHF and CF n is 0 to 3; m is 4 to 1; and x is selected from the group consisting of Si and Ti.
2. A compound as defined in claim 1 wherein the aliphatic alcohol is 1H,1H,11H-eicosa-fluoro 1 undecanol and X is Ti.
3. Textile material having affixed thereto in soil repellent amount a waxy solid as defined in claim 1, where R is an alkyl group having one to six carbon atoms, Q is the fluorinated alkyl group of an aliphatic alcohol having one to twenty-two carbon atoms and three to fortyfive hydrogen atoms of which at least 70 percent has been replaced by fluorine and the terminal group is selected from CHF and CF n is 0 to 3; m is 4 to 1; and X is Si or Ti.
4. Textile material as defined in claim 3 wherein the aliphatic alcohol is 1H,1H,11H eicosa-fluoro-l-undecanol and X is Ti.
5. Textile material having affixed thereto in soil repellent amount, a waxy solid as defined in claim 1, said textile material and waxy solid having been cured at a temperature in the range of room temperature to 350 F. for a period inversely as the temperature and about twenty-four hours at room temperature.
6. Textile material as set forth in claim 5 wherein curing is carried out in the presence of acid catalyst.
7. Textile material as set forth in claim 5 wherein curing is carried out in the presence of alkaline catalyst.
References Cited UNITED STATES PATENTS 2,878,144 3/1959 Conbere et al 117139.5 2,878,273 3/1959 Conbere et a1. 117-l39.5 X 2,892,859 6/1959 McBee et al. 260-448.8 2,917,409 12/1959 Green 117121 WILLIAM D. MARTIN, Primary Examiner.
T. G. DAVIS, Assistant Examiner.
Claims (2)
1. WAXY SOLIDS HAVING A COMPOSITION CORRESPONDING TO THE FORMULA
3. TEXTILE MATERIAL HAVING AFFIXED THERETO IN SOIL REPELLENT AMOUNT A WAXY SOLID AS DEFINED IN CLAIM 1, WHERE R IS AN ALKYL GROUP HAVING ONE TO SIX CARBON ATOMS, Q IS THE FLUORINATED ALKYL GROUP OF AN ALIPHATIC ALCOHOL HAVING ONE TO TWENTY-TWO CARBON ATOMS AND THREE TO FORTYFIVE HYDROGEN ATOMS OF WHICH AT LEAST 70 PERCENT HAS BEEN REPLACED BY FLUORINE AND THE TERMINAL GROUP IS SELECTED FROM CHF2 AND CF3; N IS 0 TO 3; M IS 4 TO 1; AND X IS SI OR TI.
Priority Applications (1)
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US30863963 US3342630A (en) | 1963-09-13 | 1963-09-13 | Silicate and titanate orthoesters and soil-proofed textile materials |
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Application Number | Priority Date | Filing Date | Title |
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US30863963 US3342630A (en) | 1963-09-13 | 1963-09-13 | Silicate and titanate orthoesters and soil-proofed textile materials |
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US30863963 Expired - Lifetime US3342630A (en) | 1963-09-13 | 1963-09-13 | Silicate and titanate orthoesters and soil-proofed textile materials |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2878273A (en) * | 1956-09-06 | 1959-03-17 | Arnold Hoffman & Co Inc | Quaternary ammonium salts |
US2878144A (en) * | 1957-10-21 | 1959-03-17 | Arnold Hoffman & Co Inc | Quaternary ammonium salts and fabric coated therewith |
US2892859A (en) * | 1955-05-20 | 1959-06-30 | Research Corp | Fluorine-containing alkoxyalkylsilanes |
US2917409A (en) * | 1958-12-31 | 1959-12-15 | Du Pont | Fluorine compounds, process of preparing said compounds, and process of rendering textile oil repellent |
-
1963
- 1963-09-13 US US30863963 patent/US3342630A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2892859A (en) * | 1955-05-20 | 1959-06-30 | Research Corp | Fluorine-containing alkoxyalkylsilanes |
US2878273A (en) * | 1956-09-06 | 1959-03-17 | Arnold Hoffman & Co Inc | Quaternary ammonium salts |
US2878144A (en) * | 1957-10-21 | 1959-03-17 | Arnold Hoffman & Co Inc | Quaternary ammonium salts and fabric coated therewith |
US2917409A (en) * | 1958-12-31 | 1959-12-15 | Du Pont | Fluorine compounds, process of preparing said compounds, and process of rendering textile oil repellent |
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