US2359750A - Viscose spinning solution - Google Patents
Viscose spinning solution Download PDFInfo
- Publication number
- US2359750A US2359750A US396543A US39654341A US2359750A US 2359750 A US2359750 A US 2359750A US 396543 A US396543 A US 396543A US 39654341 A US39654341 A US 39654341A US 2359750 A US2359750 A US 2359750A
- Authority
- US
- United States
- Prior art keywords
- polyoxyethylene
- spinning
- glycol ethers
- per molecule
- esters
- 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
- 238000009987 spinning Methods 0.000 title description 35
- 229920000297 Rayon Polymers 0.000 title description 18
- -1 polyoxyethylene Polymers 0.000 description 112
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 51
- 125000006353 oxyethylene group Chemical group 0.000 description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 29
- 150000002148 esters Chemical class 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 23
- 150000002894 organic compounds Chemical class 0.000 description 13
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000001117 sulphuric acid Substances 0.000 description 10
- 235000011149 sulphuric acid Nutrition 0.000 description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 10
- 235000009529 zinc sulphate Nutrition 0.000 description 10
- 239000011686 zinc sulphate Substances 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 239000004627 regenerated cellulose Substances 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 229940035044 sorbitan monolaurate Drugs 0.000 description 6
- JNYAEWCLZODPBN-KVTDHHQDSA-N (2r,3r,4r)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O JNYAEWCLZODPBN-KVTDHHQDSA-N 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
- 125000001165 hydrophobic group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001241 acetals Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- ZEMPKEQAKRGZGQ-UHFFFAOYSA-N Triricinolein Natural products CCCCCCC(O)CC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCC(O)CCCCCC)COC(=O)CCCCCCCC=CCC(O)CCCCCC ZEMPKEQAKRGZGQ-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001323 aldoses Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000001593 sorbitan monooleate Substances 0.000 description 2
- 229940035049 sorbitan monooleate Drugs 0.000 description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-VBJOUPRGSA-N triricinolein Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC)COC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-VBJOUPRGSA-N 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-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
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-MGMRWDBRSA-N [(2R)-2-[(2R,3R,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] (Z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O NWGKJDSIEKMTRX-MGMRWDBRSA-N 0.000 description 1
- LWZFANDGMFTDAV-JOCBIADPSA-N [(2r)-2-[(2r,3r,4r)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O LWZFANDGMFTDAV-JOCBIADPSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Substances OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001976 hemiacetal group Chemical group 0.000 description 1
- ACGUYXCXAPNIKK-UHFFFAOYSA-N hexachlorophene Chemical compound OC1=C(Cl)C=C(Cl)C(Cl)=C1CC1=C(O)C(Cl)=CC(Cl)=C1Cl ACGUYXCXAPNIKK-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
Definitions
- This invention has for its principal object to provide improvements in the spinning operation employed in the manufacture of synthetic shapes such as yarns, filaments, films and the like.
- the compounds contemplated by the invention are the polyethylene glycol ethers of organic compounds having at least one functional aliphatic hydroxyl group and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as alcohols and polyhydric alcohols, hydroxy carboxylic acids, hydroxy esters, epoxy alcohols and hydroxy epoxy esters; polyethylene glycol esters of compounds having at least one functional aliphatic carboxyl group and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as fatty acids, polycarboxylic acids, hydroxy fatty acids, and epoxy fatty acids; polyethylene glycol acetals of organic compounds having at least one functional aliphatic aldehyde group and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as aliphatic aldehydes, aldoses; and polyethylene glycol ether-esters, ether-acetals, ester
- the compounds are nonionogenic, rela- 1 tively chemically unreactive, substantially stable under spinning conditions, and contain no free functional groups other than aliphatic hydroxy] or carbonyl.
- the compounds may contain ether, ester, acetal, or hemiacetal groups which are substantially stable under the conditions of spinning.
- the stability herein referred to is such stability that the compounds, prior to their complete decomposition in the spinning solution or the spinning bath, will exert their favorable influence in preventing clogging of the openings in the spinnerets and in thereby maintaining uniformity of filament size.
- Caprylic acid esters of polyoxyethylene glycols Pelargonic acid esters of polyoxyethylene glycols Capric acid esters of polyoxyethylene glycols Erasmus acid esters of polyoxyethylene glycols Myristic acid esters of polyoxyethylene glycols Palmitic acid esters of polyoxyethylene glycols Margaric acid esters of polyoxyethylene glycols Stearic acid esters of polyoxyethylene glycols Oleic acid esters of polyoxyethylene glycols Ricinoleic acid esters of polyoxyethylene glycols Hydroxy stearic acid esters of polyoxyethylene glycols Octyl' ethers of polyoxyethylene glycols Decyl ethers of polyoxyethylene glycols Dodecyl ethers of polyoxyethylene glycols Tetradecyl ethers of polyoxyethylene glycols Hexadecyl ethers of polyoxyethylene glycols Octadecylethers of polyoxyethylene glycols Cetyl ethers of polyoxyethylene glycols Montanyl ethers of poly
- Polyoxyethylene glycol ethers of mannita monolaurate Polyoxyethylene glycol ethers of sorbitan monolaurate Polyoxyethylene glycol ethers of sorbitan monooleate acyl glycol ethers of mannitan monomyristate Polyoxyethylene glycol ethers of mannitan mono.
- polyethylene glycol group or groups may be connected in the same compound by either or both ether and ester groups depending upon the parent substances from which they are derived and the method of producing the compounds therefrom.
- oxyethylene units may replace the hydrogen
- all Of the oxyethylene units may be in a single chain or theymay be present in the compound in the form 01 two or more chains, the latter situation being common when the compound is produced by reacting ethylene oxide with a parent substance having at least two functional groups whether hydroxyl, aldehyde, carboxyl or any combination of these three. It is only essential that the total number of oxyethylene units in the one or more chains add up to a total of at least eight. Some or all of the oxyethylene units or chains of such units may have either or both of their'ends connected to the remainder of, the compound through ether, ester or acetal linkages. I
- the common methods of making the compounds with which the invention is concerned generally result in the formation of mixtures of compounds having a greater or less number of oxyethylene units per molecule and analytical determinations of such complex mixtures indicate the average number of such units per molecule throughout the mass of the compound analyzed.
- the compounds employed in accordance with this invention may comprise molecules containing less than 8 oxyethylene units in admixture with'others containing 8 or more'such units. Accordingly, in the specification' and the claims the definition of these compounds is intended to include not only those having a uniform and constant constitution throughout but also such complexmixtures as have an effective portion containing at' least 8 oxyethylene units per molecule.
- the various surface active compounds may be produced in any suitable manner. Generally, they may be produced by reacting ethylene oxide with the selected fatty acid, alcohol, hydroxy fatty acid, hydroxy fatty acid ester or related compound within the scope of the general class described above.
- the reaction products of ethylene oxide with sorbitan monolaurate may be prepared by introducing sorbitan monolaurate with a small amount of sodium methylate as a catalyst into a stirring autoclave and raising the temperature to C., gradually adding ethylene oxide to this mixture and maintaining the temperature between C. and
- the degree to which the reaction with the ethylene oxide is carried out depends upon the compound with which it is reacted and the character of the spinning solution or precipitating bath in which it is to be used. The reaction is carried out to such a degree that the reaction products are soluble in the spinning bath or spinning solution in which they are used.v
- the invention is applicable in forming regenerated cellulose shapes by extruding viscose solution into an acid precipitating bath and is found particularly advantageous where the precipitating bath contains a high concentration of metallic salts, especially zinc, in concentrations of the order of 3% to 10%.
- the invention is also advantageous in spinning other cellulose solutions including cuprammonium and cellulose derivatives such as cellulose acetate as well as other synthetic materials, including cop'olymers of vinyl chloride and vinyl acetate.
- a small amount of the surface active material of the same order may be dissolved in the precipitating medium or may be added to both the spinning solution and the precipitating medium.
- a multifllament regenerated cellulos am is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of and between 0.02 and 0.03% of organic compounds comprising a sorbitan monolaurate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyethylene units per molecule.
- a multifllament regenerated cellulose yarn is formed-by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a sorbitan monolaurate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 8 oxyethylene units per molecule.
- a multifllament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid' spinning bath containing a high concentatlon of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a sorbitan monooleate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyethylene units per molecule.
- a multifllament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentation of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a mannitan monomyristate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyethylene units per molecule.
- a multifllament regenerated cellulose yarn is formed by, extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a mannitan monolaurate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oiwethylene units per molecule.
- a multifllament regenerated cellulose yarn is formed by extruding a viscose solution through a spinneret into an aqueous sulphuric acid spinning bathcontaining a high concentration of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a mannitan monooleate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyetln'lene units per molecule.
- a multifllament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between 0.02
- mannitan monopalmitate having atleast 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyethylene units per molecule.
- a multifllament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between v a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising lauryl alcohol in which the hydroxyl group has been replaced by a 'hydroxy polyoxyethylene group and the average oxyethylene content is 20 oxyethylene units per molecule.
- a multifllament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising triricinolein in which at least 1 free hydroxyl group has been replaced 'by a hydroxy polyoxyethylene group and the average oxyethylene content is 20 oxyethylene units per molecule.
- a viscosespinning solution containing a small amount of a substantially stable surface achydrophobic group containing at least 8 carbon atoms in a straight chain and at least one polyoxyethylene group, the oxyethylene content being at least 8 oxyethylene units per molecule and a suiiicient number of such units in excess of eight to render the hexitan derivative substantially soluble in the viscose solution.
- a viscose spinning solution containing a small amount of a substituted sorbitan monolaurate having at least one polyoxyethylene and 0.03% of organic compounds comprising .a 25
- the oxyethylene content being at least 8 oxyethylene units per molecule and a sumcient content being at least 8 oxyethylene units per molecule and a, sufficient number of such units in excess of 8 to render the alcohol condensation product substantially soluble in a viscose solution.
Description
Patented Oct. 10, 1%44 VISCOSE SPINNING SOLUTION Benjamin WQCollins, Swarthmore, Pa., assignor to American Viscose Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application April 19, 1941,
Serial No. 389,325. Divided and this application June 4, 1941, Serial No. 396,543
7 Claims.
spun by extruding the solution through a spinneret or jet having a minute opening or openings into a coagulating or precipitating medium. During the spinning operation obstructions tend to form in the minute openings in the spinneret or jet and they become fouled or clogged. This results, in the case of yarn or filament spinning, in a lack of uniformity in the filament sizes and weak and broken filaments in the finished product and,.in the case of producing films, in a lack of uniformity in thickness. In order to avoid these dimculties it is the present practice to inspect the spinnerets or jets at short intervals of time and replace those in which the openings have become fouled. This interrupts the continuity of the spinning operation and causes delays which are time consuming and costly.
This invention has for its principal object to provide improvements in the spinning operation employed in the manufacture of synthetic shapes such as yarns, filaments, films and the like.
Other objects of the invention will be apparentfrom the following description and appended claims.
It has now been found that fouling of the spinnerets and the need for frequent inspection and replacement and the lack of uniformity in yarns, filaments and films can be largely eliminated by extruding the spinning solution in the presence of a small amount of a surface active, non-ionogenic organic compound comprising at least one hydrophobic group having a hydrocarbon chain of at least 8 carbon atoms and a hydrophilic polyoxyethylene content sumcient to render the compound water-soluble so that it is readily soluble in the spinning bath or in the spinning solution. The polyoxyethylene content should be at least 8 oxyethylene units per molecule. Generally, the greater the extent to which the compound is hydrophobic, the larger th number of oxyethylene units that are required to render the compound sufliciently soluble for the purposes of the invention. I
In general, the compounds contemplated by the invention are the polyethylene glycol ethers of organic compounds having at least one functional aliphatic hydroxyl group and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as alcohols and polyhydric alcohols, hydroxy carboxylic acids, hydroxy esters, epoxy alcohols and hydroxy epoxy esters; polyethylene glycol esters of compounds having at least one functional aliphatic carboxyl group and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as fatty acids, polycarboxylic acids, hydroxy fatty acids, and epoxy fatty acids; polyethylene glycol acetals of organic compounds having at least one functional aliphatic aldehyde group and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as aliphatic aldehydes, aldoses; and polyethylene glycol ether-esters, ether-acetals, ester-acetals or ether-ester-acetals of organic compounds having various combinations of hydroxyl, aldehyde and carboxyl groups and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as hydroxy fatty acids, polyhydroxy fatty acids, aldoses, and -uronic acids. The compounds are nonionogenic, rela- 1 tively chemically unreactive, substantially stable under spinning conditions, and contain no free functional groups other than aliphatic hydroxy] or carbonyl. The compounds may contain ether, ester, acetal, or hemiacetal groups which are substantially stable under the conditions of spinning. The stability herein referred to is such stability that the compounds, prior to their complete decomposition in the spinning solution or the spinning bath, will exert their favorable influence in preventing clogging of the openings in the spinnerets and in thereby maintaining uniformity of filament size.
The following are examples of specific compounds that may be used in carrying out this invention:
Caprylic acid esters of polyoxyethylene glycols Pelargonic acid esters of polyoxyethylene glycols Capric acid esters of polyoxyethylene glycols Laurie acid esters of polyoxyethylene glycols Myristic acid esters of polyoxyethylene glycols Palmitic acid esters of polyoxyethylene glycols Margaric acid esters of polyoxyethylene glycols Stearic acid esters of polyoxyethylene glycols Oleic acid esters of polyoxyethylene glycols Ricinoleic acid esters of polyoxyethylene glycols Hydroxy stearic acid esters of polyoxyethylene glycols Octyl' ethers of polyoxyethylene glycols Decyl ethers of polyoxyethylene glycols Dodecyl ethers of polyoxyethylene glycols Tetradecyl ethers of polyoxyethylene glycols Hexadecyl ethers of polyoxyethylene glycols Octadecylethers of polyoxyethylene glycols Cetyl ethers of polyoxyethylene glycols Montanyl ethers of polyoxyethylene glycols Oleyl ethers of polyoxyethylene glycols Polyoxyethylene Polyoxyethylene glycol ethersof-diethylene glycol monoacyl esters Polyoxyethylene glycol ethers of polyethylene glycol monoacyl esters Polyoxyethylene glycol ethers of propylene glycol monoacyl esters Polyoxyethylene glycol ethers of glycerol monoacyl esters Polyoxyethylene glycol ethers of glycerol diaoyl esters Polyoxyethylene glycol ethers of polyglycerol acyl partial esters Polyoxyethylene glycol ethers of erythritol acyl partial esters Polyox-yethylene glycol ethers of pentaerythritol acyl partial esters Polyoxyethylene glycol ethers of hexitol acyl partial esters Polyoxyethylene glycol ethers of mannitol acyl partial esters Polyoxyethylene glycol ethers of sorbitol acyl partial esters Polyoxyethylene glycol ethers of hexitan acyl partial esters Polyoxyethylene glycol ethers of mannitan acyl partial esters Polyoxyethylene glycol ethers of sorbitan acyl partial esters Polyoxyethylene glycol ethers 01' hexide partial esters Polyoxyethylene' glycol ethers of mannide acyl partial esters Polyoxyethylene glycol ethers of .sorbide acyl partial esters Polyoxyethylene glycol ethers of cyclotol acyl partial esters v Polyoxyethylene glycol ethers of inositol a'cyl partialesters Polyoxyethylene glycol ethers of monosaccharide acyl partial esters Polyoxyethylene glycol ethers of oligosaccharide acyl partial esters The acyl esters may be the esters of fatty acids having 8 carbon atoms in a straight chain, such as caprylic, pelargonic, capric, lauric, myristlc, palmitic, margarlc, stearic, oleic, ricinoleic, and hydroxy stearic.
More specific combinations are:
Polyoxyethylene glycol ethers of mannita monolaurate Polyoxyethylene glycol ethers of sorbitan monolaurate Polyoxyethylene glycol ethers of sorbitan monooleate acyl glycol ethers of mannitan monomyristate Polyoxyethylene glycol ethers of mannitan mono.-
palmitate Polyoxyethylene glycol ethers of mannitan monostearate Polyoxyethylene glycol ethers of maImitan monooleate Polyoxyethyleneglycol ethers of triricinolein Polyoxyethylene glycol acetals of lauric aldehyde The polyethylene glycol group or groups may be connected in the same compound by either or both ether and ester groups depending upon the parent substances from which they are derived and the method of producing the compounds therefrom. For example, if ricinoleic acid, hydroxy stearic acid or other bi-functional compounds are reacted with ethylene oxide, part of the oxyethylene units may replace the hydrogen It should be noted that all Of the oxyethylene units may be in a single chain or theymay be present in the compound in the form 01 two or more chains, the latter situation being common when the compound is produced by reacting ethylene oxide with a parent substance having at least two functional groups whether hydroxyl, aldehyde, carboxyl or any combination of these three. It is only essential that the total number of oxyethylene units in the one or more chains add up to a total of at least eight. Some or all of the oxyethylene units or chains of such units may have either or both of their'ends connected to the remainder of, the compound through ether, ester or acetal linkages. I
The common methods of making the compounds with which the invention is concerned generally result in the formation of mixtures of compounds having a greater or less number of oxyethylene units per molecule and analytical determinations of such complex mixtures indicate the average number of such units per molecule throughout the mass of the compound analyzed. For this reason the compounds employed in accordance with this invention may comprise molecules containing less than 8 oxyethylene units in admixture with'others containing 8 or more'such units. Accordingly, in the specification' and the claims the definition of these compounds is intended to include not only those having a uniform and constant constitution throughout but also such complexmixtures as have an effective portion containing at' least 8 oxyethylene units per molecule.
The various surface active compounds may be produced in any suitable manner. Generally, they may be produced by reacting ethylene oxide with the selected fatty acid, alcohol, hydroxy fatty acid, hydroxy fatty acid ester or related compound within the scope of the general class described above. For example, the reaction products of ethylene oxide with sorbitan monolaurate may be prepared by introducing sorbitan monolaurate with a small amount of sodium methylate as a catalyst into a stirring autoclave and raising the temperature to C., gradually adding ethylene oxide to this mixture and maintaining the temperature between C. and
C. For reasons stated above, the degree to which the reaction with the ethylene oxide is carried out depends upon the compound with which it is reacted and the character of the spinning solution or precipitating bath in which it is to be used. The reaction is carried out to such a degree that the reaction products are soluble in the spinning bath or spinning solution in which they are used.v
The invention is applicable in forming regenerated cellulose shapes by extruding viscose solution into an acid precipitating bath and is found particularly advantageous where the precipitating bath contains a high concentration of metallic salts, especially zinc, in concentrations of the order of 3% to 10%. The invention is also advantageous in spinning other cellulose solutions including cuprammonium and cellulose derivatives such as cellulose acetate as well as other synthetic materials, including cop'olymers of vinyl chloride and vinyl acetate.
In carrying out the invention a small amount of the surface active material of the order of 0.01
to 0.05% may be dissolved in the spinning solution and the spinning solution is extruded into a precipitating medium. Where a liquid precipitating medium or bath is used, a small amount of the surface active material of the same order may be dissolved in the precipitating medium or may be added to both the spinning solution and the precipitating medium.
The following examples are illustrative of the invention:
1. A multifllament regenerated cellulos am is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of and between 0.02 and 0.03% of organic compounds comprising a sorbitan monolaurate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyethylene units per molecule.
2. A multifllament regenerated cellulose yarn is formed-by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a sorbitan monolaurate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 8 oxyethylene units per molecule.
3. A multifllament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid' spinning bath containing a high concentatlon of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a sorbitan monooleate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyethylene units per molecule.
4. A multifllament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentation of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a mannitan monomyristate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyethylene units per molecule.
5. A multifllament regenerated cellulose yarn is formed by, extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a mannitan monolaurate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oiwethylene units per molecule.
6. A multifllament regenerated cellulose yarn is formed by extruding a viscose solution through a spinneret into an aqueous sulphuric acid spinning bathcontaining a high concentration of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a mannitan monooleate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyetln'lene units per molecule.
7. A multifllament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between 0.02
mannitan monopalmitate having atleast 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyethylene units per molecule. v
8. A multifllament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between v a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising lauryl alcohol in which the hydroxyl group has been replaced by a 'hydroxy polyoxyethylene group and the average oxyethylene content is 20 oxyethylene units per molecule.
10. A multifllament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulphuric acid spinning bath containing a high concentration of zinc sulphate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising triricinolein in which at least 1 free hydroxyl group has been replaced 'by a hydroxy polyoxyethylene group and the average oxyethylene content is 20 oxyethylene units per molecule.
It was found that in carrying out the spinning operation in accordance with the present invention it is necessary to change less than 50% as many spinnerets as where ordinary methods of spinning are followed. Where multifllament yarn 40 is formed the filaments are of uniform crosssection and the yarn is of generally improved quality.
While preferred embodiments of the invention have been shown, it is to be understood that changes and variations may be made without departing from the'spirit and scope of the invention as defined by the appended claims.
What I claim is:
1. A viscosespinning solution containing a small amount of a substantially stable surface achydrophobic group containing at least 8 carbon atoms in a straight chain and at least one polyoxyethylene group, the oxyethylene content being at least 8 oxyethylene units per molecule and a suiiicient number of such units in excess of eight to render the hexitan derivative substantially soluble in the viscose solution.
3. A viscose spinning solution containing a small amount of a substituted sorbitan monolaurate having at least one polyoxyethylene and 0.03% of organic compounds comprising .a 25
group, the oxyethylene content being at least 8 oxyethylene units per molecule and a sumcient content being at least 8 oxyethylene units per molecule and a, sufficient number of such units in excess of 8 to render the alcohol condensation product substantially soluble in a viscose solution.
6. A viscose spinning solution containing a small amount of a condensation product of ethylene oxide with lauryl alcohol having at least 8 oxyethylene units per molecule. 3
7. A viscose spinning solution containing a small amount of a condensation product of ethylene oxide with lauryl alcohol, having an average of about 20 oxyethylene units pen'nolecule.
BENJAIVHN W. COLLINS.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US396543A US2359750A (en) | 1941-04-19 | 1941-06-04 | Viscose spinning solution |
US751136A US2519227A (en) | 1941-04-19 | 1947-05-28 | Manufacture of yarns and the like |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US389325A US2359749A (en) | 1941-04-19 | 1941-04-19 | Manufacture of synthetic yarns and the like |
US396543A US2359750A (en) | 1941-04-19 | 1941-06-04 | Viscose spinning solution |
Publications (1)
Publication Number | Publication Date |
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US2359750A true US2359750A (en) | 1944-10-10 |
Family
ID=27012647
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US396543A Expired - Lifetime US2359750A (en) | 1941-04-19 | 1941-06-04 | Viscose spinning solution |
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US (1) | US2359750A (en) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2451558A (en) * | 1944-11-06 | 1948-10-19 | Rayonier Inc | Chemically treated wood pulp and a method of producing a cellulosic product |
US2459298A (en) * | 1944-11-17 | 1949-01-18 | Stamberger Paul | Plastic compositions made with vulcanized, polyethylene glycol esters as plasticizers |
US2481693A (en) * | 1944-04-29 | 1949-09-13 | Rayonier Inc | Raw cotton for conversion into rayon |
US2508036A (en) * | 1950-05-16 | Compounds having high wetting | ||
US2519227A (en) * | 1941-04-19 | 1950-08-15 | American Viscose Corp | Manufacture of yarns and the like |
US2525786A (en) * | 1948-06-18 | 1950-10-17 | Edward M Filachione | Polyhydric alcohol esters of acyloxycarboxylic acids |
US2573701A (en) * | 1948-06-18 | 1951-11-06 | Edward M Filachione | Polyethylene glycol esters of acyloxycarboxylic acids |
US2578684A (en) * | 1948-06-18 | 1951-12-18 | Edward M Filachione | Glycol esters of acyloxycarboxylic acids |
US2592234A (en) * | 1949-02-16 | 1952-04-08 | Eastman Kodak Co | Plasticized cellulose acetate-butyrate and cellulose acetatepropionate |
US2599803A (en) * | 1948-11-01 | 1952-06-10 | Shell Dev | Lubricating composition |
US2665443A (en) * | 1949-06-04 | 1954-01-12 | Chicopee Mfg Corp | Astatic brush for grooming the hair |
US2694021A (en) * | 1951-03-30 | 1954-11-09 | Atlas Powder Co | Textile bearing a starch size |
US2805169A (en) * | 1955-07-18 | 1957-09-03 | Rayonier Inc | High-alpha cellulose |
US2892729A (en) * | 1954-11-03 | 1959-06-30 | American Viscose Corp | Process of producing viscose rayon |
US2895787A (en) * | 1954-12-30 | 1959-07-21 | American Viscose Corp | Process of producing all skin rayon |
US3240819A (en) * | 1960-02-17 | 1966-03-15 | Monsanto Co | Ethenoxy-substituted alkanols |
US3418405A (en) * | 1962-09-10 | 1968-12-24 | Kurashiki Rayon Co | Method of manufacturing flat viscose fibers |
US3431127A (en) * | 1963-09-12 | 1969-03-04 | Union Carbide Corp | Process of improving the anti-blocking characteristics of regenerated cellulose tubing and the product resulting from said process |
-
1941
- 1941-06-04 US US396543A patent/US2359750A/en not_active Expired - Lifetime
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2508036A (en) * | 1950-05-16 | Compounds having high wetting | ||
US2519227A (en) * | 1941-04-19 | 1950-08-15 | American Viscose Corp | Manufacture of yarns and the like |
US2481693A (en) * | 1944-04-29 | 1949-09-13 | Rayonier Inc | Raw cotton for conversion into rayon |
US2451558A (en) * | 1944-11-06 | 1948-10-19 | Rayonier Inc | Chemically treated wood pulp and a method of producing a cellulosic product |
US2459298A (en) * | 1944-11-17 | 1949-01-18 | Stamberger Paul | Plastic compositions made with vulcanized, polyethylene glycol esters as plasticizers |
US2525786A (en) * | 1948-06-18 | 1950-10-17 | Edward M Filachione | Polyhydric alcohol esters of acyloxycarboxylic acids |
US2573701A (en) * | 1948-06-18 | 1951-11-06 | Edward M Filachione | Polyethylene glycol esters of acyloxycarboxylic acids |
US2578684A (en) * | 1948-06-18 | 1951-12-18 | Edward M Filachione | Glycol esters of acyloxycarboxylic acids |
US2599803A (en) * | 1948-11-01 | 1952-06-10 | Shell Dev | Lubricating composition |
US2592234A (en) * | 1949-02-16 | 1952-04-08 | Eastman Kodak Co | Plasticized cellulose acetate-butyrate and cellulose acetatepropionate |
US2665443A (en) * | 1949-06-04 | 1954-01-12 | Chicopee Mfg Corp | Astatic brush for grooming the hair |
US2694021A (en) * | 1951-03-30 | 1954-11-09 | Atlas Powder Co | Textile bearing a starch size |
US2892729A (en) * | 1954-11-03 | 1959-06-30 | American Viscose Corp | Process of producing viscose rayon |
US2895787A (en) * | 1954-12-30 | 1959-07-21 | American Viscose Corp | Process of producing all skin rayon |
US2805169A (en) * | 1955-07-18 | 1957-09-03 | Rayonier Inc | High-alpha cellulose |
US3240819A (en) * | 1960-02-17 | 1966-03-15 | Monsanto Co | Ethenoxy-substituted alkanols |
US3418405A (en) * | 1962-09-10 | 1968-12-24 | Kurashiki Rayon Co | Method of manufacturing flat viscose fibers |
US3431127A (en) * | 1963-09-12 | 1969-03-04 | Union Carbide Corp | Process of improving the anti-blocking characteristics of regenerated cellulose tubing and the product resulting from said process |
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