US2180133A - Softening agent - Google Patents
Softening agent Download PDFInfo
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- US2180133A US2180133A US137374A US13737437A US2180133A US 2180133 A US2180133 A US 2180133A US 137374 A US137374 A US 137374A US 13737437 A US13737437 A US 13737437A US 2180133 A US2180133 A US 2180133A
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- alcohol
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- softening agent
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- Expired - Lifetime
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- 239000004902 Softening Agent Substances 0.000 title description 24
- 239000000047 product Substances 0.000 description 35
- 239000000203 mixture Substances 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 235000019271 petrolatum Nutrition 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 230000019635 sulfation Effects 0.000 description 20
- 238000005670 sulfation reaction Methods 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 16
- 239000004753 textile Substances 0.000 description 15
- 239000004264 Petrolatum Substances 0.000 description 14
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 14
- 229940066842 petrolatum Drugs 0.000 description 14
- 239000000123 paper Substances 0.000 description 13
- -1 aliphatic alcohols Chemical class 0.000 description 11
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 8
- 229960000541 cetyl alcohol Drugs 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 239000010985 leather Substances 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 7
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000001180 sulfating effect Effects 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 235000019809 paraffin wax Nutrition 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 235000019737 Animal fat Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/262—Sulfated compounds thiosulfates
-
- 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
- Y10S516/03—Organic sulfoxy compound containing
-
- 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
- Y10S516/924—Significant dispersive or manipulative operation or step in making or stabilizing colloid system
- Y10S516/927—Significant dispersive or manipulative operation or step in making or stabilizing colloid system in situ formation of a colloid system making or stabilizing agent which chemical reaction
Definitions
- This invention relates to treating agents for paper and textiles, and more particularly to agents for softening leather, paper, and textile fibers. Still more particularly the invention relates to a new type of product based on longchain aliphatic alcohols having twelve to twenty carbon atoms. This invention relates specifically to the sulfation of mixtures of long-chain aliphatic alcohols and aliphatic hydrocarbons, such as the oils and waxes derived from petroleum, under conditions which do not cause condensation of the components.
- This invention has as an object the preparation of softening agents for leather, paper and tex- 15 tiles, combining the surface lubricating properties of aliphatic hydrocarbons with the softening properties of long-chain alcohol sulfate ester salts.
- the alcohol sulfate ester salts have the property of making fibrous materials, such as cotton, hemp, jute, linen, wool, silk, regenerated cellulose, cellulose acetate and wood pulp, when in the form of filaments or sheets, pliable so that they become very soft when handled.
- the alcohol sulfate ester salts lack surface lubri- 25 eating properties.
- a softening agent have surface lubricating properties in addition to the property of making the fibrous materials pliable as the feeling, or tactual response, of leather, paper, yarn or a fabric is most desirable when it feels very smooth to the touch in addition to being pliable. It is important, though, that the quantity of surface lubricant applied to the fibrous material be carefully adjusted to avoid the excessive quantities which would make it feel greasy. It is further necessary to have surface lubricating properties in softening agents to be used in sizing textiles with starches or other weighting agents in order to soften the starch film in addition to softening the textile material and giving it a smooth surface.
- a suitable softening agent for treating fibrous materials particularly for textile fabrics, form dilute aqueous emulsions which will remain stable even after having been boiled for thirty to forty minutes. Separation of the oily constituents of the softening agent 55 would cause objectionable oily spots 60 be formed on the material being processed, requiring the material to be reprocessed to remove the spots with consequent loss of time and labor.
- the objects of this invention are accomplished by the sulfation above 0 C. of mixtures of longchain aliphatic alcohols and aliphatic hydrocarbons, such as refined petroleum oils, petrolatums, and/or waxes with sulfating agents such as sulphuric acid, sulphur trioxide, chlorsulfonic acid and sulfuryl dichloride without the formation of condensation products between the components.
- the acid mixture is neutralized with an aqueous solution of a metallic base, or with an organic base.
- the invention consists of thoroughly mixing a 15 definite proportion of the aliphatic hydrocarbon and the long-chain alcohol, adding not to exceed 100% of the theoretical quantity of the sulfating agent required for complete sulfation of the alcohol, and of neutralizing the mass under conditions of controlled temperature above 0 C. and agitation.
- sulfation of the long-chain aliphatic alcohols does not go to completion even with chlorsulfonic acid, sulfation under these conditions Will leave a portion of the alcohol unsulfated. This improves the stability and finishing properties of the product.
- Example 1 19.3 parts by weight of stearyl alcohol (technical) and 12.8 parts by weight of refined petrolatum (m. p. range -50 0.; iodine No. 1020) are melted together, and 7.6 parts by weight of 35 chlorsulfonic acid (92% of theory on weight of stearyl alcohol) are added during agitation of the mass over a period of 30-40 minutes with the temperature maintained at 55-65 C.
- the product is an homogeneous white paste in appearance. It emulsifies readily in warm 5 water with simple agitation. Dilute emulsions even up to 5% will not separate after thirty to forty minutes boiling nor even while cooling from the boiling point.
- the sulfation may also be carried out to obtain still less complete sulfation of the aliphatic alcohol in order to change the finishing effect of the product.
- Example 2 245.1 parts by weight of stearyl alcohol (technical) and 8.0 parts by weight of refined petrolatum (m. p. range 40-50" C.; iodine No. 10--20) are melted together, and 7.3 parts by weight of chlorsulfonic acid (70% of theory on weight of stearyl alcohol) are added during agitation of the mass over a period of 30-40 minutes with the temperature maintained at 55-65 C.
- the product is an homogeneous white paste in appearance and in general similar to the product of Example 1, except for differences in finishing properties.
- Example 3 24.3 parts by weight of cetyl alcohol (technical) and 7.0 parts by weight of refined mineral oil (100 Saybolt units viscosity at 100 F.) are melted together, and 9.4 parts by Weight of 98% sulphuric acid (100% of theory on the weight of the cetyl alcohol) are added during agitation of the mass over a period of 50-60 minutes with the temperature maintained at 55-65 C.
- the product is an homogeneous white paste in appearance and in general similar to the prod uct of Example 1 except for differences in the finishing properties.
- Example 4 20.2 parts by weight of cetyl alcohol (technical) and 11.1 parts by weight of paraffin wax (m. p. range 5560 C.) are melted together, and 7.8 parts by weight of chlorsulfonic acid of theory on weight of cetyl alcohol) are added during agitation of the mass over a period of 30-40 minutes with the temperature maintained at 55-65 C.
- the product is an homogeneous white paste in appearance and in general similar to the product of Example 1 except for differences in finishing properties. It will produce a more waxy and stiffer finish than the product of Example 1.
- Example 5 The mass is then stirred for 4-5 minutes to allow the reaction to come to an end. 12.8 parts by weight of diethyl cyclohexyl amine are added to the reaction mass slowly during stirring.
- the product is an homogeneous, thick paste which is yellowish in color. It produces finishes of similar character tothe product of Example 4 but may be more readily removed from the treated textile fibers for processes where it is desirable to remove the finishing agents. It requires no additional detergents or other assistants in the water in whichit is to be rinsed from the textile fibers.
- organic bases besides diethyl cyclohexyl amine with which neutralization may be carried out are dimethyl cyclohexyl amine, mono cyclohexyl amine, and methyl amine.
- the aliphatic hydrocarbons be mixed with the long-chain aliphatic alcohol before sulfation in order to produce a product which will be stable during and after boiling in dilute aqueous emulsions.
- paraflin wax, or petrolatum is added to sodium alcohol sulfate paste, after sulfation and neutralization of the alcohol, in proportions to duplicate the composition of Example 1, the paraflin wax or petrolatum will blend with the alcohol sulfate paste to form an homogeneous paste.
- the paste thus prepared will form dilute aqueous emulsions which show no separation during boiling, but from which liquefied paraflin wax or petrolatum separates on cooling below the boiling point.
- the ratio of the aliphatic hydrocarbon to the long-chain alcohol should not exceed certain limits in order to minimize the risk of separation of the hydrocarbon from hot dilute aqueous emulsions of the sulfation product.
- the limits are dependent on the specific hydrocarbon or hydrocarbon mixture, on the specific alcohol or alcohol mixture, and also on the neutralizing base used.
- a preferred preparation which is made from equal parts of petrolatum (m. p. range 40-50 C.; iodine No. 17) and technical stearyl alcohol sulfated with approximately of the theoretical quantity of chlorsulfonic acid on the weight of the alcohol shows no separation of petrolatum from hot dilute aqueous emulsions.
- the ratio of petrolatum to alcohol usually does not exceed 4:5.
- the product prepared by the process of Example 1 has the advantage over paper and textile softening agents prepared by the sulfation of long-chain aliphatic alcohols that it provides an oily lubricating film of the aliphatic hydrocarbon mixture in petrolatum on the surface of paper and of textile fibers in addition to making them pliable through the action of the alcohol'sulfate.
- This type of product provides a more suitable lubricating film than the unsulfated long-chain alcohols, and it is more economically prepared as the aliphatic hydrocarbons from petroleum are in general much cheaper than long-chain aliphatic alcohols.
- Light mineral oils of 50-100 Saybolt units viscosity at 100 F., heavy mineral oils of 100-300 Saybolt units viscosity at 100 F., petrolatums, and/or paraffin waxes of the many different types available may be mixed with the different long-chain aliphatic alcohols having twelve to twenty carbon atoms and sulfated. It is, of course, preferable that the aliphatic hydrocarbons be mixed with the alcohols before sulfation and that the ratio of hydrocarbon to alcohol not exceed that which will produce a product forming dilute aqueous emulsions stable to prolonged heating.
- the leather, paper, and textile softening agents formed in the preferred processes, as illustrated in Examples 1-4 incl. have the distinct advantage over those softening agents well known to the art, such as sulfonated fats and oils from animal and vegetable sources, that they will not turn rancid during storage or hot calendering or hot ironing to develop objectionable odors and to discolor the paper or textiles to which they have been applied. This is an important property as leather, paper, and textiles are frequently spoiled with consequent loss in value by deterioration of the sulfonated fats or oils with which they have been treated.
- Paper is softened by passing it through a box preferably in the calender stack containing a 5% solution of the product of Example 1 or similar products prepared according to the process of the invention. It will have a smooth, pliable finish adding to its desirability for many purposes such as towelling, absorbent padding, and similar purposes for which soft paper is required. The treatment will also improve the absorbency of the paper.
- Textiles in the form of the loose fibers, yarns or woven fabrics are softened by treating them in aqueous solutions of the product of Example 1 or similar products prepared according to the invention.
- Cotton raw stock can be softened and its carding or combing and spinning properties improved after dyeing in a circulating type machine by adding 3 pounds of the product of Example 1 per 1000 pounds of cotton to the rinse waters after the dyeing is completed.
- Cotton and viscose yarns can be softened and the winding properties improved by the use 'of 5 ounces of the product of Example 1 per 100 gallons of water.
- Woven fabrics of cotton are given a very soft, smooth finish by treating them in a pad mangle with the various products of the invention as indicated in the following examples.
- Example 6 Light weight printed dress fabric- 7 pounds of the product of Example 1 are mixed with 100 gallons of water and preferably applied at 60-80 C.
- Example 7 Medium weight printed shirting fabric-2 pounds of the product of Example 1, pound of glycerine, and 12 pounds corn starch are mixed with 100 gallons of water. The mixture is boiled for 3 minutes and preferably applied at 60-80 C.
- Example 8 Bleached suiting fabric-41 pounds of the product of Example 3, 20 pounds of corn starch,
- Example 9 Dyed heavy suit lining fabric-9 pounds of the product of Example 4 and 1 pound glycerine are mixed with 100 gallons of water and preferably applied at 60-80 C.
- the products of this invention are also useful, in addition to their applications in leather, paper,
- a process of preparing a softening agent which comprises reacting a mixture of a substantially saturated higher aliphatic petroleum hydrocarbon and a long chain aliphatic alcohol having from 12 to 20 carbon atoms with a quantity of a sulfating agent which is not greater than that required for complete sulfation of the alcohol in the'mixture under relatively mild conditions to avoid the condensation of the components of the mixture.
- a process of preparing a softening agent which comprises reacting a mixture of a higher aliphatic petroleum hydrocarbon selected from the group consisting of mineral oils, petrolatums, and paraffin waxes and a long chain aliphatic alcohol having from 12 to 20 carbon atoms with a quantity of a sulfating agent which is not greater than that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with a solution of an alkali metal hydroxide.
- a higher aliphatic petroleum hydrocarbon selected from the group consisting of mineral oils, petrolatums, and paraffin waxes and a long chain aliphatic alcohol having from 12 to 20 carbon atoms
- a sulfating agent which is not greater than that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture
- a process of manufacturing a softening agent which comprises reacting a mixture of technical stearyl alcohol and refined petrolatum with a quantity of chlorsulfonic acid which does not exceed that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with a solution of sodium hydroxide.
- a process of manufacturing a softening agent which comprises reacting a mixture of cetyl alcohol and paraflln wax with a quantity of chlorsulfonic acid which does not exceed that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with a solution of sodium hydroxide.
- a softening agent prepared according to the process defined in claim 1 which contains some unsulfated alcohol.
- a process of preparing a softening agent which comprises reacting a mixture of a higher aliphatic petroleum hydrocarbon selected from the group consisting of mineral oils, petrolatums, and paramn waxes and a long chain aliphatic alcohol having from 12 to 20 carbon atoms with a quantity of a sulfating agent which is not greater than that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with an organic base.
- a higher aliphatic petroleum hydrocarbon selected from the group consisting of mineral oils, petrolatums, and paramn waxes and a long chain aliphatic alcohol having from 12 to 20 carbon atoms
- a sulfating agent which is not greater than that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with an organic base.
- a process of manufacturing a softening agent which comprises reacting a mixture of cetyl alcohol and paraffin wax with a quantity of chlorsulfonic acid which does not exceed that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with an organic base.
Description
Patented Nov. 14, 1939 UNITED STATES PATENT OFFICE SOFTENING AGENT No Drawing.
Application April 16, 1937,
Serial No. 137,374
12 Claims.
This invention relates to treating agents for paper and textiles, and more particularly to agents for softening leather, paper, and textile fibers. Still more particularly the invention relates to a new type of product based on longchain aliphatic alcohols having twelve to twenty carbon atoms. This invention relates specifically to the sulfation of mixtures of long-chain aliphatic alcohols and aliphatic hydrocarbons, such as the oils and waxes derived from petroleum, under conditions which do not cause condensation of the components.
This invention has as an object the preparation of softening agents for leather, paper and tex- 15 tiles, combining the surface lubricating properties of aliphatic hydrocarbons with the softening properties of long-chain alcohol sulfate ester salts. The alcohol sulfate ester salts have the property of making fibrous materials, such as cotton, hemp, jute, linen, wool, silk, regenerated cellulose, cellulose acetate and wood pulp, when in the form of filaments or sheets, pliable so that they become very soft when handled. However, the alcohol sulfate ester salts lack surface lubri- 25 eating properties. It is very desirable that a softening agent have surface lubricating properties in addition to the property of making the fibrous materials pliable as the feeling, or tactual response, of leather, paper, yarn or a fabric is most desirable when it feels very smooth to the touch in addition to being pliable. It is important, though, that the quantity of surface lubricant applied to the fibrous material be carefully adjusted to avoid the excessive quantities which would make it feel greasy. It is further necessary to have surface lubricating properties in softening agents to be used in sizing textiles with starches or other weighting agents in order to soften the starch film in addition to softening the textile material and giving it a smooth surface.
It has been heretofore possible to obtain surface lubricating properties in long-chain alcohol sulfate softeners by leaving a portion of the alcohol unsulfated. The possibilities of this procedure have been found very limited as the longchain alcohols do not permit a wide variety of surface lubricating effects.
It is also essential that a suitable softening agent for treating fibrous materials, particularly for textile fabrics, form dilute aqueous emulsions which will remain stable even after having been boiled for thirty to forty minutes. Separation of the oily constituents of the softening agent 55 would cause objectionable oily spots 60 be formed on the material being processed, requiring the material to be reprocessed to remove the spots with consequent loss of time and labor.
The objects of this invention are accomplished by the sulfation above 0 C. of mixtures of longchain aliphatic alcohols and aliphatic hydrocarbons, such as refined petroleum oils, petrolatums, and/or waxes with sulfating agents such as sulphuric acid, sulphur trioxide, chlorsulfonic acid and sulfuryl dichloride without the formation of condensation products between the components. The acid mixture is neutralized with an aqueous solution of a metallic base, or with an organic base.
The invention consists of thoroughly mixing a 15 definite proportion of the aliphatic hydrocarbon and the long-chain alcohol, adding not to exceed 100% of the theoretical quantity of the sulfating agent required for complete sulfation of the alcohol, and of neutralizing the mass under conditions of controlled temperature above 0 C. and agitation. As the sulfation of the long-chain aliphatic alcohols does not go to completion even with chlorsulfonic acid, sulfation under these conditions Will leave a portion of the alcohol unsulfated. This improves the stability and finishing properties of the product.
Thefollowing examples illustrate the process of the invention.
Example 1 19.3 parts by weight of stearyl alcohol (technical) and 12.8 parts by weight of refined petrolatum (m. p. range -50 0.; iodine No. 1020) are melted together, and 7.6 parts by weight of 35 chlorsulfonic acid (92% of theory on weight of stearyl alcohol) are added during agitation of the mass over a period of 30-40 minutes with the temperature maintained at 55-65 C.
The mass is then stirred for 4 to 5 minutes to allow the reaction to come to an end. 60.3 parts by weight of 5.4% sodium hydroxide at 30 C. are added to the reaction mass slowly during stirring.
The product is an homogeneous white paste in appearance. It emulsifies readily in warm 5 water with simple agitation. Dilute emulsions even up to 5% will not separate after thirty to forty minutes boiling nor even while cooling from the boiling point.
The sulfation may also be carried out to obtain still less complete sulfation of the aliphatic alcohol in order to change the finishing effect of the product.
Example 2 245.1 parts by weight of stearyl alcohol (technical) and 8.0 parts by weight of refined petrolatum (m. p. range 40-50" C.; iodine No. 10--20) are melted together, and 7.3 parts by weight of chlorsulfonic acid (70% of theory on weight of stearyl alcohol) are added during agitation of the mass over a period of 30-40 minutes with the temperature maintained at 55-65 C.
The mass is then stirred for 4-5 minutes to allow the reaction to come to an end. 60.6 parts by weight of 5.2% sodium hydroxide at 30 C. are added to the reaction mass slowly during stirring.
The product is an homogeneous white paste in appearance and in general similar to the product of Example 1, except for differences in finishing properties.
The following example illustrates the use of refined mineral oil instead of petrolatum.
Example 3 24.3 parts by weight of cetyl alcohol (technical) and 7.0 parts by weight of refined mineral oil (100 Saybolt units viscosity at 100 F.) are melted together, and 9.4 parts by Weight of 98% sulphuric acid (100% of theory on the weight of the cetyl alcohol) are added during agitation of the mass over a period of 50-60 minutes with the temperature maintained at 55-65 C.
The mass is then stirred for 20-25 minutes to allow the reaction to come to an end. 59.3 parts by weight of 6.7% sodium hydroxide at 30 C. are added to the reaction mass slowly during stirring.
The product is an homogeneous white paste in appearance and in general similar to the prod uct of Example 1 except for differences in the finishing properties.
The following examples illustrate the use of parafiin wax as the aliphatic hydrocarbon.
Example 4 20.2 parts by weight of cetyl alcohol (technical) and 11.1 parts by weight of paraffin wax (m. p. range 5560 C.) are melted together, and 7.8 parts by weight of chlorsulfonic acid of theory on weight of cetyl alcohol) are added during agitation of the mass over a period of 30-40 minutes with the temperature maintained at 55-65 C.
The mass is then stirred for 4-5 minutes to allow the reaction to come to an end. 60.9 parts by weight of 5.4% sodium hydroxide at 30 C. are added to the reaction mass slowly during stirring.
The product is an homogeneous white paste in appearance and in general similar to the product of Example 1 except for differences in finishing properties. It will produce a more waxy and stiffer finish than the product of Example 1.
Example 5 The mass is then stirred for 4-5 minutes to allow the reaction to come to an end. 12.8 parts by weight of diethyl cyclohexyl amine are added to the reaction mass slowly during stirring.
The product is an homogeneous, thick paste which is yellowish in color. It produces finishes of similar character tothe product of Example 4 but may be more readily removed from the treated textile fibers for processes where it is desirable to remove the finishing agents. It requires no additional detergents or other assistants in the water in whichit is to be rinsed from the textile fibers.
Other organic bases besides diethyl cyclohexyl amine with which neutralization may be carried out are dimethyl cyclohexyl amine, mono cyclohexyl amine, and methyl amine.
It has been found essential that the aliphatic hydrocarbons be mixed with the long-chain aliphatic alcohol before sulfation in order to produce a product which will be stable during and after boiling in dilute aqueous emulsions. If paraflin wax, or petrolatum is added to sodium alcohol sulfate paste, after sulfation and neutralization of the alcohol, in proportions to duplicate the composition of Example 1, the paraflin wax or petrolatum will blend with the alcohol sulfate paste to form an homogeneous paste. The paste thus prepared will form dilute aqueous emulsions which show no separation during boiling, but from which liquefied paraflin wax or petrolatum separates on cooling below the boiling point.
It has also been found that the same difllculty of separation of the petrolatum is encountered if the procedure of Example 1 is revised to the addition of the petrolatum after sulfation of the alcohol, but before neutralization of the sulfation mass. Petrolatum separates from dilute aqueous emulsions after cooling from the boiling point.
It has been found desirable that the ratio of the aliphatic hydrocarbon to the long-chain alcohol should not exceed certain limits in order to minimize the risk of separation of the hydrocarbon from hot dilute aqueous emulsions of the sulfation product. The limits are dependent on the specific hydrocarbon or hydrocarbon mixture, on the specific alcohol or alcohol mixture, and also on the neutralizing base used. A preferred preparation which is made from equal parts of petrolatum (m. p. range 40-50 C.; iodine No. 17) and technical stearyl alcohol sulfated with approximately of the theoretical quantity of chlorsulfonic acid on the weight of the alcohol shows no separation of petrolatum from hot dilute aqueous emulsions. In similar preparations made from a technical mixture of cetyl and stearyl alcohols, the ratio of petrolatum to alcohol usually does not exceed 4:5. However, it is not intended to limit the ratio of petroleum hydrocarbon to alcohol to these particular proportions.
As previously stated, the product prepared by the process of Example 1 has the advantage over paper and textile softening agents prepared by the sulfation of long-chain aliphatic alcohols that it provides an oily lubricating film of the aliphatic hydrocarbon mixture in petrolatum on the surface of paper and of textile fibers in addition to making them pliable through the action of the alcohol'sulfate. This type of product provides a more suitable lubricating film than the unsulfated long-chain alcohols, and it is more economically prepared as the aliphatic hydrocarbons from petroleum are in general much cheaper than long-chain aliphatic alcohols.
The variety of combinations of aliphatic hydrocarbons from petroleum and long-chain ali- 'phatic alcohols which it is possible to obtain permit the preparation of a wide variety of products which make available to the art new types -of softening efi'ects not hitherto obtainable.
Light mineral oils of 50-100 Saybolt units viscosity at 100 F., heavy mineral oils of 100-300 Saybolt units viscosity at 100 F., petrolatums, and/or paraffin waxes of the many different types available may be mixed with the different long-chain aliphatic alcohols having twelve to twenty carbon atoms and sulfated. It is, of course, preferable that the aliphatic hydrocarbons be mixed with the alcohols before sulfation and that the ratio of hydrocarbon to alcohol not exceed that which will produce a product forming dilute aqueous emulsions stable to prolonged heating.
The leather, paper, and textile softening agents formed in the preferred processes, as illustrated in Examples 1-4 incl. have the distinct advantage over those softening agents well known to the art, such as sulfonated fats and oils from animal and vegetable sources, that they will not turn rancid during storage or hot calendering or hot ironing to develop objectionable odors and to discolor the paper or textiles to which they have been applied. This is an important property as leather, paper, and textiles are frequently spoiled with consequent loss in value by deterioration of the sulfonated fats or oils with which they have been treated.
Leather is softened and fattened by treating it in a bath containing a l-% solution of the product of Example 1 or similar products prepared according to the process of the invention.
Paper is softened by passing it through a box preferably in the calender stack containing a 5% solution of the product of Example 1 or similar products prepared according to the process of the invention. It will have a smooth, pliable finish adding to its desirability for many purposes such as towelling, absorbent padding, and similar purposes for which soft paper is required. The treatment will also improve the absorbency of the paper.
Textiles in the form of the loose fibers, yarns or woven fabrics are softened by treating them in aqueous solutions of the product of Example 1 or similar products prepared according to the invention. Cotton raw stock can be softened and its carding or combing and spinning properties improved after dyeing in a circulating type machine by adding 3 pounds of the product of Example 1 per 1000 pounds of cotton to the rinse waters after the dyeing is completed.
Cotton and viscose yarns can be softened and the winding properties improved by the use 'of 5 ounces of the product of Example 1 per 100 gallons of water.
Woven fabrics of cotton are given a very soft, smooth finish by treating them in a pad mangle with the various products of the invention as indicated in the following examples.
Example 6 Light weight printed dress fabric- 7 pounds of the product of Example 1 are mixed with 100 gallons of water and preferably applied at 60-80 C.
Example 7 Medium weight printed shirting fabric-2 pounds of the product of Example 1, pound of glycerine, and 12 pounds corn starch are mixed with 100 gallons of water. The mixture is boiled for 3 minutes and preferably applied at 60-80 C.
Example 8 Bleached suiting fabric-41 pounds of the product of Example 3, 20 pounds of corn starch,
and 10 pounds tapioca starch are mixed with 100 gallons of water: The mixture is boiled 3 minutes and preferably applied at 60-80" C. This white bleached fabric will not develop discoloration when it is hot ironed nor develop rancid odors as it might were it softened with a sulfonated vegetable oil or a sulfonated animal fat.
Example 9 Dyed heavy suit lining fabric-9 pounds of the product of Example 4 and 1 pound glycerine are mixed with 100 gallons of water and preferably applied at 60-80 C.
These latter examples illustrate the use of products of this invention on textiles in actual mill practice. The fabrics treated with the products have a smoother and softer finish than when treated with equal quantities of softening agents made from long-chain alcohols alone. The fabrics treated in this manner are free from the danger of discoloration developing on white or lightly colored portions when hot calendered or hot ironed and are free from the danger of rancid odors developing during storage in warm places as compared with fabrics treated with those softening agents most generally used heretofore which were prepared by sulphonation of oils and fats from animal and vegetable sources.
The products of this invention are also useful, in addition to their applications in leather, paper,
, and textile processing, in the preparation of luor variation therefrom which conforms to the spirit of the invention is intended to be included within the scope of the appended claims.
I claim:
1. A process of preparing a softening agent which comprises reacting a mixture of a substantially saturated higher aliphatic petroleum hydrocarbon and a long chain aliphatic alcohol having from 12 to 20 carbon atoms with a quantity of a sulfating agent which is not greater than that required for complete sulfation of the alcohol in the'mixture under relatively mild conditions to avoid the condensation of the components of the mixture.
2. A process of preparing a softening agent which comprises reacting a mixture of a higher aliphatic petroleum hydrocarbon selected from the group consisting of mineral oils, petrolatums, and paraffin waxes and a long chain aliphatic alcohol having from 12 to 20 carbon atoms with a quantity of a sulfating agent which is not greater than that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with a solution of an alkali metal hydroxide.
' 3. A process of manufacturing a softening agent which comprises reacting a mixture of technical stearyl alcohol and refined petrolatum with a quantity of chlorsulfonic acid which does not exceed that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with a solution of sodium hydroxide.
4. A process of manufacturing a softening agent which comprises reacting a mixture of cetyl alcohol and paraflln wax with a quantity of chlorsulfonic acid which does not exceed that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with a solution of sodium hydroxide.
5. A softening agent prepared according to the process defined in claim 1 which contains some unsulfated alcohol.
6. A softening agent prepared according to the process defined in claim 2 which contains some unsulfated alcohol.
7. A softening agent manufactured according to the process set forth in claim 3 which contains some stearyl alcohol.
8. A softening agent manufactured according to the process set forth in claim 4 which contains some cetyl alcohol.
9. A process of preparing a softening agent which comprises reacting a mixture of a higher aliphatic petroleum hydrocarbon selected from the group consisting of mineral oils, petrolatums, and paramn waxes and a long chain aliphatic alcohol having from 12 to 20 carbon atoms with a quantity of a sulfating agent which is not greater than that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with an organic base.
10. A process of manufacturing a softening agent which comprises reacting a mixture of cetyl alcohol and paraffin wax with a quantity of chlorsulfonic acid which does not exceed that required for complete sulfation of the alcohol in the mixture under relatively mild conditions to avoid the condensation of the components of the mixture, and neutralizing the sulfated mixture with an organic base.
11. A softening agent prepared according to the process defined in claim 9 which contains some unsulfated alcohol.
12. A softening agent manufactured according to the process set forth in claim 10 which contains some cetyl alcohol.
LUTHER B. ARNOLD, JR.
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US137374A US2180133A (en) | 1937-04-16 | 1937-04-16 | Softening agent |
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US137374A US2180133A (en) | 1937-04-16 | 1937-04-16 | Softening agent |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2555684A (en) * | 1949-03-26 | 1951-06-05 | Nopco Chem Co | Compositions for treating leather and textiles |
-
1937
- 1937-04-16 US US137374A patent/US2180133A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2555684A (en) * | 1949-03-26 | 1951-06-05 | Nopco Chem Co | Compositions for treating leather and textiles |
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