US2966422A - Low viscosity cellulose acetate spinning solutions - Google Patents

Low viscosity cellulose acetate spinning solutions Download PDF

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US2966422A
US2966422A US699192A US69919257A US2966422A US 2966422 A US2966422 A US 2966422A US 699192 A US699192 A US 699192A US 69919257 A US69919257 A US 69919257A US 2966422 A US2966422 A US 2966422A
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solution
cellulose acetate
viscosity
sulfonate
sulfonates
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US699192A
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John D Brandner
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Atlas Powder Co
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Atlas Powder Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

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  • the present invention relates to low viscosity cellulose acetate spinning solutions. More particularly it pertains to spinning solutions of cellulose acetate in acetone which have a reduced viscosity due to the presence of a small amount of a salt of an alkyl aryl sulfonic acid.
  • Another object of this invention is the production of low viscosity spinning solutions without sacrificing tensile strength development of fibers spun therefrom.
  • a further object of this invention is the formulation of spinning solutions containing a viscosity-reducing additive which additive need not be removed from the spun fibers.
  • solutions of cellulose acetate of reduced viscosity are obtained if a small proportion of a salt of a higher alkyl benzene sulfonic acid is included in them.
  • These salts may be those formed by alkali metals, ammonia or lower alkyl amines.
  • Some representative salts which are within the scope of this invention are as follows: (a) alkali metal saltspotassium dodecyl benzene sulfonate, sodium dodecyl benzene sulfonate (b) ammonia salts-ammonium dodecyl benzene sulfonate, ammonium decyl benzene sulfonate and (c) amine salts--isopropyl amine dodecyl benzene sulfonate, ethyl amine dodecyl benzene sulfonate, and isopropyl amine dinonyl benzene sulfonate.
  • the additive may be mixed with the cellulose acetate solution in any convenient manner either in the solvent for the cellulose acetate or in the cellulose acetate solution.
  • Aromatic petroleum fractions are useful for this purpose and do not in themselves appreciably affect solution viscosity.
  • any amount of additive which will produce the desired lowering of viscosity may be used.
  • amounts below 0.5% by weight of the cellulose acetate are not sufiiciently effective for best results and amounts above 2.0% also seem to produce less desirable results. Amounts between these two values are preferable and the most effective viscosity-reducing amount usually lies between aboutl and 1.8% of the weight of cellulose acetate.
  • cellulose acetate is intended to means acetone-soluble cellulose acetates, such as that sold under the name LH-l. These cellulose acetates, which are usually marketed in flake form, preferably contain from 57% acetyl radicals and, on a molal basis, have approximately 2.2 mols of acetyl radical per mol of glucose radical.
  • the term cellulose acetate is not intended to cover acetates such as cellulose tri-acetate, which contains 62.5% acetyl radicals and is not soluble in acetone. This distinction between cellulose acetate which are suitable for spinning and those which are not is well recognized in the prior art.
  • compositions of this invention were shown by preparing and testing the following spinning solution formulations:
  • Example I A spinning solution was prepared using 20 parts by weight of a cellulose acetate (LH-l) and 80 parts by weight of acetone.
  • the initial viscosity of a 200 gram sample of this solution was measured at 25 C. with a Brookfield Viscometer using the No. 4 spindle at 6 r.p.m.
  • the initial viscosity of this control solution was assigned an arbitrary value of 100% and all later determinations of viscosity were related to this percentage.
  • Example 11 To a'portion of the solution of Example I was added sufficient water to make the weight percent of water (based on the cellulose acetate content) 1.2%. The initial viscosity of this solution at 25 C. was determined to be 81.7% of that of the solution of Example I. This determination is representative of the prior art.
  • Example III A 50% solution of isopropyl amine dodecyl benzene sulfonate was prepared using an aromatic hydrocarbon having a specific gravity of 0.893 (60/60), a flash point of F., and an initial boiling point of 367 F.
  • the solvent is sold under the trademark Solvesso 150.
  • Example I To a 200 gram sample of the solution of Example I was added sufiicient sulfonate solution to make the sulfonate concentration 1% by weight, based on the cellulose acetate content.
  • the initial viscosity was measured at 25 C. and found to be 74.7% of the initial viscosity of the solution of Example I, an improvement of 25.3%.
  • Example IV A 50% solution of tri-isopropyl amine dodecyl benzene sulfonate in Solvesso 150 was prepared as in Example III. To a 200 gram sample of the solution of Example I was added sufiicient sulfonate solution to make the sulfonate concentration 1% by weight based on the cellulose acetate content.
  • the initial viscosity was measured at 25 C. and found to be 57.8% of the initial viscosity of'the solution of Example I, an improvement of 42.2%.
  • Example V A 50% solution of ethyl amine dodecyl benzene sulfonate in Solvesso 150 was prepared as in Example III.
  • Example I To a 200 gram sample of the solution of Example I was added sufficient sulfonate solution to make the sulfonate concentration 1% by weight based on the cellulose acetate content of the spinning solution.
  • the initial viscosity was measured at 25 C. and found to be 57.8% of the initial viscosity of the solution of Example I, an improvement of 42.2%.
  • Example VI A 50% solution of isopropyl amine dinonyl benzene sulfonate in Solvesso 150 was prepared as in Example III.
  • Example I To a sample of the solution of Example I was added sufiicient sulfonate solution to make the sulfonate concentration 1% by weight, based on the cellulose acetate content of the spinning solution.
  • the initial viscosity was measured at 25 C. and found to be 83.6% of the initial viscosity of the solution of Example I. After 8 days storage the viscosity of the solution of Example I was 122.5% of its initial viscosity whereas the viscosity of the solution containing isopropyl amine dinonyl benzene sulfonate was only 89.8% of the initial viscosity of the solution of Example I.
  • Example VII The spinning solution of Example V was allowed to age for 8 days. Its viscosity, which had initially been 57.8% of the initial viscosity of the control solution (the solution of Example I) only increased to 61.2% of the initial viscosity of the control whereas, as has been stated above, the 8 day viscosity of the control was 122.5% of its initial value.
  • Example VIII The isopropyl amine dodecyl benzene sulfonate solution prepared as in Example III was added to a sample of the spinning solution of Example I in an amount to make the sulfonate concentration 1.8% by weight, based on the cellulose acetate content.
  • the initial viscosity was measured at 25 C. and found to be 70% of the initial viscosity of the solution of Example I.
  • the sulfonates may be added to the spinning solution after the cellulose has been dissolved or, alternatively, they may be added to the acetone before dissolving the cellulose. In either case, the effect is substantially the same.
  • Spinning solutions containing the additives of the invention are spun in any manner which is conventional for cellulose acetate, such as extrusion through spinnerettes.
  • the fibers thus produced will develop tensile strength rapidly and thus be capable of optimum stretching and orientation.
  • the instant additives need not be removed from the fibers since they have no deleterious effect upon them.
  • a spinning solution comprising cellulose acetate, a solvent for said acetate, and from 0.5 to about 2% by weight, based on the weight of said cellulose acetate, of a higher alkyl substituted benzene sulfonate, said sulfonate being selected from the group consisting of alkali metal sulfionates, ammonium sulfonates, and amine sulfonates.
  • composition of claim 2 wherein the alkali metal is sodium.
  • composition of claim 1 wherein said sulfonates are amine sulfonates.
  • composition of claim 4 wherein the amine is isopropyl amine.
  • composition of claim 4 wherein the amine is tii-isopropyl amine.
  • composition of claim 1 wherein said sulfonates are ammonium sulfonates.
  • a spinning solution consisting essentially of cellulose acetate, a solvent for said acetate, and from 0.5 to about 2% by Weight, based on the weight of said cellulose, of a higher alkyl substituted benzene sulfonate, said sulfonate being selected from the group consisting of alkali metal sulfonates, ammonium sulfonates and amine sulfonates.
  • composition of claim 1 wherein said higher alkyl substituent is dodecyl.

Description

United States Patent LOW VISCOSITY CELLULOSE ACETATE SPINNING SOLUTIONS John D. Brandner, Wilmington, Del., assignor to Atlas Powder Company, Wilmington, Del., a corporation of Delaware No'Drawing. Filed-Nov. 27,-1957, Ser. No. 699,192 lllClaims. (Cl. 106-196) The present invention relates to low viscosity cellulose acetate spinning solutions. More particularly it pertains to spinning solutions of cellulose acetate in acetone which have a reduced viscosity due to the presence of a small amount of a salt of an alkyl aryl sulfonic acid.
ing constituent'of the solution, it is desirable to use as high a concentration of it as possible. However, there is a positive correlation between the concentration of the acetate and the viscosity of the solution. As the concentration increases the viscosity increases until, eventually, the solution becomes too viscous for use in any practical extrusion or fiber forming process.
In the prior art, this problem of high viscosity was solved by adding a small amount of water to the spinning solution. The addition of this water lowers the viscosity to the point where the solution becomes workable and consequently, water is commonly found in spinning solution. Unfortunately, the use of water retards development of tensile strength in the fibers which are spun from such solutions. The retarded development of fiber strength, in turn, prevents stretching and orientation of the fibers. The water is also but slowly removable from the fibers.
It is an object of this invention to formulate cellulose acetate spinning solutions which have a relatively low viscosity.
Another object of this invention is the production of low viscosity spinning solutions without sacrificing tensile strength development of fibers spun therefrom.
A further object of this invention is the formulation of spinning solutions containing a viscosity-reducing additive which additive need not be removed from the spun fibers.
Additional objects of the invention will be apparent to those skilled in the art from a consideration of the description which follows.
According to the present invention, it has been found that solutions of cellulose acetate of reduced viscosity are obtained if a small proportion of a salt of a higher alkyl benzene sulfonic acid is included in them. These salts may be those formed by alkali metals, ammonia or lower alkyl amines.
Some representative salts which are within the scope of this invention are as follows: (a) alkali metal saltspotassium dodecyl benzene sulfonate, sodium dodecyl benzene sulfonate (b) ammonia salts-ammonium dodecyl benzene sulfonate, ammonium decyl benzene sulfonate and (c) amine salts--isopropyl amine dodecyl benzene sulfonate, ethyl amine dodecyl benzene sulfonate, and isopropyl amine dinonyl benzene sulfonate.
2,966,422 Patented Dec. 27, 1960 -'A preferred additive is ethyl aminedode'cyl benzene sulfonate.
The additive may be mixed with the cellulose acetate solution in any convenient manner either in the solvent for the cellulose acetate or in the cellulose acetate solution. For ease of mixing, it is often expedient to add the viscosity-reducing agent in solution form. Aromatic petroleum fractions are useful for this purpose and do not in themselves appreciably affect solution viscosity.
Any amount of additive which will produce the desired lowering of viscosity may be used. Usually, amounts below 0.5% by weight of the cellulose acetate are not sufiiciently effective for best results and amounts above 2.0% also seem to produce less desirable results. Amounts between these two values are preferable and the most effective viscosity-reducing amount usually lies between aboutl and 1.8% of the weight of cellulose acetate.
Whenever the term cellulose acetate is used throughout this disclosure it is intended to means acetone-soluble cellulose acetates, such as that sold under the name LH-l. These cellulose acetates, which are usually marketed in flake form, preferably contain from 57% acetyl radicals and, on a molal basis, have approximately 2.2 mols of acetyl radical per mol of glucose radical. The term cellulose acetate is not intended to cover acetates such as cellulose tri-acetate, which contains 62.5% acetyl radicals and is not soluble in acetone. This distinction between cellulose acetate which are suitable for spinning and those which are not is well recognized in the prior art.
The superiority of compositions of this invention was shown by preparing and testing the following spinning solution formulations:
Example I A spinning solution was prepared using 20 parts by weight of a cellulose acetate (LH-l) and 80 parts by weight of acetone.
The initial viscosity of a 200 gram sample of this solution was measured at 25 C. with a Brookfield Viscometer using the No. 4 spindle at 6 r.p.m. The initial viscosity of this control solution was assigned an arbitrary value of 100% and all later determinations of viscosity were related to this percentage.
Example 11 To a'portion of the solution of Example I was added sufficient water to make the weight percent of water (based on the cellulose acetate content) 1.2%. The initial viscosity of this solution at 25 C. was determined to be 81.7% of that of the solution of Example I. This determination is representative of the prior art.
Example III A 50% solution of isopropyl amine dodecyl benzene sulfonate was prepared using an aromatic hydrocarbon having a specific gravity of 0.893 (60/60), a flash point of F., and an initial boiling point of 367 F. The solvent is sold under the trademark Solvesso 150.
To a 200 gram sample of the solution of Example I was added sufiicient sulfonate solution to make the sulfonate concentration 1% by weight, based on the cellulose acetate content.
The initial viscosity was measured at 25 C. and found to be 74.7% of the initial viscosity of the solution of Example I, an improvement of 25.3%.
Example IV A 50% solution of tri-isopropyl amine dodecyl benzene sulfonate in Solvesso 150 was prepared as in Example III. To a 200 gram sample of the solution of Example I was added sufiicient sulfonate solution to make the sulfonate concentration 1% by weight based on the cellulose acetate content.
The initial viscosity was measured at 25 C. and found to be 57.8% of the initial viscosity of'the solution of Example I, an improvement of 42.2%.
Example V A 50% solution of ethyl amine dodecyl benzene sulfonate in Solvesso 150 was prepared as in Example III.
To a 200 gram sample of the solution of Example I was added sufficient sulfonate solution to make the sulfonate concentration 1% by weight based on the cellulose acetate content of the spinning solution.
The initial viscosity was measured at 25 C. and found to be 57.8% of the initial viscosity of the solution of Example I, an improvement of 42.2%.
Example VI A 50% solution of isopropyl amine dinonyl benzene sulfonate in Solvesso 150 was prepared as in Example III.
To a sample of the solution of Example I was added sufiicient sulfonate solution to make the sulfonate concentration 1% by weight, based on the cellulose acetate content of the spinning solution.
The initial viscosity was measured at 25 C. and found to be 83.6% of the initial viscosity of the solution of Example I. After 8 days storage the viscosity of the solution of Example I was 122.5% of its initial viscosity whereas the viscosity of the solution containing isopropyl amine dinonyl benzene sulfonate was only 89.8% of the initial viscosity of the solution of Example I.
Example VII The spinning solution of Example V was allowed to age for 8 days. Its viscosity, which had initially been 57.8% of the initial viscosity of the control solution (the solution of Example I) only increased to 61.2% of the initial viscosity of the control whereas, as has been stated above, the 8 day viscosity of the control was 122.5% of its initial value.
Example VIII The isopropyl amine dodecyl benzene sulfonate solution prepared as in Example III was added to a sample of the spinning solution of Example I in an amount to make the sulfonate concentration 1.8% by weight, based on the cellulose acetate content.
The initial viscosity was measured at 25 C. and found to be 70% of the initial viscosity of the solution of Example I.
. The sulfonates may be added to the spinning solution after the cellulose has been dissolved or, alternatively, they may be added to the acetone before dissolving the cellulose. In either case, the effect is substantially the same.
Spinning solutions containing the additives of the invention are spun in any manner which is conventional for cellulose acetate, such as extrusion through spinnerettes. The fibers thus produced will develop tensile strength rapidly and thus be capable of optimum stretching and orientation. In addition, unlike the viscosity reducing additive of the prior art, the instant additives need not be removed from the fibers since they have no deleterious effect upon them.
Having described my invention, what is claimed is:
1. A spinning solution comprising cellulose acetate, a solvent for said acetate, and from 0.5 to about 2% by weight, based on the weight of said cellulose acetate, of a higher alkyl substituted benzene sulfonate, said sulfonate being selected from the group consisting of alkali metal sulfionates, ammonium sulfonates, and amine sulfonates.
2. The-composition of claim 1 wherein said sulfonates are alkali metal sulfonates.
3. The composition of claim 2 wherein the alkali metal is sodium.
4. The composition of claim 1 wherein said sulfonates are amine sulfonates.
5. The composition of claim 4 wherein the amine is isopropyl amine.
6. The composition of ethyl amine.
7. The composition of claim 4 wherein the amine is tii-isopropyl amine.
8. The composition of claim 1 wherein said sulfonates are ammonium sulfonates.
9. A spinning solution consisting essentially of cellulose acetate, a solvent for said acetate, and from 0.5 to about 2% by Weight, based on the weight of said cellulose, of a higher alkyl substituted benzene sulfonate, said sulfonate being selected from the group consisting of alkali metal sulfonates, ammonium sulfonates and amine sulfonates.
10. The composition of claim 1 wherein said higher alkyl substituent is dodecyl.
claim 4 wherein the amine is References Cited in the file of this patent UNITED STATES PATENTS 1,954,326 Murray et al Apr. 10, 1934 1,957,912 Seel May 8, 1934 2,286,822 Malm et al June 16, 1942 Sisley et al.: Encyclopedia of Surface Active Agents 1952 p. 388.

Claims (1)

1. A SPINNING SOLUTION COMPRISING CELLULOSE ACETATE, A SOLVENT FOR SAID ACETATE, AND FROM 0.5 TO ABOUT 2% BY WEIGHT, BASED ON THE WEIGHT OF SAID CELLULOSE ACETATE, OF A HIGHER ALKYL SUBSTITUTED BENZENE SULFONATE, SAID SULFONATE BEING SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL SULFONATES, AMMONIUM SULFONATES, AND AMINE SULFONATES.
US699192A 1957-11-27 1957-11-27 Low viscosity cellulose acetate spinning solutions Expired - Lifetime US2966422A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347689A (en) * 1961-08-24 1967-10-17 Teijin Ltd Method of reducing the viscosity of a solution of cellulose derivative
US4316867A (en) * 1979-10-10 1982-02-23 Eastman Kodak Company Process for removing impurities from polymer solutions
US4379865A (en) * 1980-02-01 1983-04-12 Daicel Chemical Industries, Ltd. Binder for casting sand and resin-coated grains of sand
US4888147A (en) * 1987-10-08 1989-12-19 Mitsubishi Rayon Co., Ltd. Process for production of cellulose acetate molding materials
WO1994002557A1 (en) * 1992-07-27 1994-02-03 Henkel Kommanditgesellschaft Auf Aktien Thinner for aqueous adhesives

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1954326A (en) * 1930-09-12 1934-04-10 Eastman Kodak Co Cellulosic comosition of matter containing cyclohexanone and ortho-cresyl para-toluene sulphonate
US1957912A (en) * 1929-12-24 1934-05-08 Eastman Kodak Co Moisture resistant fibrous material
US2286822A (en) * 1939-03-10 1942-06-16 Eastman Kodak Co Recovery of cellulose esters from scrap

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1957912A (en) * 1929-12-24 1934-05-08 Eastman Kodak Co Moisture resistant fibrous material
US1954326A (en) * 1930-09-12 1934-04-10 Eastman Kodak Co Cellulosic comosition of matter containing cyclohexanone and ortho-cresyl para-toluene sulphonate
US2286822A (en) * 1939-03-10 1942-06-16 Eastman Kodak Co Recovery of cellulose esters from scrap

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3347689A (en) * 1961-08-24 1967-10-17 Teijin Ltd Method of reducing the viscosity of a solution of cellulose derivative
US4316867A (en) * 1979-10-10 1982-02-23 Eastman Kodak Company Process for removing impurities from polymer solutions
US4379865A (en) * 1980-02-01 1983-04-12 Daicel Chemical Industries, Ltd. Binder for casting sand and resin-coated grains of sand
US4888147A (en) * 1987-10-08 1989-12-19 Mitsubishi Rayon Co., Ltd. Process for production of cellulose acetate molding materials
WO1994002557A1 (en) * 1992-07-27 1994-02-03 Henkel Kommanditgesellschaft Auf Aktien Thinner for aqueous adhesives

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