US3232779A - Methods of producing regenerated cellulose - Google Patents

Methods of producing regenerated cellulose Download PDF

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Publication number
US3232779A
US3232779A US854219A US85421959A US3232779A US 3232779 A US3232779 A US 3232779A US 854219 A US854219 A US 854219A US 85421959 A US85421959 A US 85421959A US 3232779 A US3232779 A US 3232779A
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United States
Prior art keywords
cellulose
viscose
regenerated cellulose
moles
carbon atoms
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Expired - Lifetime
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US854219A
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English (en)
Inventor
Schonfeldt Nikolaus Augustin
Grunewald Kurt Helmut
Steijner Olof Rune
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Mo och Domsjo AB
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Mo och Domsjo AB
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B16/00—Regeneration of cellulose
    • 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

Definitions

  • Regenerated cellulose is produced by converting cellulose to a soluble compound thereof and in a subsequent step reforming the cellulose.
  • the most widely used process of producing regenerated cellulose is the viscose process in which the cellulose is converted to cellulose xanthate. Briefly described, this process comprises mercerizing cellulose with caustic soda to produce alkali cellulose. After squeezing out excess soda, the alkali cellulose is comminuted in a mill and is then stored for a period of time to undergo aging. Thereupon, carbon disulfide is introduced whereby cellulose xanthate is formed.
  • the cellulose xanthate is dissolved in dilute alkali to form a viscous solution called viscose.
  • the viscose is filtered and stored for a few days whereupon it is extruded through fine holes in spinnerets into a spinning bath, which usually comprises sulfuric acid and various salts. Thereby, the viscose is coagulated and solidified with reformation of the cellulose in the form of filaments or fibers, which are subjected to washing and other treatments and is then dried.
  • the viscose may also be extruded through dies adapted to form films,
  • the regenerated cellulose will be obtained in by the cuprammonium process, which is similar to the viscose process, but uses a solution of cuprammonium hydroxide to dissolve the cellulose.
  • cuprammonium process which is similar to the viscose process, but uses a solution of cuprammonium hydroxide to dissolve the cellulose.
  • the processes of producing regenerated cellulose are well-known and de scribed in the technical and patent literature, and will not be described in detail here.
  • additives serve the purpose of facilitating and improving the process Depending on which object the additives have to fulfill, they may be entirely different in their chemical constitution and properties.
  • the additives are used for example to improve the filtering characteristics of the viscose, to prevent yarn milkiness, to reduc the gel swelling during the spinning or as anti-clogging agents or as finishing agents (avivage agents) to soften the finished fiber, etc.
  • Additives are used not only in the production of viscose rayon but also in the productionof cuprammonium rayon. I
  • a further circumstance which is to be considered is the chemical resistance of the additives in various stages of the process.
  • it When adding it prior to spinning, it will be subjected to alkalies, in the spinning bath it is exposed to sulfuric acid and to salts at an elevated temperature. If the agent in question is resistant to alkali, but is attacked in the spinning bath by sulfuric acid or the salts' present in the spinning bath, precipitates may be formed which may affect the spinning process adversely.
  • the action of the spinning bath becomes still stronger in the evaporation of the spinning bath, which often takes place at 80 or higher temperatures, so that decompositions of the additives may occur, which may in which R represents hydrocarbon radical having from 6 to 22 carbon atoms, x is l to 5, and z is 2 to 3.
  • the compounds used according to this inventon are ethylene oxide and propylene oxide adducts of said polyamines, wherein the number of ethylene oxide or propylene oxicle units is from 1 to 10. These compounds are used in amounts ranging from 0.1 to 4% by weight based on the cellulose.
  • the radical R may be, e.g., an "aliphatic straight-chain or branched-chain, saturated or unsaturated hydrocarbon grouping. Representative examples include ethylhexyl, d-odecyl, hexadecyl, octadecenyl and octade-cyl groups. Furthermore, R may be an aryl or alkylaryl or aralkyl group. benzene and nonylnaphthalene groups.
  • Compounds of the above type may be obtained by cond'ensing an appropriate polyamine (such as, e.g., ethylene diarnine, diethylene triamine, triethylene tetram-ine, dipropylene triamine, ethyl dipropylene triamine etc., or mixtures of such polyamines) with a compound containing the radical R linked to a reactive group, such as halogen, and then condensing the substances thus obtained with an alkylene oxide, such as ethylene oxide or propylene oxide to introduce into the compound one or more alkylene oxide units per mole of the compound. Since the nitrogen atoms of the resulting compounds are linked only to carbon atoms, these compounds are chemically very resistant even after addition of the alkylene oxide.
  • an appropriate polyamine such as, e.g., ethylene diarnine, diethylene triamine, triethylene tetram-ine, dipropylene triamine, ethyl dipropylene triamine etc., or mixtures of such polyamine
  • the compounds are to be used as additives in various stages of the production, e.g., be added to the spinning 'bath or the viscose or even earlier in the process, the
  • this period may be increased to about 30 minutes, i.e. about 10 times, by adding 1 g. of the above compound.
  • Compounds of the above formula may exhibit marked surface-active properties, resulting in a decrease in the surface tension of the viscose and the spinning bath.
  • the radical R By varying the radical R, the polyamines used and the amount of ethylene oxide, the surface tension reduction can be kept within suitable limits.
  • At least one of the nitrogen atoms can be quaternized by treatment with, e.g., dimethyl sulfate, diethyl sulfate, ethyl chloride etc.
  • the compounds can also be condensed with formaldehyde or acetic anhydride to increase their stability to light. Quaternized compounds as well as such formaldehyde and acetic anhydride condensation products are within the ambit of this invention.
  • the amount of additive to be employed in the production of regenerated cellulose can vary to a relatively large extent. In the case of adding it in the mill, an amount of 0.1 to 0.4% based on the weight of cellulose, is often sufficient, in the case of adding it tothe viscose, preferably 0.3 to 0.5 g./l. will be used. As an additive to the spinning bath, it is customary to use 1 to 4 gs. per kg. of fiber. As an all skin agent an addition of 1 to 3 gs. per liter of viscose is advantageous.
  • the term all skin agent also called greening agent denotes a substance, the action of which is that the fiber throughout its cross-section is imparted the properties which normally are present in its surface (skin). Such additives reduce the gel swelling.
  • an amount of softening agent in the case of rayon staple fiber, of 0.4 to 0.5%, and in the case of rayon filaments 0.7 to 0.8% is often advantageous.
  • the substance of the present invention may be used in the form of the pure compounds, but it is also possible to employ mixtures containing two or more compounds of the above formula.
  • Example 1 1 mole of keryl chloride obtained by chlorination of kerosene is reacted at 150 to 160 C. with 1.2 moles of diethylene triamine whereupon the product is condensed with 8 moles of ethylene oxide, 2 gs. of this product per 4 kg. of finished yarn added to the spinning bath improves the spinning properties (e.g., less slubbing, prevention of spinneret incrustation) considerably.
  • Example 2 One mole of cocoa fat chloride obtained from cocoa fat alcohol by replacing the hydroxyl group by chlorine, is
  • Example 3 204 gs. of dodecyl chloride 15 reacted at 160 C. with 200 gs. of polyethylene polyamines obtained as distillation residue after distilling off diethylene triamine and triethylene tetramine from a polyethylene polyamine mixture obtained by reaction of ethylene dichloride and ammonia. The reaction is complete after 3 hours. The resulting product is condensed with 6 moles of ethylene oxide, 1 g. of this product per liter of viscose reduces swelling of the gel fiber.
  • Example 4 Keryl benzene is reacted in a known manner with formaldehyde and gaseous hydrogen chloride in the presence of zinc chloride to form kerylphenyl chloride. 500 parts by weight of this substance are reacted with 200 parts by weight of polyamines in accordance with Example 3. Thereupon 10 moles of ethylene oxide are condensed with the resulting product. An addition of 0.5 g. per liter of spinning bath improves the extrusion of the viscose and prevents the spinneret incrustation.
  • compounds of the above types can be I quaternized, e.,g., with dimethyl sulfate, ethyl chloride, benzyl chloride etc. They can also, if desired, be treated with formaldehyde or acetic anhydride especially if the product is to be used as a finishing agent, in order to improve their resistance to light. Thereby formyl or acetyl groups are linked to certain of the nitrogen atoms.
  • Example 5 1 mole of octadecyl chloride is condensed with 4 moles of dipropylene triamine at 155 C. for 5 hours. Thereupon 1 mole of sodium hydroxide is introduced, whereupon excess of dipropylene triamine is distilled off. The octadecyl dipropylene triamine is then reacted with 2 moles of ethylene oxide. Thereupon the product is reacted with 1 mole of acetic acid anhydride at elevated temperature. If rayon fiber is softened with this product, the properties in the subsequent spinning and weaving steps can be substantially improved.
  • Example 6 1 mole of dodecyl tetraethylene pentamine is condensed with 6 moles of propylene oxide. 5 gs. of this product per liter of bath are used to soften rayon staple fiber.
  • Example 7 1 mole of 9,10-octadecenyl chloride is reacted at C. with 4 moles of triethylene tetramine.
  • 1 mole of sodium hydroxide is added to neutralize the hydrogen chloride formed, whereupon excess of triethylene tetramine is distilled off, suitably under vacuum.
  • After separating sodium chloride precipitated 5 moles of ethylene oxide are reacted with the product.
  • the 9,10-octadecen yl triethylene tetramine polyethylene polyglycol ether is then quaternized with 2 moles of di methyl sulfate. 0.4 g. of this product per liter of viscose improves the filtering properties.
  • a process for producing regenerated cellulose from cellulose which includes the step of using as an additive, in any stage of the process, an amount within the range from about 0.1 to about 4% by weight, based on the cellulose, of a compound selected from the group consisting of (l) the reaction product of (a) from about one to about .ten moles of an alkylene oxide having from two to three carbon atoms with (b) one mole of at least one polyamine having the formula:
  • R is a hydrocarbon radical having from about six to about twenty-two carbon atoms, 2 is an integer from 2 to 3, and x is a number from 1 to 5;
  • a process for producing regenerated cellulose from cellulose which includes the step of using as an additive, in any stage of the process, an amount within the range from about 0.1 to about 4% by weight, based on the cellulose, of the reaction product of (a) from about one to about ten moles of an alkylene dioxide having from two to three carbon atoms with (b) one mole of at least one polyamine having the formula:
  • R is a hydrocarbon radical having from about six to about twenty-two carbon atoms
  • z is an integer from 2 to 3
  • x is a number from 1 to 5.
  • a viscose spinning solution containing from about 3% to about 4%, based on the weight of the cellulose in the viscose, of a modifier corresponding to the formula R (onlmo) ,11
  • NomotnomN ruoumno x (o n 2nO 1H wherein R is a fatty alkyl hydrocarbon chain having between 8 and 18 carbon atoms, n is a Whole number of at least 2 but not greater than 3, x, y and z are whole numbers and the sum of x, y and z is about 10.
  • a viscose spinning solution containing from about 0.1 to about 4% by weight of the cellulose in the viscose of a modifier selected from the group consisting of (1) the reaction product of (a) from about one to about ten moles of an alkylene oxide having from two to three carbon atoms with (b) one mole of at least one polyamide having the formula:
  • R is a hydrocarbon radical having from about six to about twenty-two carbon atoms, z is an integer from 2 to 3, and x is a number from 1 to 5;

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
US854219A 1955-01-20 1959-11-20 Methods of producing regenerated cellulose Expired - Lifetime US3232779A (en)

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Application Number Priority Date Filing Date Title
SE54355 1955-01-20

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US (1) US3232779A (en, 2012)
BE (1) BE544526A (en, 2012)
CH (2) CH352777A (en, 2012)
FR (1) FR1145356A (en, 2012)
GB (1) GB795771A (en, 2012)
NL (2) NL97266C (en, 2012)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3381075A (en) * 1962-05-28 1968-04-30 Teijin Ltd Process for preparation of viscose regenerated cellulose fibers
US5582637A (en) * 1993-04-23 1996-12-10 Akzo Nobel Surface Chemistry Ab Method for improving the rheology and the processability of cellulose-based spinning solutions

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4661288A (en) 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4659802A (en) 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4597898A (en) * 1982-12-23 1986-07-01 The Proctor & Gamble Company Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
US4551506A (en) 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
DE3380259D1 (en) * 1982-12-23 1989-08-31 Procter & Gamble Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2593466A (en) * 1948-07-16 1952-04-22 Ind Rayon Corp Viscose spinning solution
US2674619A (en) * 1953-10-19 1954-04-06 Wyandotte Chemicals Corp Polyoxyalkylene compounds
US2759975A (en) * 1952-05-28 1956-08-21 Gen Aniline & Film Corp Mixed alkyl-benzyl-alkylol quaternary ammonium salts
US2792281A (en) * 1953-09-21 1957-05-14 American Viscose Corp Viscose composition and method of spinning
US2852333A (en) * 1954-05-21 1958-09-16 Du Pont Viscose spinning process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2593466A (en) * 1948-07-16 1952-04-22 Ind Rayon Corp Viscose spinning solution
US2759975A (en) * 1952-05-28 1956-08-21 Gen Aniline & Film Corp Mixed alkyl-benzyl-alkylol quaternary ammonium salts
US2792281A (en) * 1953-09-21 1957-05-14 American Viscose Corp Viscose composition and method of spinning
US2674619A (en) * 1953-10-19 1954-04-06 Wyandotte Chemicals Corp Polyoxyalkylene compounds
US2852333A (en) * 1954-05-21 1958-09-16 Du Pont Viscose spinning process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3381075A (en) * 1962-05-28 1968-04-30 Teijin Ltd Process for preparation of viscose regenerated cellulose fibers
US5582637A (en) * 1993-04-23 1996-12-10 Akzo Nobel Surface Chemistry Ab Method for improving the rheology and the processability of cellulose-based spinning solutions

Also Published As

Publication number Publication date
BE544526A (en, 2012)
NL97266C (en, 2012)
CH352777A (de) 1961-03-15
FR1145356A (fr) 1957-10-25
CH360457A (de) 1962-02-28
GB795771A (en) 1958-05-28
NL203771A (en, 2012)

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