US3118725A - Treatment of cellulose products - Google Patents

Treatment of cellulose products Download PDF

Info

Publication number
US3118725A
US3118725A US47959A US4795960A US3118725A US 3118725 A US3118725 A US 3118725A US 47959 A US47959 A US 47959A US 4795960 A US4795960 A US 4795960A US 3118725 A US3118725 A US 3118725A
Authority
US
United States
Prior art keywords
fibers
formaldehyde
solution
fiber
polymeric acetal
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
Application number
US47959A
Other languages
English (en)
Inventor
Charles L Henry
Bernard J Barrett
Jr Clyde M Guest
Floros Nicholas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzona Inc
Original Assignee
American Enka Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE606822D priority Critical patent/BE606822A/xx
Priority to NL267756D priority patent/NL267756A/xx
Application filed by American Enka Corp filed Critical American Enka Corp
Priority to US47959A priority patent/US3118725A/en
Priority to ES0269457A priority patent/ES269457A1/es
Priority to GB28316/61A priority patent/GB933998A/en
Priority to FR869919A priority patent/FR1296878A/fr
Priority to DEA38076A priority patent/DE1166140B/de
Application granted granted Critical
Publication of US3118725A publication Critical patent/US3118725A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—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 oxygen
    • D06M13/137—Acetals, e.g. formals, or ketals
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
    • 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
    • D06M13/10—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 oxygen
    • D06M13/12—Aldehydes; Ketones

Definitions

  • This invention relates to a new process for the chemical modification of cellulose products whereby said products have improved properties and characteristics. More specifically, this invention is a process for the treatment of rayon fibers and filamentary yarns with a polymeric acetal derived from ethylene glycol and formaldehyde together with monomeric formaldehyde under a specific set of conditions as regards concentrations, catalysts, buffer, pH, and drying and curing temperatures.
  • the object of this invention is to provide a process for improving these properties by chemically modifying the cellulose fibers or yarns.
  • Another object is to provide a process whereby this chemical modification is obtained economically and permanently without substantial losses in tensile strengths or abrasion resistance and without use of nitrogen-containing agents which could cause retention of chlorine during bleaching.
  • a major portion of the art of chemically modifying cellulose textile products relates to the use of formaldehyde or products which possess functional groups derived from formaldehyde.
  • Formaldehyde alone has limited use for the chemical modification of rayon fibers or filaments, as the fibers or filaments are embrittled to the extent that their processability into fabrics and their utility are impaired so that they are commercially unacceptable.
  • formaldehyde can be successfully employed to modify rayon fibers or filaments without substantial embrittlement by using it in conjunction with a polymeric acetal of the type described in United States Patents 2,785,949 and 2,786,081, provided the treatment is carried out under the specific conditions hereinafter described.
  • the use of the mixture is preferred over the use of the polymeric acetal alone, as the mixture offers an economic advantage and also, for comparable concentrations, produces the desired effects to a greater extent on the fibers or filaments and consequently on the fabrics produced therefrom.
  • the objects of this invention are accomplished by applying to the cellulose fibers or filamentary yarns an aqueous solution of pH 5.0-7.5 containing (1) a polymeric acetal derived from ethylene glycol and formaldehyde of the following formula:
  • n l and X and Y are either H or CH OH, (2) monomeric formaldehpde, (3) an organic acid with at least one carboxylic acid group with an ionization constant lying between 1 l0- and l l0' and (4) magnesium chloride. Then, after excess liquid is pressed out from the cellulose mass to give the desired percentage pick-up, it is dried and a reaction between the cellulose, formaldehyde and polymeric acetal is effected by uniformly heating at an elevated temperature.
  • Concentrations of the components in the treating bath may be varied according to the magnitude of the effects desired on the fiber or filament properties. The following ranges are preferred for a pick-up of about to 200%. All percentages are based on the weight of the bath.
  • the ratio of monomeric formaldehyde to polymeric acetal in the treating solution is determined by the magnitude of the fiber or filament modification desired; the higher the ratio the greater the effect.
  • the organic acid (as its metal salt) serves the function of bulfering the solution at any selected pH between 5.0 and 7.5. This pH range is preferred as cellulose degradation is controlled during the drying and curing operations.
  • the magnesium chloride serves as a catalyst during the curing operation to effect a reaction between the cellulose, formaldehyde, and polymeric acetal.
  • the cellulosic mass is dried by heating uniformly at about 70 C. to C. Afterwards the mass is then cured by heating uniformly at C. to C. for 5 to 30 minutes. The correct combination of time and temperature is easily determined by experiment; higher temperatures require shorter times.
  • a suitable method for preparing the polymeric acetal used in the invention consists of mixing the following components in an apparatus equipped with a reflux condenser and a water trap.
  • EXAMPLE 1 Samples of 1100 denier, gel-state viscose rayon yarn containing 720 filaments, were immersed for one hour in solutions containing 2.0% formaldehyde, 0.1% maleic acid (sodium salt), 0.4% magnesium chloride, and varying amounts of the polymeric acctal derived from cthylene glycol and formaldehyde. The pH of the solution was 7. After excess liquid was pressed out to give a pickup of about 125%, the samples were dried at 90 C. and then cured at 140 C. for 20 minutes in a forced draft oven. The resulting data are shown in Table l.
  • EXAMPLE IV More samples of the yarn used in Example II were treated with a solution containing 1.0% polymeric acetal, 2.5% formaldehyde, and 0.1% maleic acid of varying pH values. The results in Table IV show that higher elongations and ten-acities are obtained with a solution pH of 5.0 or greater.
  • Fiber swelling was reduced from 61% to 49%, and the fibers were insoluble in cupriethylene-di-amine.
  • the fibers were then water washed, finish applied, dried, and processed into 30/1 spun yarn. Properties of the spun yarn so prepared are compared in Table V with properties of spun yarn prepared from untreated control fibers.
  • the chemical modification of the fibers may be combined with a finishing treatment. This has a great economical advantage in that it eliminates the normal steps of washing and drying the fibers, applying a finish emulsion, and redrying.
  • a process of chemically modifying rayon fibers which comprises applying to the fibers an aqueous solution having a pH between 5.0 and 7.5 and containing by weight of the solution 0.25% to about 5.0% ethylene glycol-formaldehyde polymeric acetal, 0.25% to about 5.0% monomeric formaldehyde, 0.05% to about 0.5% of an alkali metal salt of an organic acid, and 0.2% to about 2.0% of a catalyst, removing the excess liquid whereby a pickup of between and 200% is efiected, drying the fiber at between about 70 C. and C., and thereafter curing the same by uniformly heating at between C. and C. for from 5 to 30 minutes.
  • a process of chemically modifying rayon fibers which comprises applying to the fibers an aqueous solution having a pl-I between 5.0 and 7.5 and containing by weight of the solution 0.25% to about 5.0% ethylene glycolformaldehyde polymeric acetal, 0.25% to about 5.0% monomeric formaldehyde, 0.05% to about 0.5% of an alkali metal salt of an organic acid, and 0.2% to about 2.0% of magnesium chloride, removing the excess liquid, drying the fibers at between about 70 C. and about 110 C., and finally curing the same by uniformly heating at etween 120 C. and 160 C. for 5 to 30 minutes.
  • a process of chemically modifying rayon fibers which comprises applying to the fibers an aqueous solution having a pH between 5.0 and 7.5 and containing by weight of the solution 0.25% to about 5.0% ethylene glycol-formaldehyde polymeric acetal, 0.25% to about 5.0% monomeric formaldehyde, 0.05% to about 0.5% of an alkali metal salt of an organic acid, a nonionic polyoxyethylene sorbitol tallow finish, and 0.2% to about 2.0% of magnesium chloride, removing the excess liquid, drying the fibers at between about 70 C. to about 110 C., and finally curing the same by uniformly heating at between 120 C. to 160 C. for 5 to 30 minutes.
  • a process of chemically modifying viscose rayon fibers which comprises applying to the fibers an aqueous solution having a pH between 5.0 and 7.5 and containing by weight of the solution 0.25% to about 5.0% ethylene glycol-formaldehyde polymeric acetal, 0.25 to about 5.0% monomeric formaldehyde, 0.05% to 0.5% of the sodium metal salt of an organic acid with at least one carboxylic acid group with an ionization constant lying between 1X10 and 1x10 a nonionic polyoxyethyl ene sorbitol tallow finish, and 0.2% to about 2.0% of magnesium chloride, removing the excess liquid. drying the fibers at between about 70 C. to about 110 C., and finally curing the same by uniformly heating at between 120 C. to 160 C. for 5 to 30 minutes.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US47959A 1960-08-08 1960-08-08 Treatment of cellulose products Expired - Lifetime US3118725A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BE606822D BE606822A (en, 2012) 1960-08-08
NL267756D NL267756A (en, 2012) 1960-08-08
US47959A US3118725A (en) 1960-08-08 1960-08-08 Treatment of cellulose products
ES0269457A ES269457A1 (es) 1960-08-08 1961-07-29 Un procedimiento para mejorar las propiedades de filamentos continuos o fibras cortadas de celulosa regenerada
GB28316/61A GB933998A (en) 1960-08-08 1961-08-03 A process for improving the properties of continuous filaments or staple fibers of regenerated cellulose
FR869919A FR1296878A (fr) 1960-08-08 1961-08-03 Procédé pour améliorer les propriétés de fils ou de fibres discontinues de cellulose régénérée ainsi que les fils ou les fibres discontinues ainsi améliorés
DEA38076A DE1166140B (de) 1960-08-08 1961-08-07 Verfahren zur Verbesserung der Eigenschaften von kontinuierlichen Faeden oder Stapelfasern aus regenerierter Cellulose

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US47959A US3118725A (en) 1960-08-08 1960-08-08 Treatment of cellulose products

Publications (1)

Publication Number Publication Date
US3118725A true US3118725A (en) 1964-01-21

Family

ID=21951979

Family Applications (1)

Application Number Title Priority Date Filing Date
US47959A Expired - Lifetime US3118725A (en) 1960-08-08 1960-08-08 Treatment of cellulose products

Country Status (6)

Country Link
US (1) US3118725A (en, 2012)
BE (1) BE606822A (en, 2012)
DE (1) DE1166140B (en, 2012)
ES (1) ES269457A1 (en, 2012)
GB (1) GB933998A (en, 2012)
NL (1) NL267756A (en, 2012)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287083A (en) * 1961-06-30 1966-11-22 Bancroft & Sons Co J Formaldehyde modification of cellulose catalyzed by a lewis acid salt and formic acid generated in situ by a peroxide
US3617199A (en) * 1964-10-30 1971-11-02 Johnson & Johnson Alkali metal chlorides and nitrates used to inhibit cellulose degradation in acid catalyzed cross-linking processes

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2108520A (en) * 1934-10-16 1938-02-15 Bohme Fettchemie Ges Textile and method of finishing
US2541457A (en) * 1947-05-23 1951-02-13 Alrose Chemical Company Cellulosic textile shrinkage control and crease resistance with inhibited tenderizing action
US2585949A (en) * 1949-08-17 1952-02-19 Vanton Pump Corp Pump
US2826514A (en) * 1955-11-17 1958-03-11 Shell Dev Treatment of textile materials and composition therefor
US2945738A (en) * 1958-01-29 1960-07-19 Chicopee Mfg Corp Low cover factor woven cellulose textile material resistant to corrugation in washing and tumble drying

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2903328A (en) * 1956-12-19 1959-09-08 Quaker Chemical Products Corp Process for the dimensional control of cellulosic materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2108520A (en) * 1934-10-16 1938-02-15 Bohme Fettchemie Ges Textile and method of finishing
US2541457A (en) * 1947-05-23 1951-02-13 Alrose Chemical Company Cellulosic textile shrinkage control and crease resistance with inhibited tenderizing action
US2585949A (en) * 1949-08-17 1952-02-19 Vanton Pump Corp Pump
US2826514A (en) * 1955-11-17 1958-03-11 Shell Dev Treatment of textile materials and composition therefor
US2945738A (en) * 1958-01-29 1960-07-19 Chicopee Mfg Corp Low cover factor woven cellulose textile material resistant to corrugation in washing and tumble drying

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287083A (en) * 1961-06-30 1966-11-22 Bancroft & Sons Co J Formaldehyde modification of cellulose catalyzed by a lewis acid salt and formic acid generated in situ by a peroxide
US3617199A (en) * 1964-10-30 1971-11-02 Johnson & Johnson Alkali metal chlorides and nitrates used to inhibit cellulose degradation in acid catalyzed cross-linking processes

Also Published As

Publication number Publication date
DE1166140B (de) 1964-03-26
BE606822A (en, 2012)
ES269457A1 (es) 1961-11-16
GB933998A (en) 1963-08-14
NL267756A (en, 2012)

Similar Documents

Publication Publication Date Title
US3046079A (en) Process of reacting partially swollen cotton textiles with aqueous solutions of specific aldehydes containing acid catalysts to produce wet and dry crease resistance
US2436076A (en) Method of stabilizing against shrinkage textile materials of regenerated cellulose
US3038777A (en) Process for improving the properties of regenerated cellulose fibrous material
US2681846A (en) Process for producing textile cellulose sulfo-ethyl ether cation-exchange material
US2469409A (en) Treatment of textile materials
US2158494A (en) Treatment of textile materials
US3113826A (en) Method of modifying cellulose with formaldehyde using lewis acid catalysts, solutions for use in such method, and products thereof
US2530175A (en) Stabilization of regenerated cellulose
US2824779A (en) Carbamoylethyl, carboxyethyl, and aminoethyl cellulose ether textile fibers and process of making the same
US3215488A (en) Novel treatments of textiles and textiles treated accordingly
GB1248840A (en) Wet fixation of resins in fiber systems for durable press products
US3118725A (en) Treatment of cellulose products
US2395791A (en) Stabilizing wool
US2107852A (en) Sizing fabric
US3125406A (en) Process for making them
US2473308A (en) Treatment of cellulosic textiles with strong hydroxide and acrylonitrile
US3015584A (en) Wrinkle resistance treatment for cellulosic textile fabrics
US3128147A (en) Process for treating polynosic fibers and products obtained thereby
Frick et al. Carbamoylethylation of Cotton with Acrylamide
US3312521A (en) Process of creaseproofing cellulose fibers with both glyoxal and formaldehyde
US2793930A (en) Process for treatment of cyanoethylated cotton fibers with amines to improve their physical properties
US3119715A (en) Processes for treating cellulosic textiles with acid colloids of methylolmelamine
US3224182A (en) Process for production of cross-linked cellulosic yarns
US2786735A (en) Process for producing cyanoethylated native cotton fibers by reacting cellulose fibers with acrylonitrile in vapor phase
US2686103A (en) Process of modifying regenerated cellulose and product resulting therefrom