US3199943A - Process for lowering the swelling in water of viscose cellulose by cyanoethylation in the presence of specific alkali metal salts - Google Patents

Process for lowering the swelling in water of viscose cellulose by cyanoethylation in the presence of specific alkali metal salts Download PDF

Info

Publication number
US3199943A
US3199943A US228025A US22802562A US3199943A US 3199943 A US3199943 A US 3199943A US 228025 A US228025 A US 228025A US 22802562 A US22802562 A US 22802562A US 3199943 A US3199943 A US 3199943A
Authority
US
United States
Prior art keywords
product
swelling
water
alkali metal
acrylonitrile
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
US228025A
Inventor
Paulusma Pieter
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
Application filed by American Enka Corp filed Critical American Enka Corp
Application granted granted Critical
Publication of US3199943A publication Critical patent/US3199943A/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
    • D06M13/322—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 nitrogen
    • D06M13/345—Nitriles
    • D06M13/348—Nitriles unsaturated, e.g. acrylonitrile
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
    • D06M11/65—Salts of oxyacids of nitrogen

Definitions

  • This invention relates generally to the production of I improved regenerated cellulose products and more particularly to a process for lowering the degree of swelling of regenerated cellulose products in water, especially viscose rayon fibers and fabrics.
  • Another object of this invention is to provide a process for treating regenerated cellulose products to lower their degree of swelling in water.
  • Still another object of this invention is to provide a process for producing regenerated cellulose products that absorb less moisture from the atmosphere.
  • regenerated cellulose products are first treated with an acqueous hydroxide solution that has a normality not higher than 0.70 and containsat least one salt of an alkali metal hydroxide and an inorganic acid derived from one of the first five anions of the lyotropic series according to Hofmeister (see E. A. Hauser, Collodial Phenomena, page 132, First Edition, 1939). Thereafter, the pro-ducts are treated with an azeotropic mixture of acrylonitrile and where A is the weight of the air dried cellulose pro-duct and B is the weight of the product after it had been soaked in water for two hours and centrifuged for ten minutes.
  • the normality of the hydroxide solution is higher than 0.70, the treated products have a cce higher degree of swelling than do the untreated products.
  • the normality of the hydroxide solution must be below 0.70.
  • the alkaline metal hydroxides that may be'used in the process include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. However, for economy reasons, it is preferred to use sodium hydroxide.
  • the salts added to the caustic solution may be lithium salt, sodium salt, potassium salt, rubidium salt, or cesium salt, although, also for economy reasons, it is preferred to use sodium salts.
  • the :salts are derived from an alkali metal hydroxide and any one of the following acids: sulfuric acid, hydrofluoric acid, nitric acid, hydrochloric acid, and hydrobr-omic acid. The anions of these acids are the first five members of the lyotropic series according to H-ofmeister.
  • sodium sulphate or sodium chloride is added to the caustic solution since these salts are commercially available at a low price.
  • the reaction may be accelerated by increasing the amount of salt in the caustic solution, the amount of salt added being dependent on the desired decrease in the degree of swelling in the product treated.
  • the temperature at which the treatment with the hydroxide solution is carried out may vary between wide limits. However, higher temperatures are desirable since the wet strength of the product decreases to a lesser extent. Also, the time during which the products are treated with the hydroxide solution preferably should be as short as possible to limit the decrease in the wet strength of the product. If needed, a wetting agent may be added to the hydroxide solution.
  • the products After the products have been treated with the hydroxide solution, excess liquid may be removed by centrifuging or pressing.
  • the products are then treated with a mixture of acrylonitrile and a small amount of water.
  • the temperature of the acrylonitrile mixture i maintained as high as possible in order that the/treatment may be short, thus allowing the process to be carried out in a continuous manner.
  • the treatment may be carried out at 70 C. using an azeotropic mixture consisiting of 88% of acrylonitrile and 12% water. If the treatment is carried out under pressure, even higher temperatures may be used.
  • a mixture of acrylonitrile and a diluent, such as benzene, toluene, acetone, or chloroform may be used.
  • the amount of acrylonitrile reacting with the products may vary within wide limits depending on the decrease in the degree of swelling desired.
  • Products treated in accordance with this invention not only have a lower degree of swelling in water, but also absorb less moisture in air.
  • the percentage of moisture absorbed from air may be reduced to below 8%. which corresponds to a moisture absorption of about 1 2% for untreated products of regenerated celiulose in air at 20 C. and a relative humidity of 65%.
  • Viscose rayon staple fibers having a denier of 1 /2 were separated into several samples and each sample treated with an aqueous sodium hydroxide and salt solution.
  • the numberof cyanoethyl groups may Run3 11 to 15 Show that y mcfreaslng the Sodlllm $111 be determined and such determination expressed as the P Content the reactlonls' conslderably accelelatfidweight percent of acryloni-trile bound to the final product. Runs 15 to 19 Show the afflicts Obtained using Sodium After the treatment with acrylonit-rile, the samples were 20 chlfmde, Potasslum Sulfate, Sodium nitrate, and Sodium successively washed with dilute acetic acid and warm wafluoflde as the Salts added 0 h Caustic Soluti n.
  • EX MPLE V The conditions and results of runs 1 to 10 are et A fabric having a warp conslsting of 120 denier comforth in Table I. tinuous filament viscose rayon threads and a weft consist- Table I Hydrox- Percent Tempera- Acryloni- Percent Moisture Normal- Percent Temp. ids soluincrease ture acrytrile treatacryloni- Deg.
  • 0.1 NSZSOA- 20 90 1 44 70 5 19.1 NaOH 0.1 NaCl- 5 90 1 44 70 5 12.2 Na-OHW 0.1 K1S01 5 90 7 1 45 70 5 13.4 NaOH 0.1 NaNO 5 90 .1 41 70 5 16.6 NaOH 0.1 NaF 5 90 1 38 70 5 20.6 NaOH--- 0. 2 KI 46 90 1 96 70 2% 23.1 NaOH.-- 0.1 Na2HPO4. 25 90 1 44 70 5 0.4 NaOH 0.1 NazSOr--- 5 20 1 44 70 5 16.5
  • the table shows that using a sodiurnhydroxide solution having a normality of 0.7 or lower results in a decrease of swelling.
  • the untreatedcontrol fibers had a degree of swelling of 75. Fibers treated according to runs 1 to 5 had a degree of swelling of 55, 58, 60,44 and7l,
  • the weight of the treated fabric was 124.7% of its original weight.
  • the fabric was immersed in water and afterwards centrifuged. It then contained about 63% by weight water.
  • EXAMPLE IV A selfsupporting film made from viscose was passed through an aqueous bath maintained at 90 C. containing 1% by weight sodium hydroxide and 5% by weight sodium sulfate. The residence time of the him in the bath was one minute. The film was passed between two rollers thereby removing excess liquid. Thereafter, the film was passed through a bath maintained at 70 C. containing 88% by weight acrylonitrile and 12% by weight water. Residence time in this bath was 1 /2 minutes. The film thus treated was passed between two rollers to remove excess liquid and successively washed with dilute acetic acid and warm water. After drying the film was immersed in water and centrifuged. The increase in weight of the film was only 65% in contrast with untreated film, similarly immersed in water and centrifuged which increased 98% in weight.
  • a process for lowering the degree of swelling in water of a dry viscose regenerated cellulose product comprising the steps of treating said product with an aqueous solution of an alkali metal hydroxide having a maximum normality of 0.70 for a suflicient period of time to effect cyanoethylation of the product upon subsequent treatment with acrylonitrile, said solution having present therein in addition to said alkali metal hydroxide a small amount of at least one salt of an alkali metal hydroxide and an acid derived from one of the first five anions of the lyotropic series of Hofmeister, treating the alkali impregnated product with acrylonitrile for a sufiicient period of time to cyanoethylate the product and to reduce the degree of swelling of the product upon contact with water, and thereafter drying the resulting product.
  • a process for treating a dry viscose regenerated cellulose product to lower its degree of swelling in water comprising the steps of immersing said product in an aqueous solution of an alkali metal hydroxide having a maximum normality of 0.70 for a sutlicient period of time to eifect cyanoethylation of the product upon subsequent treatment with acrylonitrile, said solution having present therein in addition to said alkali metal hydroxide a small amount of at least one salt of an alkali metal hydroxide and an acid derived from one of the first five anions of the lyotropic series of Hofmeister, immersing the alkali impregnated product in acrylonitrile for a sufficient period of time to bind to the product from about 6.7% to about acrylonitrile, based on the weight of the final cyanoethylated product, and thereafter drying the thustreated product.
  • a process for treating a dry viscose regenerated cellulose product to lower its degree of swelling in water comprising the steps of immersing said product for about 70 one minute in an aqueous solution of an alkali metal hydroxide having a maximum normality of 0.50 and a temperature of about 90 (3., said solution having present therein in addition to said alkali metal hydroxide a small amount of at least one salt of an alkali metal hydroxide and an acid selected from the group consisting of sulfuric acid, hydrofluoric acid, nitric acid, hydrochloric acid, and hydrobromic acid, immersing the alkali impregnated product in an azeotropic mixture of acrylonitrile and water for a sufficient period of time to bind to the product from about 6.7% to about 35% acrylonitrile, based on the weight of the final cyanoethylated product, washing the product, and thereafter drying the thus-treated prodnot.
  • a process for treating a dry viscose regenerated cellulose product to lower its degree of swelling in water comprising the steps of immersing said product for a maximum of two minutes in an aqueous solution of an alkali metal hydroxide having a maximum normality of 0.70, said solution having present therein in addition to said alkali metal hydroxide 5% by weight of said solution of at least one salt of an alkali metal hydroxide and an acid selected from the group consisting of sulfuric acid, hydrofiuoric acid, nitric acid, hydrochloric acid, and hydrobromic acid, immersing the alkali impregnated product in an azeotropic mixture of acrylonitrile and water main tained at a temperature ranging from 15 C.30 C. for a sufiicient period of time to bind to the product from about 6.7% to about 35% acrylonitrile, based on the weight of the final cyanoethylated product, washing the product, and thereafter drying the thus-treated product.
  • alkali metal hydroxide is sodium hydroxide and the salt is a sodium salt.
  • a process for treating a dry viscose regenerated cellulose product to lower its degree of swelling in water comprising the steps of immersing said product in an aqueous solution of an alkali metal hydroxide having a maximum normality of 0.70 for a sufficient period of time to increase the weight of the product by at least 38% after centrifuging, said solution having present therein in addition to said alkali metal hydroxide 5% by weight of at least one salt of an alkali metal hydroxide and an acid selected from the group consisting of sulfuric acid, hydrofluoric acid, nitric acid, hydrochloric acid, and h drobromic acid, immersing the alkali impregnated product in an azeotropic mixture of acrylonitrile and water maintained at a temperature of C. for a sufircient period of time to bind to the product from about 6.7% to about 35% acrylonitrile, based on the weight of the final cyanoethylated product, washing the product, and thereafter drying the

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Description

United States Patent Pieter Paulusma, Arnhem, Netherlands, assignor to American Enira Corporation, Erika, N.C., a corporation of Delaware No Drawing. Filed Diet. 3, 1962, 'Ser. No. 228,025 Claims priority, application Netheriands, Oct. 9, 1961,
9 Claims. 0!. 8-1162) .This invention relates generally to the production of I improved regenerated cellulose products and more particularly to a process for lowering the degree of swelling of regenerated cellulose products in water, especially viscose rayon fibers and fabrics.
It is known that the degree of swelling of regenerated cellulose products in water can be changed by successively treating them with an aqueous solution of an alkali metal hydroxide and acrylonitrile. However, by this process the degree of swelling of, for example, rayon staple fibers, is substantially increased. While such a relatively high degree of swelling may be favorable when the staple fibers are used in guaze bandages or analogous products, it is generally not desirable. Under most circumstances staple fibers or threads of regenerated cellulose should have a relatively low swelling value, particularly if they are processed into woven or knitted fabrics. This is because the dimensions of woven and knit-ted fabrics of regenerated cellulose yarns are, as is known, less stable than fabrics made of cotton fibers, which have a lower degree of swelling in water than do staple fibers or threads of regenerated cellulose.
. It is therefore an object of this invention to provide regenerated cellulose products that have a low degree of swelling in water.
Another object of this invention is to provide a process for treating regenerated cellulose products to lower their degree of swelling in water.
Still another object of this invention, is to provide a process for producing regenerated cellulose products that absorb less moisture from the atmosphere. I
These and other objects will become apparent from the following detailed disclosure In accordance with applicants invention, regenerated cellulose products are first treated with an acqueous hydroxide solution that has a normality not higher than 0.70 and containsat least one salt of an alkali metal hydroxide and an inorganic acid derived from one of the first five anions of the lyotropic series according to Hofmeister (see E. A. Hauser, Collodial Phenomena, page 132, First Edition, 1939). Thereafter, the pro-ducts are treated with an azeotropic mixture of acrylonitrile and where A is the weight of the air dried cellulose pro-duct and B is the weight of the product after it had been soaked in water for two hours and centrifuged for ten minutes.
Surprisingly, if the normality of the hydroxide solution is higher than 0.70, the treated products have a cce higher degree of swelling than do the untreated products. Thus, in order to obtain low swelling products, the normality of the hydroxide solution must be below 0.70. Moreover, applicant has discovered that the decrease in degree of swelling of treated products increases as the normality of the caustic solution decreases.
The alkaline metal hydroxides that may be'used in the process include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. However, for economy reasons, it is preferred to use sodium hydroxide. The salts added to the caustic solution may be lithium salt, sodium salt, potassium salt, rubidium salt, or cesium salt, although, also for economy reasons, it is preferred to use sodium salts. The :salts are derived from an alkali metal hydroxide and any one of the following acids: sulfuric acid, hydrofluoric acid, nitric acid, hydrochloric acid, and hydrobr-omic acid. The anions of these acids are the first five members of the lyotropic series according to H-ofmeister. Preferably, sodium sulphate or sodium chloride is added to the caustic solution since these salts are commercially available at a low price.
It has been found that the reaction may be accelerated by increasing the amount of salt in the caustic solution, the amount of salt added being dependent on the desired decrease in the degree of swelling in the product treated. The temperature at which the treatment with the hydroxide solution is carried out may vary between wide limits. However, higher temperatures are desirable since the wet strength of the product decreases to a lesser extent. Also, the time during which the products are treated with the hydroxide solution preferably should be as short as possible to limit the decrease in the wet strength of the product. If needed, a wetting agent may be added to the hydroxide solution.
After the products have been treated with the hydroxide solution, excess liquid may be removed by centrifuging or pressing. The products are then treated witha mixture of acrylonitrile and a small amount of water. The temperature of the acrylonitrile mixture i maintained as high as possible in order that the/treatment may be short, thus allowing the process to be carried out in a continuous manner. For example, the treatment may be carried out at 70 C. using an azeotropic mixture consisiting of 88% of acrylonitrile and 12% water. If the treatment is carried out under pressure, even higher temperatures may be used. Alternatively, a mixture of acrylonitrile and a diluent, such as benzene, toluene, acetone, or chloroform may be used. The amount of acrylonitrile reacting with the products may vary within wide limits depending on the decrease in the degree of swelling desired.
Products treated in accordance with this invention not only have a lower degree of swelling in water, but also absorb less moisture in air. As a result of the treatment, the percentage of moisture absorbed from air may be reduced to below 8%. which corresponds to a moisture absorption of about 1 2% for untreated products of regenerated celiulose in air at 20 C. and a relative humidity of 65%.
'The invention will .be more clearly understood from the following examples. However, these examples are not to be construed as limitative. Percentages are given by weight unless otherwise indicated.
EXAMPLE I Viscose rayon staple fibers having a denier of 1 /2 were separated into several samples and each sample treated with an aqueous sodium hydroxide and salt solution.
ment lasted one minute. After the treatment each sample was centrifuged and weighed. Thereaftenthe samples were treated with acrylonitrile containing 2% water at 20 C. With the exception of run 4, the duration of the treatments was such'that equal percentages of acry- EXAMPLE 11 Samples of staple fibers from thesame batch as those .lonltrrle were bound to all samples. vThe reaction be- Example I Were treated sodlllm hydfoxlde and tween the regenerated cellulose and acrylonitrile to pro- Salt $0111t1011 In a mannfif analogous that Of EXample duce a cyanoethylated product may be expressed by the In runs I0 however, the sodlum Sulphate 0011- f ll i ti tent was varied. The fibers pre-treated with the sodium 7 81k 10 hydroxide .solution were then treated with an azeotropic regen. cellulose0H GH =CHCN mixture of 88% by weight acrylonitrile and 12% by regen.cellulose0CHzCHzCN weight water at about 70 C. In runs 16 to 21 salts The percentage acrylonitnile bound to the regenerated other 'E sodlllm Sulfate were added to h Sodium "cellulose is calculated-by determining the amount of nitrohydrQxlde 5Q11l11011- In I 22 the temperature of thc genin the dry final product according to the well-known caustic solution was C. The results are set forth 1n Kjeldahl method. From the amount of nitrogen present Table p I in the final product, the numberof cyanoethyl groups may Run3 11 to 15 Show that y mcfreaslng the Sodlllm $111 be determined and such determination expressed as the P Content the reactlonls' conslderably accelelatfidweight percent of acryloni-trile bound to the final product. Runs 15 to 19 Show the afflicts Obtained using Sodium After the treatment with acrylonit-rile, the samples were 20 chlfmde, Potasslum Sulfate, Sodium nitrate, and Sodium successively washed with dilute acetic acid and warm wafluoflde as the Salts added 0 h Caustic Soluti n. AS ter and then dried. shown in runs 20 and 21, salts which are not derived from The degree of wellin was determin d f th the first five anions of thelyotropic series not now effect a formula: decrease in the degree of swelling of the fibers. In run 22 A 25 the disadvantage of using a low hydroxide solution tem- X 100% perature is shown. Thus, the use of a low temperature in the treatment yields fibers of considerably lower strength where A is the weight of the air dried fibers and B is the than does the use of a high temperature. weight of the fibers immediately following soaking in wa- I A ter for two hours and centrifuging for 1() minutes. EX MPLE V The conditions and results of runs 1 to 10 are et A fabric having a warp conslsting of 120 denier conforth in Table I. tinuous filament viscose rayon threads and a weft consist- Table I Hydrox- Percent Tempera- Acryloni- Percent Moisture Normal- Percent Temp. ids soluincrease ture acrytrile treatacryloni- Deg. 0i Wet absorp- Hydroxityofhy- Salt saltinhyhydroxtiontreatin Weight lonitrile/ ment in trile swelling strgh., tion in ide droxide droxide ide solument after cen- H2O, time bound to inwater gJd. air at solution solution tion, C. time trifuging .G. (minutes) fibers 20 (3.,
. (minutes) 5 RH. 65%
Control 1 NaOH- 0.10 Nagsol- 5 90 1 20 720 19 11.7 0. 20 M12801 5 90 1 20 240 19 7. s 0. 50 Na SO4 5 90 1 20 150 19 7. 7 0. 50 Na SO 5 90 1 63 20 240 35 6. 1 0. Na2s04 5 1 73 20 19 7. 7 0.80 Nafls 4- 5 90 1 s0 20 90 19 7.8 1.0 Naflso4 5 90- 1 s9 20' 5 80 19 7.9 1. 6 Nagsol 5 90 1 20 40 19 7. 6 2. 5 Na-2S04 5 90 1 241 20 15 19 7.8 0. 5 Nflasol 5 90 1 42 30 300 19 Table 11 Hydrox- Percent Acrylo- Percent Normal- Percent. Hydroxide solu increase Temperanitrile acrylo 7 Deg. of Wet Hydroxity of Salt salt in ide solution in weight ture acrytreat ient nitrile swelling strength, ide hydroxide hydroxide tion treatment after cenlonitrile/ time bound to in water g./d.
solution solution temp, O. time triiuging water, O. (minutes) fibers (minutes) ControL. '11 NaOH. 0.1 Na2sO4 1 90 1 40 70 5 6.7 NaOH 0.1 NazSOl--- 5 90 1 39 70 5 15. 9 NaOH--- 0.1 N8zSO4-.. 10 90 1 41 70 5 17. 2 NaOH 0. 1 Na2SO4 15 90 1 43 70 5 1s. 7 NaOH... 0.1 NSZSOA- 20 90 1 44 70 5 19.1 NaOH 0.1 NaCl- 5 90 1 44 70 5 12.2 Na-OHW 0.1 K1S01 5 90 7 1 45 70 5 13.4 NaOH 0.1 NaNO 5 90 .1 41 70 5 16.6 NaOH 0.1 NaF 5 90 1 38 70 5 20.6 NaOH--- 0. 2 KI 46 90 1 96 70 2% 23.1 NaOH.-- 0.1 Na2HPO4. 25 90 1 44 70 5 0.4 NaOH 0.1 NazSOr--- 5 20 1 44 70 5 16.5
The table shows that using a sodiurnhydroxide solution having a normality of 0.7 or lower results in a decrease of swelling. The untreatedcontrol fibers had a degree of swelling of 75. Fibers treated according to runs 1 to 5 had a degree of swelling of 55, 58, 60,44 and7l,
.ing of a yarn made of-1 /2 denier viscoserayon staple fibers, waspassed through an aqueous bathmaintained at 90 C. containing 1% by weight sodium hydroxide and 5% by weight sodiunrsulfate, The residence time'of the 75 fabric in the bath was one minute. Excess liquid was removed from the fabric by means of pressure rollers. The fabric was then passed through a bath maintained at about 7 C., containing 88% by weight acrylonitrile and 12% by weight water. The residence time of the fabric in this bath was 2 minutes. Excess liquid was removed from the fabric by means of pressure rollers and the fabric was then successively treated with dilute acetic acid and warm water. Thereafter, the fabric was dried. The weight of the treated fabric was 124.7% of its original weight. The fabric was immersed in water and afterwards centrifuged. It then contained about 63% by weight water. A similar sample of untreated fabric, after wetting and centrifuging, contained about 97% by weight water.
EXAMPLE IV A selfsupporting film made from viscose was passed through an aqueous bath maintained at 90 C. containing 1% by weight sodium hydroxide and 5% by weight sodium sulfate. The residence time of the him in the bath was one minute. The film was passed between two rollers thereby removing excess liquid. Thereafter, the film was passed through a bath maintained at 70 C. containing 88% by weight acrylonitrile and 12% by weight water. Residence time in this bath was 1 /2 minutes. The film thus treated was passed between two rollers to remove excess liquid and successively washed with dilute acetic acid and warm water. After drying the film was immersed in water and centrifuged. The increase in weight of the film was only 65% in contrast with untreated film, similarly immersed in water and centrifuged which increased 98% in weight.
Various modifications and changes within the scope of the invention will be apparent to those skilled in the art. Therefore, the invention is intended to be limited only as set forth in the following claims.
What is claimed is:
1. A process for lowering the degree of swelling in water of a dry viscose regenerated cellulose product comprising the steps of treating said product with an aqueous solution of an alkali metal hydroxide having a maximum normality of 0.70 for a suflicient period of time to effect cyanoethylation of the product upon subsequent treatment with acrylonitrile, said solution having present therein in addition to said alkali metal hydroxide a small amount of at least one salt of an alkali metal hydroxide and an acid derived from one of the first five anions of the lyotropic series of Hofmeister, treating the alkali impregnated product with acrylonitrile for a sufiicient period of time to cyanoethylate the product and to reduce the degree of swelling of the product upon contact with water, and thereafter drying the resulting product.
2. A process for treating a dry viscose regenerated cellulose product to lower its degree of swelling in water comprising the steps of immersing said product in an aqueous solution of an alkali metal hydroxide having a maximum normality of 0.70 for a sutlicient period of time to eifect cyanoethylation of the product upon subsequent treatment with acrylonitrile, said solution having present therein in addition to said alkali metal hydroxide a small amount of at least one salt of an alkali metal hydroxide and an acid derived from one of the first five anions of the lyotropic series of Hofmeister, immersing the alkali impregnated product in acrylonitrile for a sufficient period of time to bind to the product from about 6.7% to about acrylonitrile, based on the weight of the final cyanoethylated product, and thereafter drying the thustreated product.
3. A process for treating a dry viscose regenerated cellulose product to lower its degree of swelling in water comprising the steps of immersing said product for about 70 one minute in an aqueous solution of an alkali metal hydroxide having a maximum normality of 0.50 and a temperature of about 90 (3., said solution having present therein in addition to said alkali metal hydroxide a small amount of at least one salt of an alkali metal hydroxide and an acid selected from the group consisting of sulfuric acid, hydrofluoric acid, nitric acid, hydrochloric acid, and hydrobromic acid, immersing the alkali impregnated product in an azeotropic mixture of acrylonitrile and water for a sufficient period of time to bind to the product from about 6.7% to about 35% acrylonitrile, based on the weight of the final cyanoethylated product, washing the product, and thereafter drying the thus-treated prodnot.
4. A process for treating a dry viscose regenerated cellulose product to lower its degree of swelling in water comprising the steps of immersing said product for a maximum of two minutes in an aqueous solution of an alkali metal hydroxide having a maximum normality of 0.70, said solution having present therein in addition to said alkali metal hydroxide 5% by weight of said solution of at least one salt of an alkali metal hydroxide and an acid selected from the group consisting of sulfuric acid, hydrofiuoric acid, nitric acid, hydrochloric acid, and hydrobromic acid, immersing the alkali impregnated product in an azeotropic mixture of acrylonitrile and water main tained at a temperature ranging from 15 C.30 C. for a sufiicient period of time to bind to the product from about 6.7% to about 35% acrylonitrile, based on the weight of the final cyanoethylated product, washing the product, and thereafter drying the thus-treated product.
5. A process according to claim 4 in which the alkali metal hydroxide is sodium hydroxide and the salt is a sodium salt.
6. The process of claim 5 in which the salt is sodium sulfate.
'7. The process of claim 5 in which the salt is sodium chloride.
8. The process of claim t in which the regenerated cellulose product is viscose rayon staple fiber.
9. A process for treating a dry viscose regenerated cellulose product to lower its degree of swelling in water comprising the steps of immersing said product in an aqueous solution of an alkali metal hydroxide having a maximum normality of 0.70 for a sufficient period of time to increase the weight of the product by at least 38% after centrifuging, said solution having present therein in addition to said alkali metal hydroxide 5% by weight of at least one salt of an alkali metal hydroxide and an acid selected from the group consisting of sulfuric acid, hydrofluoric acid, nitric acid, hydrochloric acid, and h drobromic acid, immersing the alkali impregnated product in an azeotropic mixture of acrylonitrile and water maintained at a temperature of C. for a sufircient period of time to bind to the product from about 6.7% to about 35% acrylonitrile, based on the weight of the final cyanoethylated product, washing the product, and thereafter drying the thus-treated product.
References Cited by the Examiner UNITED STATES PATENTS 2,332,049 10/43 Bock et a1. 2,786,735 3/57 Compton et 211. 2,857,239 10/58 Bikales. 3,018,156 1/62 Bikales. 3,101,276 8/63 Hendriks 8--116 XR FOREIGN PATENTS 732,779 6/ 55 Great Britain. 812,063 4/59 Great Britain.
NORMAN G. TORCHIN, Primary Examiner.

Claims (1)

1. A PROCESS FOR LOWERING THE DEGREE OF SWELLING IN WATER OF A DRY VISCOSE REGENERATED CELLULOSE PRODUCT COMPRISING THE STEPS OF TREATING SAID PRODUCT WITH AN AQUEOUS SOLUTION OF AN ALKALI METAL HYDROXIDE HAVING A MAXIMUM NORMALITY OF 0.70 FOR A SUFFICIENT PERIOD OF TIME TO EFFECT CYANOETHYLATION OF THE PRODUCT UPON SUBSEQUENT TREATMENT WITH ACRYLONITRILE, SAID SOLLUTION HAVING PRESENT THEREIN IN ADDITION TO SAID ALKALI METAL HYDROXIDE A SMALL AMOUNT OF AT LEAST ONE SALT OF AN ALKALI METAL HYDROXIDE AND AN ACID DERIVED FROM ONE OF THE FIRST FIVE ANIONS OF THE LYOTRIPIC SERIES OF HOFMEISTER, TREATING THE ALKALI IMPREGNATED PRODUCT WITH ACRYLONITRILE FOR A SUFFICIENT PERIOD OF TIME TO CYANOETHYLATE THE PRODUCT AND TO REDUCE THE DEGREE OF SWELLING OF THE PRODUCT UPON CONTACT WITH WATER, AND THEREAFTER DRYING THE RESULTING PRODUCT.
US228025A 1961-10-09 1962-10-03 Process for lowering the swelling in water of viscose cellulose by cyanoethylation in the presence of specific alkali metal salts Expired - Lifetime US3199943A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL270070 1961-10-09

Publications (1)

Publication Number Publication Date
US3199943A true US3199943A (en) 1965-08-10

Family

ID=19753332

Family Applications (1)

Application Number Title Priority Date Filing Date
US228025A Expired - Lifetime US3199943A (en) 1961-10-09 1962-10-03 Process for lowering the swelling in water of viscose cellulose by cyanoethylation in the presence of specific alkali metal salts

Country Status (8)

Country Link
US (1) US3199943A (en)
BE (1) BE622899A (en)
CH (1) CH385159A (en)
DE (1) DE1186617B (en)
ES (1) ES281360A1 (en)
FR (1) FR1337579A (en)
GB (1) GB955306A (en)
NL (1) NL270070A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3880831A (en) * 1973-01-18 1975-04-29 Ryoichi Senju Process of producing carbamoylalkyl derivatives of high molecular compounds

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2332049A (en) * 1942-01-17 1943-10-19 Rohm & Haas Process of preparing organic solvent-soluble cellulose derivatives
GB732779A (en) * 1950-12-15 1955-06-29 Inst Textile Tech Improvements in method of treating cotton
US2786735A (en) * 1954-06-10 1957-03-26 Inst Textile Tech Process for producing cyanoethylated native cotton fibers by reacting cellulose fibers with acrylonitrile in vapor phase
US2857239A (en) * 1955-06-30 1958-10-21 American Cyanamid Co Method for the cyanoethylation of cotton textile fibers
GB812063A (en) * 1954-08-09 1959-04-15 American Cyanamid Co Cyanoethylation of cellulosic materials
US3018156A (en) * 1958-01-06 1962-01-23 American Cyanamid Co Process of cyanoethylating cellulose in the presence of salts
US3101276A (en) * 1957-07-08 1963-08-20 Du Pont Process for grafting polymers to cellulose substrates

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2332049A (en) * 1942-01-17 1943-10-19 Rohm & Haas Process of preparing organic solvent-soluble cellulose derivatives
GB732779A (en) * 1950-12-15 1955-06-29 Inst Textile Tech Improvements in method of treating cotton
US2786735A (en) * 1954-06-10 1957-03-26 Inst Textile Tech Process for producing cyanoethylated native cotton fibers by reacting cellulose fibers with acrylonitrile in vapor phase
GB812063A (en) * 1954-08-09 1959-04-15 American Cyanamid Co Cyanoethylation of cellulosic materials
US2857239A (en) * 1955-06-30 1958-10-21 American Cyanamid Co Method for the cyanoethylation of cotton textile fibers
US3101276A (en) * 1957-07-08 1963-08-20 Du Pont Process for grafting polymers to cellulose substrates
US3018156A (en) * 1958-01-06 1962-01-23 American Cyanamid Co Process of cyanoethylating cellulose in the presence of salts

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3880831A (en) * 1973-01-18 1975-04-29 Ryoichi Senju Process of producing carbamoylalkyl derivatives of high molecular compounds

Also Published As

Publication number Publication date
ES281360A1 (en) 1962-12-16
BE622899A (en)
FR1337579A (en) 1963-09-13
DE1186617B (en) 1965-02-04
CH385159A (en) 1965-03-15
NL270070A (en)
GB955306A (en) 1964-04-15
CH1115062A4 (en) 1964-08-31

Similar Documents

Publication Publication Date Title
US1989098A (en) Manufacture of artificial threads
US2780511A (en) Methiod of making cellulose acetate teixtile fibers by acetylization of relgenerated cellulose fibers
US3199943A (en) Process for lowering the swelling in water of viscose cellulose by cyanoethylation in the presence of specific alkali metal salts
US2452130A (en) Method of spinning high tenacity viscose rayon
US2265033A (en) Method of purifying textile materials
US3337671A (en) Method of making regenerated cellulose filaments
US2724632A (en) Cyanoethylated cellulose textiles modified with chromic and periodic acids and process of making same
US3018158A (en) Viscose process
US3146116A (en) Cyanoethylation and xanthation of alkali cellulose
US3107970A (en) Process for the manufacture of high tenacity viscose rayon
US3351696A (en) Method for producing regenerated cellulose products
US3102112A (en) Modification of cellulose with epoxypropyl amine compounds
US3109698A (en) Method for making high tenacity regenerated cellulose staple fiber
US2787517A (en) Manufacture of artificial viscose products
US3086835A (en) Process of increasing the tensile strength of cyanoethylated cotton textile fibers by soaking in specific chemicals and products produced thereby
US2225431A (en) Art of cuproammonium rayon manufacture
US2591315A (en) Alkali treatment of agave and manila hemp fibers to produce flexible fibers
US3124860A (en) Textile process and product
US2278284A (en) Stabilizing cellulose yarns
US2792279A (en) Viscose composition and method of spinning
US3046082A (en) Viscose process for the manufacture of low-shrink rayon
US2389015A (en) Manufacture of artificial textile fibers
US2518123A (en) Method of preparing nonpyrogenic medical absorbent wadding
US2792278A (en) Viscose composition and method of spinning
US2702228A (en) Method of modifying cellulose fibers with alkali solutions of copper or nickel biuret