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
  • D06M13/12—Aldehydes; Ketones
  • D06M13/13—Unsaturated aldehydes, e.g. acrolein; Unsaturated ketones; Ketenes ; Diketenes
• • 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
  • D06M11/01—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 hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof

Definitions

• This invention relates to a method for further modifying cellulosic materials containing carbonyl t'adicals and also relates to ⁇ he cellulosic materials so modified.
• the invention relates to a method for treating cellulosic materials containing carbonyl radicals with a reducing agent.
• US. Patent No. 2,711,971 and US. Patent No. 3,109,695 describe methods of treating cellulosic textile fabrics to introduce carbonyl radicals into the cellulose polymer.
• British Patent No. 959,522 describes a process in which a cellulosic textile fabric is treated to introduce acrolein, a carbonyl radical containing substance.
• cellulosic materials modified by the introduction of carbonyl radicals by reaction of suitable car bonyl compounds with cellulosic polymers exhibit limited stability when exposed to various chemical substances of even moderate activity.
• a white cotton textile fabric modified by introduction of carbonyl radicals to impart wrinkle-resistance, becomes yellowed or discolored when subjected to repeated launderings.
• Such discoloration is due to the effect of exposure to alkaline conditions. It is obvious that such discoloration represents a severe disadvantage to the utility of carbonyl-containing chemicals which could otherwise be used for imparting wrinkle-resistance to cotton or cellulosic fabrics.
• cellulosic materials contain- Patented Mar. 3, 1970 ing car-bonyl radicals have poor resis ance to hydrolysis in either acid or alkylinmedia.
• the improved properties obtainable as a result of the treatment of cellulosic materials with carbonyl-containing substances are not truly permanent in the sense that exposure of the cellulosic mategial to hydrolytic conditions may result in loss of properties due to loss of the carbonyl-containing substances or toother chemical changes.
• Anoher object of the present invention is to substantially eliminate discoloration by laundering of cellulosic materials which have been treated to introduce car-bonylcontaining substances.
• one embodiment of the present invention is a method of treating a cellulosic material containing carbonyl radicals whiclncomprises the step of treating the said cellulosic material with a reducing agent having sufficient reducing power to convert at least a substantial portion of the carbonyl radicals to a reduced form.
• the present invention is intended to encompass ali'isuch modified cellulosic material regar'dles s of the na ure of the carbonyl-containing substance andthe specific 'manner of introduction thereof.
• the present invention does not distinguish between materials formedexclusively from cellulose, such as a cotton fabric, and those which contain cellulosic polymers in addition to others.
• the latter class includes, gor example, a fabric oomposed of cotton and polyester hers.
• the alkali borohydrides are typical of the preferred reducing agents suitable for use in the present invention.
• This class of materials includes sodium borohydride (NaBH potassium borohydride (KBH and lithium borohydride (LiBI-I)
• NaBH potassium borohydride KH
• lithium borohydride LiBI-I
• Application of the reducing agent to the carbonylcontaining cellulosic material can be accomplished by any convenient method.
• the cellulosic material can be immersed in a solution containing the reducing agent or, alternatively, the cellulosic material may be padded or sprayed with a solution containing the reducing agent.
• any inert solvent may be utilized to prepare the solution containing the reducing agent, aqueous solutions are preferred because of the simplicity of the operation and from the stand-point of cost.
• reducing agents may be dependent on the pH of the environment.
• Certain reducing agents such as the alkali borohydrides are more effective at a relatively high pH, of the order of 10 or more; whereas others such as morpholine borane are preferably utilized at a relatively
• the reduction of carbonyl radicals with alkali borohydrides can be implemented by the use of certain inorganic salts which act as catalysts or accelerators. This phenomenon is disclosed in U.S. 3,118,724.
• catalysts or accelerators include complex""'metal salts of copper, nickel and colbalt, and magnesium, aluminum and lithium halides.
• the effect of treatment of carbonyl-containing cellulosic materials in accordance with the present invention can be analytically determined by analysis of the change in carlgpnyl content. From a practical stand-point, the improvement obtained by treatment in accordance with the present invention may be obtained by results of tests such as the following: I
• Samples of 80 x 80 cotton print cloth were modified with his (Z-pyridinium ethyl) ketone dichloride according to the following procedure.
• the cloth was impregnated with an aqueous solution of the ketone dichloride using a laboratory padder.
• the cloth was then framed and dried Lat 60 0., treated with an aqueous sodium hydroxide solution, .saturated.with sodium chloride and maintained in a flat condition-for about one minute.
• the cloth was then rinsed-successively with dilute acetic acid, water acetone and finally washed thoroughly in a dilute non-ionic detergent solution.
• the cloth was then framed and dried.
• a control sample of the ketone dichloride modified cloth was analyzed and was found to have a weight gain of 4.75% and a carbonyl radical content of 0.92 weight percent.
• Samples A through F were exposed to alkaline hydrolytic conditions by immersion in a 0.5 N sodium hydroxide solution for a period of about 3 hours.
• the alkaline solution was maintained at about C. and a fabric-liquid weight-"ratio of about 1 to 50 was used.
• Sample A lost a significant proportion of the increase in weight attributable to the ketone dichloride treatment.
• sample A took on a yellow color and exhibited a loss in crease "recovery.
• Samples D, E and F remained white in color, lost substantially no weight and showed substantially no decrease in crease recovery.
• the samples were treated with the respective solutions using a laboratory padder. Following impregnation of the samples, they were exposed to super-heater; steam at a temperature in the range of from about l-ll0 C. in
• EXAMPLE 5 contain 5.0 weight percent of sodium borohydride and sufficient sodium hydroxide to provide a 0.2 N concentration.
• a second aqueous solution, solution B was made up to contain the same amount of sodium hydroxide and sodium borohydride as solution A and contained, in addition, 0.2% K,Ni cN Samples of x 80 cotton print cloth were modified with acetone formaldehyde precondensate irifaceordance with Example 4 of US. 2,711,971.
• Sample A was found by analysis to have a weight gain of 15.4% and a carbonyl content of 1.5%.
• Another group of samples, designated Sarriple B was found by analysis to have a weight gain of 10.2% and a carbonyl content of 1.1%.
• Samples as described above were immersed in an aqueous solution of morpholine borane of 5 weight percent. Sufficient sulfuric acid was added to the solution to give a pH of about 1.5. The solution was maintained at a temperature of about 60 (It; and the samples were immersed for about 5 hours, the fabric to solution ratio being 1 to 50.
• EXAMPLE 7 Samples, treated as above, were impregnated with an aqueous soldtion containing 1% by weight of sodium borohydride :and sufiicient sodium hydroxide to provide a concentration of 0.2 N. The impregnation was accomplished by use of a laboratory padder.
• One set of samples, SampleflA was exposed (to super-heated steam at a temperature "of 100-110 Cffor a period of two rhinutes in a laboratory steamer.
• Another set of samples, Sample B was dried in a laboratory forced air oven at a temperature er 95 C. for a period of about 5 minutes.
• reducing agents which can be used for practicing the process of the present invention are those having an value lower than about +1, r value being defined as the negative logarithm of the equilibrium hydrogen pre ssure over the solution of reducing agent (see Melliaiid Textilber 44, p. 839, 1963).
• concentration of reducing agent required to obtain the desired result is dependent upon the carbonyl content of the cellulosic material to be treated and is also dependent upon the activity of the particular reducing g nt selected. I g nera concentrations in the range of about 0.5% to 5% by weight in the treating solution are effective.
• the present invention has been shown to substantiallv increase the utility of cellulosic materials which have previously been treated to introduce carbonyl radicals.
• the carbonyl content of the cellulosic material isof little consequenceand likewise, the manner in which the carbonyl radical is introduced in the cellulosic material is of minor importance.
• the process of the present invention is -applicable regardless of Whether the cellulosic materials are side chain modified or whether they are cross-linked. It is immaterial whether the cellulosic materials have been reacted with carbonyl containing radicals in the presence of alkaline or acidic catalysts or whether reacted in the presence of swelling agents or in their absence.
• the cellulosic materials which are suitable for treatment in accordance withthe present invention may be composed wholly or in part of natural cellulose such as cotton, and regenerated cellulose such as rayon or cellophane film.
• the cellulosic materials may also include linen, flax and the like.
• the physical shape and character of the cellulosic materials which are amenable to treatment by the present invention include such well known forms as film, fiber, yarn and fabric.
• 1.3m method of treating a crosslinked cellulosic textile material containing "dimethylene ketone or die'thylena ketone crosslinks which comprises treating said crosslinked textile material with a solution comprising a reducing agent having a r value below about +1, r being defined as the negative logarithm of the equilibrium hydrogen pressure over the solution of the reducing agent.
• the method of claim 4 is morpholino borane.

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=23720391

Family Applications (1)

Country Status (5)

Cited By (2)

Citations (8)

• 0
  • CH CH1767565D patent/CH1767565D/xx unknown
• 1965
  • 1965-02-17 US US433510A patent/US3498738A/en not_active Expired - Lifetime
  • 1965-11-18 GB GB49055/65A patent/GB1116506A/en not_active Expired
  • 1965-12-13 DE DE19651469485 patent/DE1469485A1/de active Pending
• 1966
  • 1966-01-14 NL NL6600538A patent/NL6600538A/xx unknown

Patent Citations (8)

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