Classifications

• • 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
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
• • 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
  • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
  • D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

• the present invention contributes to the man-made synthetic textile fiber art. It has reference to improvements in the manufacture of certain varieties of fibers of the type that are based essentially upon acrylonitrile polymers and which are wet spun in and with aqueous saline systems to form intermediate aquagel filamentary structures which, in the final stages of manufacture, are irreversibly dried to provide the desired, characteristically hydrophobic textile fiber product.
• the present invention relates more particularly to the treatment of such aquagels with specific varieties of opening agents to prevent filamentary bonding, sticking and adhesion during their drying from the highly hydrated aquagel state to their finished textile fiber form.
• tow bundles that are comprised of from 10,000 or 50,000 to 200,000 or more individual component endless or continuous filaments.
• a major cause of fiber sticking inaquagel filaments is thought to be the high surface tension that existsbetween the wet surfaces of adjacent filaments. Such surface tension exerts a considerable bonding force between adjacent fibers.
• Other causes which contribute to sticking of aquagel filaments are. the particular chemical.
• the present invention relatesto a significant improvement in the process of irreversibly drying an acrylonitrile polymer aquagel fiber, or an aquagel structure based essentially on an acrylonitrile polymer (particularly polyacrylonitrile), to the. finally dried, characteristically hydrophobic, synthetic textile fiber form desired.
• the improvement consists ofimpregnating a wet spun and washed and, advantageously, stretched (i.e., at least partially, if not completely, oriented) acrylonitrile polymer aquagel fiber prior to its final irreversible drying in hot air with an aqueous solution of a chemical opening agent which consists of a compound, ormixture of compounds, from the class of ditertiary acetylenic glycols characterized in having any of the general structures:
• each R is independently an alkyl radical containing from 1 to about 4 carbon atoms; and each Y is independently a cyclizing linear polymethylene unit of from 4 to carbon atoms (i.e., tetramethylene or pentamethylene) which, together with the completing carbon atom to which it is biterminally afi'ixed, forms an alicyclic ring system containing a total of 5-6 carbon atoms.
• the acetylenic glycol that is employed is 4,7-dimethyl-5-decyne-4,7-diol (commercially available from the Air Reduction Chemical Company as Surfynol 102) wherein, in Formula I, each R is n-propyl.
• Surfynol 102 Surfynol
• Other beneficial acetylenic glycols that may be utilized in the practice of the present invention are the typical species set forth in the following Table I.
• the acetylenic glycols are very soluble in acetone, carbon tetrachloride, ethylene glycol, ethyl acetate, methyl ethyl ketone and the like; moderately soluble in benzene, cyclohexanone, ethanol, diethylene glycol, petroleum ether and the like; slightly soluble in kerosene; and insoluble in such solvents as mineral oil, soya bean oil and the like.
• the opening agents utilized in the practice of the present invention generally produce aqueous solutions or suspensions having surface tensions of less than about 50 dynes per square centimeter; are suificiently water-insoluble to permit their presence as incompatible oils with the fiber after the initial stages of drying (wherein a major part of the water present is removed) and during the critical finishing drying stage, wherein the majority of sticking and interfilamentary bonding occurs; impart a non-adhesive film to the surface of the acrylonitrile polymer fiber that is treated (even when nitrile alloy fibers are involved, i.e., of the type containing polyvinyllactam adjuvants or other watersoluble or, at least, hydrophilic polymeric ingredients as dye-assistants); and are capable of being efl'iciently and effectively removed near the end of the drying under the indicated conditions so as to eliminate the possibility of their chemical reaction with the fiber base and to avoid other undesirable consequences.
• Such features and characteristics secure for the acetylenic glycols the
• the acetylenic glycol opening agents of the present invention are applied to the intermediate aquagel 'fiber (0r tow bundles thereof) which has been prepared by wet spinning techniques using aqueous saline solutions to prepare the polymer dissolving spinning solutions as well as the coagulating baths therefor.
• the opening agent is applied after the aquagel has been washed completely or substantially completely from residual salt and, either concurrently with or subsequent to hot stretching for purposes of orientation of the aquagel fiber product. It is generally most convenient to apply the agent after stretch orientation and to make the application from a flushing bath, wherein the residual moisture or water content in the aquagel fiber is replaced by the applicating solution or dispersion of the acetylenic glycol opening agent. 01": course, as has been indicated, it is most expedient to employ the opening agent on the aquagel fibers in tow bundle form.
• the opening agents of the present invention are applied to strandular, filamentary and the like aquagel structural forms of fiber-forming polymers that are based upon acrylonitrile.
• These hydrated forms of the polymer may be obtained by extruding a spinning solution of the polymer into an aqueous coagulating bath wherein the spinning solvent in the extruded filamentary structure is replaced to a large extent with water.
• Such water swollen or hydrated filamentary structures can advantageously be prepared by extruding solutions or other spinnable dispersions of the fiber-forming acrylonitrile polymers in polyacrylonitrile-dissolving aqueous saline solvents into aqueous, non-polymer-dissolving coagulating spin bath solutions of the same salt or salts as used in the spinning solution.
• zinc chloride or its saline equivalents for such purpose are utilized, including such salts as calcium and other thiocyanatcs (as disclosed in US. Patents Nos.
• the aquagel fibers that are treated with the acetylenic glycol opening agents in the practice of the present invention which are based essentially on fiber-forming acrylonitrile polymers may be the usual homopolymer or copolymer compositions containing in the polymer molecule at least about percent by weight of acrylonitrile that are adapted to provide the variety of filamentary products that are conveniently referred to as being acrylic fibers.
• the basic acrylonitrile polymer composition may contain or have other beneficial. additament ingredients incorporated or combined therein. These may be the typical pigments, delusterants, textile assistants and the like (including antistatic agents) or they may be dye-assisting adjuvant materials.
• dye-receptive polymers may be incorporated in a polyacrylonitrile or other acrylonitrile polymer aquagel fiber that is treated in accordance with the present invention.
• the dyereceptive polymers may be vinyl lactam polymers, including poly-N-vinyl-2-pyrrolidone, poly-N-vinyl-Z-caprolactam, and the like; N-vinyl-2-oxazolidinone polymers, in-
• the dye-assisting adjuvant materials of nitrile alloy type fibers may also be present in the essential acrylonitrile polymer base in the form of graft or block copolymerized units of such polymers upon an already formed acrylonitrile polymer base or, alternatively, polymeric products in which the essential acrylonitrile polymer base is graft or block copolymerized on an already formed dye-assisting adjuvant polymer backbone. It is generally preferred, for purposes of terminological classification, to characterize the latter, highly advantageous variety of dye-receptive fibers as being nitrile alloy fibers in order to clearly distinguish them from the conventional, prototype, socalled acrylic fibers that were first known to the art.
• the applicating bath of the acetylenic glycol opening agent may be either a water solution or colloidal suspension thereof containing from about 0.1 to 1.3 percent, and preferably at least about 0.4 percent, of dispersed active agent. It is generally desirable for the acetylenic glycol opening agents to be formulated in the applicating compositions thereof as saturated solutions, i.e., in aqueous dispersions wherein their concentration is not in excess of that at which they form true solutions or colloidal suspensions. Such manner of employment beneficially avoids the deposition of large oily particles on the aquagel fibers being treated, which might tend to produce non-uniform effects in the treatment.
• the bath imparts between about 0.75 to 2.5 percent by weight on the Weight of the dry fiber (o.w.f.) of the opening agent on the aquagel fiber. While it is advantageous to apply the opening agent from an impregnating bath, suitable results may also be achieved by spraying, rolling or wiping (as with wick applicators) the applicating solution of the opening agent on the aquagel fibers being treated.
• the opening agents are applied to the aquagel fibers or tow bundles thereof prior to any wet-crimping operation that may be contemplated for the fibers, if and when such operation is included in the processing sequence.
• the aquagel fibers are irreversibly dried, to provide the desired, characteristically hydrophobic, synthetic textile fiber product. Drying is best accomplished in and with hot air at temperatures between about 100 and 150 C. for periods of time between about 30 and minutes.
• Fibers treated and dried in accordance with the present invention may generally be obtained in excellent finished form. They have substantially, if not completely, reduced occurrence of undesired sticking and interfilamentary bonding and are in a condition wherein the optimum properties of the fiber product is brought out to best advantage.
• acetylenic glycol opening agents that are, employed in the practice of the present invention lies in their ability to be successfully and satisfactorily recovered for re-use after their application in the process.
• the aquagel tow bundle entering the dryingoven or chamber can be shown to contain the agent.
• the irreversibly dried fiber product leaving the drying area contains none or vanishingly smalland insignificant quantities of the agent. This is experienced despite the fact that successful opening action has been accomplished and the agent has operated in the desired manner during the drying step. It is believed that the agent is removed from the aquagel structure being dried by means of steam distillation. Thus, recovery of the condensate and re-use of the agent is an attractive feature of the present invention.
• Example 1 A polyacrylonitrile spinning solution was prepared by dissolving about one part of a fiber-forming species of the polymer having an average molecular weight between about 30 and 35 thousand in about 10 parts ofa percent aqueous solution of zinc chloride.
• the "spinning solution had a viscosity of about 2200 poises at a temperature of about 25 C. It was extruded at about 30 C. through a spinnerette system into about 15 thousand separate, individual aquagel filaments. The diameter of each jet hole through which each individual 'filament was extruded was about 6 mils.
• the extruded spinning solution was coagulated in a coagulating liquid comprised of about a 43 percent aqueous solution of zinc chloride at 15 C.
• the aquagel filaments were withdrawn from the coagulating liquid and assembled in the form of a relatively flat, ribbon-like, multiple filament tow bundle.
• the wet spun tow was then passed into a water wash bath, wherein it was washed to the point at which the zinc chloride content was not in excess of about 0.05 percent.
• the washed tow was then oriented by being stretched to a total length of about 12 times its original length. By these operations there was obtained a washed and oriented filamentary tow bundle of the 15,000 individual aquagel strands.
• the total aquagel denier of the washed and oriented tow bundle was about 100,000.
• the tow bundle had an average width of about one inch and an average thickness of about 20 thousandths of an inch.
• the oriented aquagel structures contained about 2.0 parts of water for each partof fiberforming polya crylonitrile that was present therein.
• the aquagel contained about 8 percent of poly- N-vinyl-2-pyrrolidone (PVP) (based on the dry weight fiber) that had been incorporated therein as a polymeric dye-assisting adjuvant by impregnation of the watersoluble polymer (from an impregnating bath in which it was contained in aqueous solution) into the aquagel structure.
• PVP poly- N-vinyl-2-pyrrolidone
• the washed and oriented tow was then passed in a.
• the tow bundle was then tested by a standard method of analysis to determine the. number of sticks per gram in the finally obtained product.
• the analysis method employed is one common and well known to the art, wherein a card web of the, fiber is observed in order to count neps or blemishes therein. A segment of carded web fiber is visually examined after a specified number of passes through a sample card. Sticks per gram are an expression of the number of bonded fibers 'counted on a standard sample. Two passes through the sample card arefound to approximate the standard cotton carding operation performed'on a production scale. The sticks observed after such treatment provide an accurate picture orrepresentation of the frequency or number of bonded fibers present.
• the untreated tow bundle was found to have been prepared with about 280 sticks per gram after the second pass over the card web and with about 38 sticks per gram after the four passes over the sample card.
• the spinning and drying procedure was repeated on three additional tow bundle samples excepting that, immediately prior to drying the washed and stretched tow bundles, they were passed through an aqueous applicating solution of an acetylenic glycol opening agent in accordance with the practice of the present invention at room temperature with a two second residence (immersion) time of each tow bundle sample in the bath.
• Each of the treating baths employed had a different concentration of the opening agent therein.
• the treated tow bundle was not rinsed prior to drying.
• the acetylenic glycol employed was 4,7-dimethyl--decyne-4,7-diol (Surfynol 102).
• an aquagel 3 denier per filament tow bundle prepared in the same way as above described was dried in a completely relaxed state and without opening agent treatment to obtain the final synthetic fiber structure.
• the procedure was duplicated excepting to soak an identical wet tow in a 0.4 percent aqueous solution of Surfynol 102.
• each tow bundle was dipped into a 1 percent solution of Emulphor EL-719 (a synthetic detergent consisting of a nonionic acyl (fatty) polyoxyethylene glycol supplied by General Aniline & Film Corporation), squeezed, and again dried for 10 minutes in a 150 C. oven.
• Emulphor is a standard finishing agent used for antistatic and lubricating purposes for the finally dried product. It is not an opening agent.
• the product treated with opening agent had 219 sticks per gram.
• the untreated tow by way of comparison, was found to contain about 389 sticks per gram.
• Example 3 An aquagel tow bundle was prepared identically as in Example 1 with the major exception that no PVP was incorporated in the polyacrylonitrile fibers.
• the dried, treated tow bundle was exceptionally open and flufiy. Its individual component filaments were distinctly individal and non-bonded. in marked contrast therewith, an identical polyacrylonitrile aquagel tow bundle that was dried without being treated in accordance with the present invention had a significantly inferior and undesirable shredded wheat" fibrous appearance and feel.
• Example 4 Similar results are obtained when the foregoing is repeated excepting to use other forms and types of unmodified polyacrylonitrile or to employ unmodified acrylonitrile copolymer fibers or when using nitrile alloy fibers containing other polymeric dye-assisting adjuvants in place of the poly-N-vinyl-2-pyrrolidone, such as poly- N vinyl 2 oxazolidinone, poly N vinyl 5 methyl 2 oxazolidinone, poly N vinyl 3 morpholinonc, etc.
• poly-N-vinyl-2-pyrrolidone such as poly- N vinyl 2 oxazolidinone, poly N vinyl 5 methyl 2 oxazolidinone, poly N vinyl 3 morpholinonc, etc.
• an acrylonitrile polymer aquagel fiber to convert it to a synthetic, characteristically hydrophobic, textile fiber product
• said aquagel consisting essentially of an acrylonitrile polymer that contains at least about weight percent of acrylonitrile polymerized therein, any balance being another polymerized monoethylenically unsaturated monomer that is copolymerizable with acrylonitrile, said aquagel containing between about 1 and 3 parts by weight of hydrated water to each part of dry polymer therein, the improvement which consists of applying to said aquagel fiber prior to drying between about 0.75 to 2.5 percent based on the weight of the aquagel fiber, of an acetylenic glycol opening agent selected from the class consisting of those having the structural formulae:
• each R is independently an alkyl radical containing from about 1 to 4 carbon atoms; and each Y is a cyclizing linear polymethylene unit which, together with the completing carbon atom to which it is aifixed, forms an alicyclic radical of from 5 to 6 carbon atoms; then irreversibly drying the aquagel in hot air at a temperature between about and C. for a period of time between about 30 and 5 minutes.
• opening agent is applied by immersing said fiber in said applicating bath.
• said aquagel fiber is a nitrile alloy fiber which consists essentially of a composition of (1) at least about 80 weight percent
• an acrylonitrile polymer that contains at least about 80 weight percent of polymerized acrylonitrile therein, any balance being another polymerized monoethylenically unsaturated monomer that is copolymerizable with acrylonitrile, and (2) up to about 20 weight percent, based on the dry weight of the composition, of a polymerized dyeassisting adjuvant selected from the group consisting of polymerized N-vinyl-2-pyrrolidone, polymerized N-vinyl- 2-caprolactam, polymerized N-vinyl-Z-oxazolidinone, polymerized N vinyl 5 methyl 2 oxazolidinone and polymerized N-vinyl-3-morpholinone.
• a polymerized dyeassisting adjuvant selected from the group consisting of polymerized N-vinyl-2-pyrrolidone, polymerized N-vinyl- 2-caprolactam, polymerized N-vinyl-Z-oxazolidinone, polymerized N vinyl 5
• nitrile alloy fiber is comprised of polyacrylonitrile containing intimately blended therewith up to about 20 percent by Weight, based on the dry weight of the fiber, of poly- N-vinyl-Z-pyrrolidone as a dye-assisting adjuvant.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Health & Medical Sciences (AREA)
• Toxicology (AREA)
• Artificial Filaments (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Graft Or Block Polymers (AREA)

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Citations (2)

• 0
  • BE BE589115D patent/BE589115A/xx unknown
• 1958
  • 1958-04-16 US US728787A patent/US2935426A/en not_active Expired - Lifetime
• 1959
  • 1959-02-19 GB GB5809/59A patent/GB852402A/en not_active Expired
  • 1959-03-12 DE DED30197A patent/DE1122215B/de active Pending
  • 1959-03-16 FR FR789648A patent/FR1230522A/fr not_active Expired

Patent Citations (2)

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