US2920934A - Process of producing non-fibrillating acrylonitrile polymer filaments with wet steamtreatment and products produced thereby - Google Patents

Process of producing non-fibrillating acrylonitrile polymer filaments with wet steamtreatment and products produced thereby Download PDF

Info

Publication number
US2920934A
US2920934A US553714A US55371455A US2920934A US 2920934 A US2920934 A US 2920934A US 553714 A US553714 A US 553714A US 55371455 A US55371455 A US 55371455A US 2920934 A US2920934 A US 2920934A
Authority
US
United States
Prior art keywords
filaments
acrylonitrile
percent
chamber
fibers
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
US553714A
Other languages
English (en)
Inventor
Rodger L Schaefer
Edward H Sundbeck
Roy W Sudhoff
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.)
Solutia Inc
Original Assignee
Chemstrand 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 BE553539D priority Critical patent/BE553539A/xx
Application filed by Chemstrand Corp filed Critical Chemstrand Corp
Priority to US553714A priority patent/US2920934A/en
Priority to GB35779/56A priority patent/GB848696A/en
Priority to DE1956C0014134 priority patent/DE1236125C2/de
Priority to CH4086256A priority patent/CH371550A/de
Priority to FR1170239D priority patent/FR1170239A/fr
Application granted granted Critical
Publication of US2920934A publication Critical patent/US2920934A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18Monocomponent 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
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38Monocomponent 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
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/40Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/47Processes of splitting film, webs or sheets

Definitions

  • This invention relates to new and improved acryloniproved structuresformed from blends of the acrylonitrile polymers with other polymers formed from polymerizable monoolefinic monomers.
  • Polymers of acrylonitrile containing at least 70% by weight of polymerized acrylonitrile and blends thereof are well-known in the art of synthetic fiber and filament production.
  • the acrylonitrile polymers are quite useful for the production of synthetic fibers and filaments because it is possible to obtain the high tensile strength and other desirable physical properties required in salable fibers and filaments.
  • Various methods may be employed in producing structures, such as fibers and filaments, from acrylonitrile polymers including the so-called wet spinning process.
  • This process comprises extruding a solution of the acrylonitrile polymer through a spinneret into a bath comprising a liquid which will readily leach out the solvent from the polymer solution and coagulate or precipitate the polymer from its solution, the filaments being carried through the bath for a period of time sufiicient to solidify the polymer to the desired extent.
  • the filaments are subjected to a stretching operation, preferably while they are in the gel state, in order to increase their tenacity as well as otherwise to improve physical properties by orienting the polymer molecules of which the filaments are composed.
  • Filaments produced from acrylonitrile polymers by the wet spinning process have excellent physical properties but do sulfer from one serious defect, namely, fibrillation. That is, the fibers and filaments, when formed into yarns and in turn fabrics, split off fibrils when subjected to excessive wear in any given area.
  • Fibrillation is a phenomenon induced in fibrous materials by the application of stress, usually in the form of abrasion, and is characterized by the splitting off from the parent filament or fiber of longitudinal sections of material which are usually referred to as fibrils.
  • the di- Patented Jan. 12, 1960 e we mensions of the fibrils are small compared to those of the original filament fiber.
  • the splitting off of 'the' fibrils is referred to as fiber breakdown and can readily be observed under the microscope, where the presence of fibrils may be seen. In undyed fabrics, however, the presence of fibrils may be unobserved.
  • Dyed fabrics formed from filaments and fibers of acrylonitrile polymers by the wet-spinning process, and particularly those fabrics composed of surface-dyed filaments and fibers, readily display the effects of fibrillation.
  • shade changes will be produced in the area of abrasion due to the exposure of undyed, internal portions of filaments and fibers and/ or the reduced particle size of the fibrils which, through a light-scattering effect, produces an apparent color change. Obviously, such a change in color is to be avoided and so long as filaments and fibers have a tendency to fibrillate, they are practically useless in most commercial applications.
  • the acrylonitrile polymer filaments are stretched in order to orient the molecules therein.
  • the purpose of this procedure is to increase the tenacity of the filaments to a practical point.
  • fibrillation occurs in highly-oriented, crystalline filaments which are of such morphological structure that they possess high longitudinal strength and low transverse strength. It was first thought that such fibrillation could be overcome by a reduction in orientation to be accomplished by the use of lower stretch. However, such reduction in the amount of stretch, while overcoming fibrillation to a certain degree, did not produce filaments having the necessary low fibrillation and in addition, the reduction in amount of stretch resulted in a deleterious eifect on other desirable and essential properties in the filaments and fibers, such as reduction in tenacity and elongation, and the like. Accordingly, a continued effort has been made to overcome the objectionable fibrillation without deleteriously affecting the essential and desirable properties of acrylonitrile polymer structures and still produce a salable product.
  • acrylonitrile polymer structures which do not fibrillate, or fibrillate to a negligible degree, can be produced by subjecting the acrylonitrile polymer structure to a high temperature and pressure in the presence of saturated or wet steam.
  • the tow or bundle of filaments is placed in a closed chamber, such as an autoclave, or like pressure apparatus, and the chamber is evacuated. Thereafter wet steam is run into the autoclave until a pressure of 30 to- 60 pounds per square inch is registered therein.
  • the chamber is vented and again the chamber is evacuated. Then the vacuum in the chamber is broken and the tow removed therefrom and cut into staple fibers, if desired.
  • the wet steam treating cycle described above may be repeated as many times as desired. In many instances, where a large amount of filaments are being treated at one time, it is necessary to repeat the cycle several timesin order to insure efficient and complete penetration of the steam throughout the entire mass.
  • the steam pressure is reduced to around 2 psi. before introducing further steam. It is to be noted that the actual time required to steam treat or anneal a. single filament is a fraction of a second. Thenumber of cycles .pounds of tow were so treated.
  • the steam pressure is an important factor in the present invention in order to obtain the desirable results, i.e., in order to obtain the optimum yarn properties, such as strength, elongation, fiber breakdown, fibrillation rating and color. It has been found that when steam pressures below 25 psi. are employed, the resulting filaments and fibers have a fibrillation rating, explained in more detailhereinafter, which is too high. When steam pressures above 60 p.s.i. are employed, the resultant yarn strength is too low and too much color is developed in the filaments and fibers. The optimum results with. respect to fiber properties are obtained when steam pressures in the range of to p.s.i. are employed.
  • the temperature of the steam when introduced into the closed chamber, be in the range of 135 to 155 C., i.e., steam under a pressure of 30 to psi. Further, the steam must be wet. It is necessary that the acrylonitrile polymer structures be wet with the steam. during treatment. Normally, very high temperatures would be necessary to overcome the internal bonding forces within the structure which are believed to cause fibrillation. However, the presence of a plasticizer, such as water in the form of wet or saturated steam, permits lower temperatures to be employed than would be otherwise possible. standpoint of undesirable color formation in the structure during treatment.
  • the final vacuum is employed in the instant process in order to cool the filaments or fibers in the chamberv or autoclave, thereby reducing color development in the filaments, and to remove excess water from the tow or bundle of filaments.
  • the present invention is applicable to. structures formed from various acrylonitrile polymers and blends thereof, for example, polyacrylonitrile, copolymers. and terpolymers of percent or more of acrylonitrile and up to 30 percent of other polymerizable mono-olefinic monomers, such as vinyl acetate and other vinyl esters of monocarbcxylic acids, vinylidene chloride, vinyl chloride and other vinyl halides, dimethyl fumarate and other dialkyl esters of fumaric acid, dimethyl maleate and other dialkyl esters of maleic acid, methyl acrylate and-other alkyl esters of acrylic acid, styrene and other vinyl-substituted aromatic hydrocarbons, methyl.
  • polyacrylonitrile polymers and blends thereof for example, polyacrylonitrile, copolymers. and terpolymers of percent or more of acrylonitrile and up to 30 percent of other polymerizable mono-olefinic monomers, such as vinyl acetate
  • methacrylate and other alkyl esters of methacrylic acid, methacrylonitrile, alpl'iaivinylpyridine and other vinyl-.substitutedfheterocyclienitrogen ring compounds such as; the vinyl imidazolesretc thealkyl-substituted vinylpyridines, Sllfihi as: 2,-meth-yl-5-vinylpyridine and the: like, vinyl allyl-.- and:
  • comonomers which contain one polymerizable olefinic radical whereby the copolymerization with acrylonitrile may be etfected and oneacidic, basic or otherwise reactive group capable of bonding the dyestuif with which the ultimate structure may be treated.
  • these non-dyeable fiber-forming copolymers may be blended with polymers or copolymers which are in themselves more dye-receptive by reason of their physi cal structure or by reason of the presence of functional groups which are chemically reactive with the dyestutf,
  • Suitable blending polymers may be polyvinylpyridine, polymers of alkylsubstituted vinylpyridines, polymers of other alkenyl-substituted N-heterocyclic compounds, the copolymers of the various alkenyl-substituted N-heterocyclic compounds,
  • non-dyeable aciylonitrile polymers of good fiber-forming properties for example, polyacrylonitrile or a copolymer of more than percent acrylonitrile and up to 15 percent of vinyl acetate, and a copolymer of vinylpyridine or an alkyl substituted vinylpyridine and acrylonitrile, the said acrylonitrile being present in substantial proportions, for example, a total of 50 to 80 percent acrylonitrile in the blend to provide heat and solvent resistance, and a substantial proportion of the pyridine or derivative thereof to render the blend receptive to acid dyestuffs.
  • compositions suitable for blending with nondyeable acrylonitrile polymers are: the polyamides prepared by condensing an alkylene diamine having up to six carbon atoms and a compound of the group consisting of crotonic acid, acrylic acid, methacrylic acid and the alkyl esters of these acids, wherein the alkyl radical has up to five carbon atoms; the polyamides prepared by condensing N-alkylazadinitriles with formaldehyde; the polyesters prepared by reacting dicarboxylic acids with glycols containing tertiary amino groups; and other polymers containing tertiary amino radicals capable of reacting chemically with the acid dyestuifs.
  • a further class of useful dye-receptive resins suitable for blending with the non-dye-receptive acrylonitrile polymers are the tertiary amino group containing polymers and copolymers described in the preceding paragraphs which have been reacted with aliphatic halides, for example, butyl bromide, chloracetic acid, methyl chloroacetate, with the esters of oxygen containing sulfur acids, which acids have ionization constants greater than 10"-, for example, methyl sulfate and methyl p-toluenesulfonate and with the various acids, such as sulfuric acid, hydrochloric acid and benzenesulfonic acid.
  • aliphatic halides for example, butyl bromide, chloracetic acid, methyl chloroacetate
  • esters of oxygen containing sulfur acids which acids have ionization constants greater than 10"-, for example, methyl sulfate and methyl p-toluenesul
  • Any of the known acrylonitrile polymer polymerization procedures may be employed in making the polymers for-usein the practice of the present invention. As in.
  • the physical properties of the polymers are of substantialrimportance. It is desirable that the polymers be uniform with respect to molecular weight, particle size, and chemical composition. Accordingly, the methods for their preparation must be selected so as to induce the uniformity of chemical and physicalproperties. In general, the molecular weight should be in excess of 10,000 and preferably in excess of 25,000, the molecular weights beingdetermined by measuring the viscosity of dilute solutions in the manner well-known in the art.
  • polymers and copolymers of desirable physical properties are those which are prepared by the aqueous suspension technique, wherein the monomers or mixture of monomers are added to an aqueous medium maintained under conditions suitable for a rapid but controlled polymerization.
  • the aqueous medium should contain a water-soluble peroxy catalyst and a dispersing agent which induces the precipitation of a finely divided polymer during the reaction.
  • a dispersing agent which induces the precipitation of a finely divided polymer during the reaction.
  • the preferred practice involves the charging of the monomers or mixtures of monomers, gradually during the course of the reaction at a uniform rate or ata varying rate which permits the maintenance of the reaction at a constant temperature, for example, the reflux temperature.
  • the fiber-forming acrylonitrile polymers are prepared by polymerization in the presence of water-soluble peroxide catalysts, such as the alkali metal salts of the various peroxy acids, for example, sodium perborate, sodium percarbonate, and potassium persulfate.
  • Stabilizing or dispersing agents such as the water-soluble salts of the sulfonated mahogany acids, salts of the formaldehyde condensed naphthalene sulfonic acids, salts of sulfonated alkylbenzenes, salts of triethanolamine, sodium stearate and other salts of carboxylic acids, and mixtures thereof prepared by the saponification of animal and vegetable oils.
  • Desirable methods for the preparation of acrylonitrile polymers of uniform molecular weight involve the use of regulators, for example, tertiary dodecyl mercaptan, beta-mercaptoethanol, thioglycolic acid, beta-mercaptopropionic acid, and acetaldehyde.
  • regulators for example, tertiary dodecyl mercaptan, beta-mercaptoethanol, thioglycolic acid, beta-mercaptopropionic acid, and acetaldehyde.
  • the nature of the other monomeric substances being polymerized with the acrylonitrile may determine the type of substance useful as a regulator.
  • thioglycolic acid is unusually beneficial.
  • the preparation of copolymers of the basic monomers such as vinylpyridine; the use of tertiary aliphatic mercaptans will be found to be very effective.
  • the present invention is applicable to the treatment of filaments and fibers formed by. the so-called dryspinning process, wherein a polymer solution in a volatile organic solvent, such as N,N-dimethylformamide, and the like, is extruded into a heated gaseous atmosphere and the solvent is evaporated leaving a coagulated filament, as well as by the wet spinning process.
  • a volatile organic solvent such as N,N-dimethylformamide, and the like
  • a solution of the polymer in a suitable solvent such as ethylene carbonate, N,N-dimethylformamide, N,N-dimethylacetamide, and the like, commonly referred to as the dope
  • a suitable solvent such as ethylene carbonate, N,N-dimethylformamide, N,N-dimethylacetamide, and the like, commonly referred to as the dope
  • the bath comprises a non-solvent for the polymer which is also a solvent for, or miscible with, the solvent in the dope.
  • the filament, or filaments, as the case may be are removed from the coagulating bath and passed through a washing medium where all residual solvent and coagulating liquid are removed therefrom.
  • Water is the preferred washing medium and is usually contained in a bath through which the filaments are passed.
  • the washing medium may flow concurrent with or countercurrent to the direction of travel of the filaments therethrough. Washing rolls or like apparatus may also be employed.
  • the filaments are dried and steam stretched, if desired.
  • a solvent stretch bath may be employed immediately following the coagulating bath Wherein the polymer molecules in the filaments are oriented. Any solvent or plasticizer for acrylonitrile polymers may be employed in the solvent stretch bath.
  • the concentration of the solvent in the bath will depend upon the chem ical characteristics of the solvent used and the temperature of the bath. Obviously, the concentration must be such that the polymer article passing therethrough will not dissolve therein. Certain solvents may be used in higher concentrations than others. For example, up to percent N,N-dimethylacetamide may be employed. This is unexpected but it has been found that acrylonitrile polymer articles will not dissolve in a pure or 100 percent N,N-dimethylacetamide bath if the article is under tension while therein. Usually, however, a solvent stretch bath containing from 10 to 85 percent solvent by weight, such as amide, and the like, is satisfactory.
  • the filaments produced in accordance with the preceding wet spinning procedure, and other similar and conventional wet-spinning procedures will fibrillate to a very undesirable extent when subjected to abrasion or normal wear in the form of yarns and fabrics.
  • these filaments are treated in accordance with the present invention, they are substantially non-fibrillating or the degree or amount of fibrillation of the filaments is reduced to a point Where it becomes a matter of insignificance commercially. This is entirely unexpected and the instant invention provides the answer to a magnanimous problem which has plagued the art for a long time.
  • the fibrillation measurement of a filament or fiber is comparative and such measurement is made on a fabric formed from the filaments or fibers.
  • the degree of fibrillation of a fiber or filament is determined on a tricot knit tape and the value obtained is called a tricot rating or TR.
  • the tricot tapes were prepared by spinning approximately six ounces of 16 singles yarn with a twist of 14 turns per inch and then knitting 24 inches of tape on a 14 guage machine with 14 ends in each of the front and back warps. All of the tapes were dyed for one hour at the boil with 2% acetate dye (Eastman Blue GLT).
  • the tapes were pressed with a steam iron and further dried at 60-70 C. Thereafter the tape is flex abraded for cycles on a Stoll abrader or Universal wear tester manufactured by Custom Scientific Instruments, Inc., of Arlington, N. I., using the flexing bar with a 2 lb. tension and /2 lb. weight on the head. Two such abrasions are made on each tape.
  • Measurement of the loss in depth of shades was made with a Photoelectric reflection meter manufactured by the Photovolt Corporation of New York City. Using the green filter, supplied with the instrument, the instrument is first adjusted to read the 72.5% reflectance of a standard porcelain plate, which is also supplied with the instrument. A blue tape, prepared as outlined above, is selected as a secondary standard with a reflectance in the range of 8-1-2%. The exact reflectance is then measured.
  • N,N-dimethylacetamide, N,N-d imethylform- '7 The abraded tape is evaluated by taking two measurements of the reflectance of the unabraded portion and one measurement on each of the abraded portions. The average of the former measurements is subtracted from the average of the latter to give the fibrillation or tricot rating (TR). Therefore, this rating (TR) is the difference of the percent reflectance of the abraded and unabraded portions of the tape.
  • TR rating would be zero.
  • a TR of 1.0-2.0 indicates a filament or fiber which is substantially non-fibrillating.
  • acrylonitrile polymer structures have had a TR rating in the range of about 3.0 to 10.0.
  • Filaments and fibers for certain specific applications in the trade, where fibrillation is not of critical importance have been acceptable with a TR rating of -6.
  • the commercial application of such filaments and fibers has been definitely limited and a great desire in the art has existed for filaments and fibers which are substantially non-fibrillating or which have a TR rating of at least as low as 2.0 and preferably lower. This long felt Want in the art has been accomplished by the present invention.
  • EXAMPLE I In this example a polymer blend was employed. A copolymer (A) was made containing 94% by weight of acrylonitrile in the polymer molecule and 6% by weight of vinyl acetate. A second copolymer (B) was made containing 50% by weight of acrylonitrile in the polymer molecule and 50% by weight of Z-methyl-S-vinylpyridine. Thereafter, a sufiicient amount of copolymer (B) was blended with copolymer (A) to give 6% by weight, based on the weight of the blend, of 2-methyl-5-vinylpyridine in the blend.
  • the polymer blend was then dissolved in N,N-dimethylacetamide to form a spinning solution or dope containing 18% solids.
  • the dope was extruded through a spinneret which was submerged in a coagulating bath containing 50% N,N-dimethylacetamide and 50% water.
  • the orifices in the face of the spinneret were of such size as to give a filament having a final denier of 3.
  • the filaments were removed from the coagulating bath and washed continously with water at a temperature of approximately 100 C. Thereafter the filaments were dried by passing over heated rollers. The dried filaments were cut into staple fibers by means of a cutter.
  • One hundred (100) pounds of the staple fibers were placed in a perforated metal container which in turn was placed in an autoclave.
  • the autoclave was evacuated and saturated steam at approximately 40 p.s.i.g. was introduced into the autoclave until the pressure therein reached 40 p.s.i.g.
  • the saturated steam introduction was stopped and the autoclave was vented to the atmosphere in order to reduce the pressure therein to atmospheric as quickly as possible. Thereafter, the above procedure or cycle was repeated 4 times with the exception that evacuation of the autoclave was eliminated between cycles.
  • the staple fiber was then removed from the autoclave and dried.
  • the staple fiber thus treated was carded on a standard cotton carding machine and spun into yarn in conventional manner.
  • the yarn was then employed in making a tricot knit tape, as outlined hereinbefore and the tape was designated as sample B.
  • a standard sample A was also prepared from the filaments of this example by cutting into staple fibers, carding, spinning into yarn and making a tricot knit tape from said yarn in the same manner as sample B.
  • the standard sample A was not annealed as described in connection with sample Comparative data was obtained and the same is tabulated below:
  • Percent breakdown indicates the percent of the total fibers carded which have a shorter fiber length after cardlng than the fiber length before carding.
  • 2 S.E.P. means Single End Product and it IS the numeriealfignre used to express single and strength and it is obtained by multiplying the strength of the strand in ounces by the yarn number.
  • EXAMPLE II The same procedure as outlined in Example I was followed here using a copolymer containing 94% by weight in the polymer molecule of acrylonitrile and 6% by weight of vinyl acetate. After cutting the dried filaments into staple fibers, one hundred (100) pounds of the fibers were placed in a perforated metal container which in turn was placed in an autoclave. The autoclave was evacuated and saturated steam, at approximately 40 p.s.i.g., introduced therein until the pressure in the autoclave reached 40 p.s.i.g. Upon reaching said pressure, steam introduction was stopped and the autoclave vented to the atmosphere. Thereafter, the above procedure was repeated 3 times with the exception that evacuation of the autoclave was eliminated between cycles. Thereafter the staple fiber was treated as outlined in Example I and the tape was designated as sample D. A standard sample C was also prepared with the exception that it was not annealed, as described in connection with sample D. Comparative data was obtained and the same is tabulated below:
  • a process for producing substantially non-fibrillating filaments comprised of a material selected from the group consisting of acrylonitrile polymers containing at least 70 percent of acrylonitrile and up to 30 percent of other polymerizable mono-olefinic monomers copolymerizable .therewith and blends of said polymers with a polymer of an alkenyl-substituted N-heterocyclic compound, said blends containing from 50 to 80 percent by weight of acrylonitrile, which comprises placing said filaments in a closed chamber while in an oriented and crystalline state, evacuating said chamber, introducing wet steam into said chamber at a pressure in the range of 30 to 60 p.s.i.g.
  • filaments are comprised of an acrylonitrile polymer containing at least 70 percent of acrylonitrile and up to 30 percent of other polymerizable mono-olefinic monomers copolymerizable therewith.
  • the filaments are comprised of a blend of (A), a copolymer containing 94 percent by weight in the polymer molecule of acrylonitrile and 6 percent of vinyl acetate and (B), a copolymer containing 50 percent by weight of acrylonitrile and 50 percent by Weight of a vinylpyridine, said copolymer (B) being employed in sufiicient amount to give 3 to 8 percent by weight of the vinylpyridine, based on the Weight of the blend.
  • filaments are comprised of a copolymer of 94 percent by weight in the polymer molecule of acrylonitrile and 6 percent by weight of vinyl acetate.
  • Filaments produced in accordance with the process of claim 1 which are substantially non-fibrillating and have a tricot rating not greater than 2.0.
  • ments are comprised of a blend of (A) a copolymer containing 90 to 98 percent by weight in the polymer molecule of acrylonitrile and 2 to 10 percent of vinyl acetate and (B) a copolymer of 10 to percent by Weight in the polymer molecule of acrylonitrile and 30 to percent of 2-methyl-5-vinylpyridine, said copolymer (B) be ing employed in sufficient amount to give 3 to 8 percent by Weight of 2-methyl-5-vinylpyridine, based on the Weight of the blend.
  • a process for producing substantially non-fibrillating filaments comprised of a material selected from the group consisting of acrylonitrile polymers containing at least 70 percent of acrylonitrile and up to 30 percent of other polymerizable mono-olefinic monomers copolymerizable therewith and blends of said polymers with a polymer of an alkenyl-substituted N-heterocyclic compound, said blends containing from 50 to 80 percent by weight of acrylonitrile which comprises placing said filaments in a closed chamber while in an oriented and crystalline state, evacuating said chamber, introducing wet steam into the chamber at a pressure in the range of 30 to 60 p.s.i.g. and a temperature in the range of to C.
  • the pressure in the chamber is in the range of 30 to 60 p.s.i.g., immediately venting the chamber to the atmosphere to reduce the pressure therein to approximately 2 p.s.i.g., thereafter repeating said process until the filaments are substantially non-fibrillating, and evacuating the chamber to cool the fibers and remove excess moisture therefrom.
  • the filaments are comprised of a blend of (A), a copolymer containing 94 percent by weight in the polymer molecule of acrylonitrile and 6 percent of vinyl acetate and (B), a copolymer containing 50 percent by weight of acrylonitrile and 50 percent by weight of a vinylpyridine, said copolymer (B) being employed in sufficient amount to give 3 to 8 percent by weight of the vinylpyridine, based on the weight of the blend.
  • filaments are comprised of a copolymer of 94 percent by weight in the polymer molecule of acrylonitrile and 6 percent by weight of vinyl acetate.

Landscapes

  • 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)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
US553714A 1955-12-19 1955-12-19 Process of producing non-fibrillating acrylonitrile polymer filaments with wet steamtreatment and products produced thereby Expired - Lifetime US2920934A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE553539D BE553539A (fr) 1955-12-19
US553714A US2920934A (en) 1955-12-19 1955-12-19 Process of producing non-fibrillating acrylonitrile polymer filaments with wet steamtreatment and products produced thereby
GB35779/56A GB848696A (en) 1955-12-19 1956-11-22 Acrylonitrile polymer filamentary materials and process for treating the same
DE1956C0014134 DE1236125C2 (de) 1955-12-19 1956-12-18 Verfahren zur nachbehandlung von faeden, fadenbuendeln, fasern, filmen oder baendern aus acrylnitrilpolymerisaten bzw. -mischpolymerisaten
CH4086256A CH371550A (de) 1955-12-19 1956-12-19 Verfahren zur Herstellung von nicht zerfasernden Gebilden aus Acrylnitrilpolymeren
FR1170239D FR1170239A (fr) 1955-12-19 1956-12-19 Produits en polyacrylonitrile améliorés

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US553714A US2920934A (en) 1955-12-19 1955-12-19 Process of producing non-fibrillating acrylonitrile polymer filaments with wet steamtreatment and products produced thereby

Publications (1)

Publication Number Publication Date
US2920934A true US2920934A (en) 1960-01-12

Family

ID=24210443

Family Applications (1)

Application Number Title Priority Date Filing Date
US553714A Expired - Lifetime US2920934A (en) 1955-12-19 1955-12-19 Process of producing non-fibrillating acrylonitrile polymer filaments with wet steamtreatment and products produced thereby

Country Status (6)

Country Link
US (1) US2920934A (fr)
BE (1) BE553539A (fr)
CH (1) CH371550A (fr)
DE (1) DE1236125C2 (fr)
FR (1) FR1170239A (fr)
GB (1) GB848696A (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3066006A (en) * 1960-04-29 1962-11-27 American Cyanamid Co Method of processing a tow
US3081516A (en) * 1958-12-05 1963-03-19 Du Pont Acrylonitrile polymer fabrics
US3083073A (en) * 1960-06-23 1963-03-26 American Cyanamid Co Method for the fluid treatment of strands of elongated material
US3089748A (en) * 1960-04-29 1963-05-14 American Cyanamid Co Method of producing polyacrylonitrile filamentary material
US3101245A (en) * 1960-08-18 1963-08-20 American Cyanamid Co Production of polyacrylonitrile fibers
US3118154A (en) * 1961-03-01 1964-01-21 American Cyanamid Co Method for the fluid treatment of strands of elongated material
US3624196A (en) * 1971-01-08 1971-11-30 American Cyanamid Co Stabilization of acrylonitrile fibers to hot-wet creep
US3895908A (en) * 1971-01-28 1975-07-22 Dow Badische Co Autoclaving procedure for textile fibers
WO1981000221A1 (fr) * 1979-07-20 1981-02-05 American Cyanamid Co Procede pour creer une etancheite a la pression

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2185789A (en) * 1936-07-01 1940-01-02 Ig Farbenindustrie Ag Thread and fiber of organic thermoplastic materials and process of producing the same
US2373093A (en) * 1943-04-22 1945-04-10 Bell Telephone Labor Inc Process for inhibiting cracking of polymeric bodies

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR985234A (fr) * 1949-04-26 1951-07-16 American Viscose Corp Procédé et appareil pour le traitement des fils textiles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2185789A (en) * 1936-07-01 1940-01-02 Ig Farbenindustrie Ag Thread and fiber of organic thermoplastic materials and process of producing the same
US2373093A (en) * 1943-04-22 1945-04-10 Bell Telephone Labor Inc Process for inhibiting cracking of polymeric bodies

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3081516A (en) * 1958-12-05 1963-03-19 Du Pont Acrylonitrile polymer fabrics
US3066006A (en) * 1960-04-29 1962-11-27 American Cyanamid Co Method of processing a tow
US3089748A (en) * 1960-04-29 1963-05-14 American Cyanamid Co Method of producing polyacrylonitrile filamentary material
US3083073A (en) * 1960-06-23 1963-03-26 American Cyanamid Co Method for the fluid treatment of strands of elongated material
US3101245A (en) * 1960-08-18 1963-08-20 American Cyanamid Co Production of polyacrylonitrile fibers
US3118154A (en) * 1961-03-01 1964-01-21 American Cyanamid Co Method for the fluid treatment of strands of elongated material
US3624196A (en) * 1971-01-08 1971-11-30 American Cyanamid Co Stabilization of acrylonitrile fibers to hot-wet creep
US3895908A (en) * 1971-01-28 1975-07-22 Dow Badische Co Autoclaving procedure for textile fibers
US4296059A (en) * 1978-08-30 1981-10-20 American Cyanamid Company Pressure sealing process
WO1981000221A1 (fr) * 1979-07-20 1981-02-05 American Cyanamid Co Procede pour creer une etancheite a la pression

Also Published As

Publication number Publication date
DE1236125B (de) 1967-03-09
CH371550A (de) 1963-08-31
GB848696A (en) 1960-09-21
DE1236125C2 (de) 1975-12-04
BE553539A (fr)
FR1170239A (fr) 1959-01-12

Similar Documents

Publication Publication Date Title
US2558735A (en) Method of forming dyed shaped articles from acrylonitrile polymerization products
US3718716A (en) Acrylic fiber and a method for manufacturing the same
US3330896A (en) Method of producing bulky yarn
US2920934A (en) Process of producing non-fibrillating acrylonitrile polymer filaments with wet steamtreatment and products produced thereby
US2888434A (en) Acrylonitrile polymer composition containing the recurring unit of a polymerized bis(2-chloroethyl) vinyl phosphonate
US5458968A (en) Fiber bundles including reversible crimp filaments having improved dyeability
US2692875A (en) Methacrylonitrile-acrylonitrile copolymers and fibers thereof
US3180913A (en) Method for producing high shrinkage fibers
US2631995A (en) Acrylonitrile polymers
US3180845A (en) Method of preparing void free fibers from acrylonitrile polymers
US2901813A (en) Textile material of regenerated cellulose containing a polyacrylamide
US3975486A (en) Process for producing anti-pilling acrylic fiber
US3264705A (en) Process for improving the pill resistance of two-component acrylonitrile polymers
US3828014A (en) High shrinkage threads,yarn and fibers from acrylonitrile polymers
US3936513A (en) Gloss-stabilised fibres and films of acrylonitrile copolymers
US4108845A (en) Highly shrinkable acrylic fibres or filaments
US3083071A (en) Treatment of synthetic fiber tow
US3099517A (en) Process of treating wet-spun acrylonitrile polymer fibers
US3268490A (en) Method of preparing polyacrylonitrile fibers
US3033813A (en) Mixtures of acrylonitrile polymers with polypyrrolidone and fiber made from same
US3885013A (en) Method for producing acrylic synthetic fibers
US3624195A (en) Process for the preparation of acrylic manmade fiber
US3104934A (en) Polypyrrolidone treatment of polyacrylonitrile gel fibers and the product thereof
US3065042A (en) Modification of crimp of composite acrylic fibers
US3507823A (en) Art of preparing dyeable polyacrylonitrile products