US3402231A - Process for preparing synthetic fibers for paper products - Google Patents

Process for preparing synthetic fibers for paper products Download PDF

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Publication number
US3402231A
US3402231A US369225A US36922564A US3402231A US 3402231 A US3402231 A US 3402231A US 369225 A US369225 A US 369225A US 36922564 A US36922564 A US 36922564A US 3402231 A US3402231 A US 3402231A
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Prior art keywords
polymer
slurry
paper
acrylonitrile
percent
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Expired - Lifetime
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US369225A
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English (en)
Inventor
George D Bynum
Gerd R Baur
Jr Byrd T Thompson
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Monsanto Co
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Monsanto Co
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Publication date
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Priority to US369225A priority Critical patent/US3402231A/en
Priority to US385177A priority patent/US3309734A/en
Priority to LU48651A priority patent/LU48651A1/xx
Priority to BE664276A priority patent/BE664276A/xx
Priority to IL23579A priority patent/IL23579A/xx
Priority to CH713265A priority patent/CH489625A/de
Priority to NL6506516A priority patent/NL6506516A/xx
Priority to GB21641/65A priority patent/GB1090478A/en
Priority to FR18013A priority patent/FR1464605A/fr
Priority to DE1965M0065325 priority patent/DE1494690A1/de
Application granted granted Critical
Publication of US3402231A publication Critical patent/US3402231A/en
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H5/00—Special paper or cardboard not otherwise provided for
    • D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
    • D21H5/20—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of organic non-cellulosic fibres too short for spinning, with or without cellulose fibres
    • D21H5/205—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of organic non-cellulosic fibres too short for spinning, with or without cellulose fibres acrylic fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/345—Extrusion nozzles comprising two or more adjacently arranged ports, for simultaneously extruding multiple strands, e.g. for pelletising
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/11—Flash-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D01D5/423—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by fibrillation of films or filaments
    • 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
    • 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
    • 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
    • D01F6/44—Monocomponent 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
    • D01F6/54—Monocomponent 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/18—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylonitriles
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/47—Processes of splitting film, webs or sheets

Definitions

  • PRO 1555 FOR PREPARING SYNTHETIC FIBERS FOR PAPER PRODUCTS Filed May 21, 1964 2 Sheets-:Sheet 2 I00- E 90- D: Q) 80- as k E 0... 0') 50...
  • the dispersion is heated in a pressure vessel to form a viscous polymer melt which is extruded into a restricted area wherein a high velocity stream of steam is directed transverse to the travel of the emerging extrudate imparting a stretch thereto.
  • the filamenary materials are comprised of loosely bonded fibrils which can be separated easily by beating or other abrasive forces.
  • the present invention relates to the production of shaped articles from acrylonitrile polymers. More particularly, the invention relates to a continuous process for preparing novel cross sectional fibers suitable for paper products which are comprised of a multitude of loosely bonded fibrils by the use of a non-solvent impregnant.
  • Filamentary materials are conventionally produced from acrylonitrile polymer by processes generally referred to by the art as wet spinning and dry spinning.
  • the basic method is the same.
  • the dry polymer is dissolved in a suitable organic solvent to form a viscous spinning solution suitable for extrusion through an orifice.
  • the extruded polymer solu-v tion is converted to solid filaments by removing the solvent.
  • the wet spinning process this is accomplished by extruding into a liquid bath in which the solvent dissolves but in which the polymer is insoluble.
  • a solid is achieved upon volatilization of the solvent. In both of these processes the loss of the solvent or the process employed to obtain recovery thereof is expensive.
  • the filaments must be highly fibrous and actively interlock when beaten to be suitable for the manufacture of synthetic paper products and the like. From the discussion above it is evident that a process to economically prepare fibrous materials from acrylonitrile polymer for the paper industry which exhibit exceptional fibrillating properties, whereby the cost of converting the fibers to a finished product is reduced, would be highly desirable.
  • Another object of the present invention is to provide a continuous process for producing shaped articles from a slurry of acrylonitrile polymer mixed with water and a suspension agent.
  • Still another object of the present invention is to provide a novel filament comprised of a multitude of loosely bonded fibrils coextensively aligned with the longitudinal axis of the fiber.
  • a further object of this invention is to produce economically acrylonitrile polymer filaments having outstanding properties for use in making paper and other non-woven products.
  • the objects of this invention have been realized by preparing a slurry of acrylonitrile polymers with water which preferably contains a small amount of a water soluble cellulose derivative such as sodium carboxymethyl cellulose (SCMS) which serves as a suspension agent and also improves the fibrillating characteristics of the product, continuously pumping the slurry through a heat exchanger while under pressure to convert the slurry to a viscous melt in a heated pressure vessel and extruding the melt through a jet into a stream of steam in a restricted stretch zone wherein a fibrous material is developed from the extruded melt and simultaneously stretched.
  • the steam in the stretch zone provides the tempertaure, humidity, and pressure necessary to form a fibrous material having novel properties.
  • viscous melt dispersed polymer particles suspended in the non-solvent solution when the slurry is subjected to suitable heat and pressure.
  • the system pressure is determined by the temperature, flow rate, slurry solids content, and the size and number of holes in the jet.
  • the polymer employed in this invention may be polyacrylonitrile, copolymers of acrylonitrile, including binary and ternary polymers containing at least percent by weight of acrylonitrile in the polymer molecule, or a blend comprising polyacrylonitrile or copolymers comprising acrylonitrile with from 2 to 50 percent of another polymeric material, the blend having an overall polymerized acrylonitrile content of at least 80 percent by weight.
  • the preferred polymers employed in the instant invention are those containing at least 80 percent of acrylonitrile, generally recognized as the fiber-forming acrylonitrile polymers, it will be understood that the invention is likewise applicable to polymers containing less than 80 percent acrylonitrile.
  • Suitable mono-olefinic monomers include acrylic, alphachloroacrylic and methacrylic acids; the acrylates, such as methylmethacrylate, ethylmethacrylate, butylmethacrylate, methoxymethyl methacrylate, beta-chloroethyl methacrylate, and the corresponding esters of acrylic and alphachloroacrylic acids; vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, 1-chloro-l-bromo-ethylene; methacrylonitrile; acrylamide and methacrylamide; alphachloroacrylamide; or monoalkyl substitution products thereof; methylvinyl ketone; vinyl carboxylates, Such as vinyl acetate, vinyl chloroacetate, vinyl
  • the polymer may be a ternary or higher interpolymer, for example products obtained by the interpolymerization of acrylonitrile and two or more of any of the monomers, other than acrylonitrile, enumerated above. More specifically, and preferably the ternary polymer comprises acrylonitrile, vinyl acetate, and styrene. For example, the ternary polymer which contains from 80 to 98 percent of acrylonitrile, from 1 to percent of styrene, and from 1 to 18 percent of another monomer such as vinyl acetate.
  • the polymerwater-SCMC slurry may contain from about 2 to 30 percent polymer solids, and preferably contains from 6 to 18 percent polymer. Lower concentrations of polymer may be used with acceptable results, but it is not economically desirable since greater quantities of slurry must be pumped and heated to produce the same quantity of paper. Polymer concentrations in excess of 30 percent are undesirable since the mixture assumes the properties of a wet polymer cake rather than a flowing slurry, and can not be pumped, but must be moved with screw conveyors and the like. Furthermore, the quality of the fiber product is generally poorer when the slurry solids are less than 6 percent or in excess of 18 percent.
  • the slurry may also contain from 0 to 20 percent sodium carboxymethyl cellulose (SCMC) based on the weight of polymer, and preferably contains from 1.0 to 5.0 percent. Concentrations of SCMC at the preferred level promotes longitudinal splitting or separation of the fibrils. When using SCMC concentrations of less than about 1.0 percent the fibrous product of the invention does not possess the high fibrillating characteristics which are desired. At SCMC concentrations greater than 5.0 percent, the fibrous product is slubby or includes small hard nodules which are undesirable for use in paper making.
  • SCMC sodium carboxymethyl cellulose
  • the polymer slurry is moved with a positive displacement pump through a first heat exchanger wherein the temperature of the slurry is increased to about C., which is less than the temperature required to form the polymer melt.
  • the hot slurry is then passed through a second exchanger wherein it has a short dwell time and is heated to about 190 to 205 C., but preferably 201 to 203 C. to form the polymer melt which is then extruded. It is desirable for optimum results that the slurry be heated in excess of 200 C., but that the exposure time at this temperature be limited to a few seconds (usually less than one minute) to prevent decomposition of the acrylonitrile polymers.
  • a two phase system consisting of a lower polymer melt layer and an upper water layer is formed.
  • the polymer melt phase is comprised of a viscous mass of polymer and water, while the water phase contains very little polymer. Both phases are extruded simultaneously through the vertically positioned jet orifices.
  • novel filaments produced in accordance with the present invention are comprised of a multitude of very fine fibrils coextensively aligned with the axis thereof and are characterized by highly porous cross-sections. On an average the pores account for approximately 60 percent of the cross-sectional area.
  • the fibrils are intermittently connected to each other to form a loosely constructed strand. This condition is imparted to the strands by the process employed in accordance with the invention as described hereafter.
  • strands having unusual crosssectional constructions characterized by large holes and fissures are developed. The larger holes are caused by the escapement of the water content of the melt flashing to steam upon entering the low pressure area.
  • the strands are formed and stretched by the force imposed on the strands from the stream of steam which is directed transversely against the extruded strands. This is accomplished by extruding into a restricted area and drafting the newly formed strands from the orifices in a stretch zone directed radially outwardly from said orifices.
  • the cavities or fissures are further elongated in the stretch zone produced by the high velocity steam passing through the restricted passageway.
  • the loosely bonded condition of the strands is believed to be caused by the combination of the escaping steam and the application of steam on the emerging strands in the restricted area at the face of the jet.
  • This position is substantiated by the fact that a melt extruded in the absence of the stream of steam is comprised of a filmy cellular substance.
  • Such a material has very little tendency to fibrillate and, accordingly, is not suitable for making paper products. Since fibrillous materials can be more readily processed for utilization in the paper making industry, the unusual tendency of the strands discussed herein to fibrillate enhances substantially the use thereof for making synthetic paper products.
  • FIGURE 1 is a microscopic view at about two power magnification of the strand in which a portion thereof has been scraped to separate the fibrils;
  • FIGURE 2 is a microscopic view at about two power magnification of a broken strand illustrating the separating propensity of the fibrils;
  • FIGURE 3 is a microscopic view at about ten power magnification of a cross-section illustrating the fibrillated structure of the strand.
  • FIGURE 4 is a graphic illustration of the physical properties shown plotted as ordinates versus percent polymer solids plotted as abscissas of each slurry beaten in a conventional beater for 60 minutes and formed into handsheets.
  • the strands or filaments of this invention are essentially continuous in nature except for occasional disruptions in their continuity which may be caused by the escapement of the non-solvent impregnant from the heated pressure vessel.
  • the tow bundle comprising the several strands can be produced in endless lengths.
  • the impregnant is flashed off at intermittent intervals randomly from the several orifices to interrupt extrusion of the filament-forming polymeric material. Because of the disrupted ends, which become entangled in the tow bundle, the tow is preferably collected in a container, but may be collected on a bobbin if desired. Thereafter, the tow can be converted into staple fiber for subsequent processing.
  • FIGURE 1 a filament in which a segment thereof has been subjected to a longitudinal scraping action is shown in FIGURE 1.
  • the bond be .tween the fibrils of strand 12 can be broken to separate the individual fibrils by scraping the thumbnail along the strand several times.
  • Another method of demonstrating the looseness of the bonds between the fibrils can be performed by breaking a filament and observing the spreading propensity of the several fibrils 14 as illustrated in FIGURE 2.
  • the filamentary materials of this invention are manufactured predominantly for utilization in the production of paper and non-woven materials. When converted into pulp on commercial paper-pulping machinery, these fila- .ments produce slurries which will form wate'rleaves having a greater tenacity than is required to permit the necessary processing thereof. Generally the filaments are not suitable for making a wide variety of textile products because of the rough and porous condition exhibited by these filaments.
  • FIGURE 3 is illustrative of the number of cracks and fissures running lengthwise the filaments.
  • the material extruded from a single hole or orifice forms a filament which may be characterized by a wide denier and strength variations. The denier may be from 40 to 80 but is preferably about 44. Average physical properties of the 44 denier filaments has been discovered to be as follows: tenacity 2.25 grams per denier; elongation 10 percent; and modulus 53.5.
  • the filaments may be cut into staple, suspended in water and beaten in a standard paper beater whereby a high degree of fibrillation will be developed.
  • the beaten 'fiber may then be laid on a screen and a desirable sheet will result therefrom.
  • Quality of the fibrous material may be tested by preparing paper sample sheets in the manner described hereinafter.
  • a collection of tow from the extruding nozzle is cut-into approximately one half inch staple lengths.
  • About 150 grams of the staple and liters of water are placed in a container and slurried to form a water slurry containing 0.75 percent fiber solids.
  • the slurry is transferred to a 1 /2 1b.
  • the degree of fibrillation can be estimated from time to time by a visual examination of a removed sample.
  • the sample is transferred to a Nobel and Wood Sheeting Machine for forming 2.5 gram hand sheets 8 x 8 inches and dried. After the sheet has been pressed and dried completely, it is subjected to a series of physical tests to determine the strength of the finished product. These tests include the Mullins burst test and the Elmendorf tear test. A 1 x 6 inch strip is broken on the Scott Model DH tensile tester to determine the tensile strength of the sample. Results obtained from these tests are the equivalent of 37 pound basis weight paper. 7
  • the cut staple may be processed dry to form a soft batt.
  • the individual fibers are subjected to a longitudinal scraping action either by carding or processing in the Rando Webber to develop a fibrillous batt which can be matted to form a soft batt.
  • Such a batt may be utilized as a padding for upholstery applications, filter media, and the like. Utilization thereof is enhanced because of the hydrophobic properties possessed by batting produced from the filaments of this invention and their ability to resist the action of certain chemicals.
  • Example I 25 parts of a copolymer comprised of 93% acrylonitrile and 7% vinyl acetate and having an average molecular weight of 110,000 was slurried in 300 parts of a water solution containing 0.50 parts of sodium carboxymethylcellulose to produce a slurry of 6.2% polymer solids. The slurry was pumped under pressure through a first heat exchanger wherein the temperature was elevated to C., and thereafter through a second heat exchanger wherein the temperature was further increased to 202 C. to form a two phase polymer melt-water system.
  • the two phase system was then extruded horizontally through a vertical spinnerette containing 27 holes 0.015 inches in diameter into a high velocity stream of steam directed vertically downward at approximately 100 p.s.i.g. where the filaments were solidified and stretched.
  • the fibrous product was produced at a rate of 2000 feet per minute and collected in a drum as a continuous tow.
  • the fibrous tow was cut to /2 inch staple and processed into sample sheets of paper as described above.
  • the physical properties of paper sheets obtained at 10 minute intervals over beating times of 40 to 90 minutes are shown in Table I.
  • Example II A slurry of the composition described in Example I was extruded at a temperature of C.
  • the physical properties of the handsheets made from these fibers after a beating time of 60 minutes are listed in Table II below and compared with values obtained for Example I.
  • Example III The process as described in Example I was repeated with five different polymer slurry concentrations as shown in Table III. Handsheets of paper made from each of the conditions were evaluated according to the procedure described above, and had physical properties as shown in Table III.
  • an important aspect of the invention is based on the discovery of producing continuous filaments more economically by utilizing a two phase system consisting of a polymer melt phase comprised of a lower polymer melt layer and an upper water layer.
  • the novel filamentary materials formed from the disclosed blends of polymers dispersed in a non-solvent may be fibrillated more easily and to a greater extent than filaments produced theretofore to thereby reduce the cost thereof.
  • the products made from the filamentary materials of this invention have a high resistance to bursting and tearing both in the wet and dry state. Another important feature of the products is their inherent ability to resist the action of certain chemicals. While the products may be made solely from fibers of the polymer blends illustrated herein, it will be appreciated that other fibrillatable fibers including synthetic, artificial and natural fibers may be combined therewith to manufacture satisfactory sheet-like materials.
  • the fibers of the present invention are compatible with natural cellulosic fibers over a wide range of proportions to obtain paper having improved physical properties.
  • a process for producing continuous synthetic filaments each comprised of randomly interconnected fiber elements suitable for utilization in the manufacture of paper products comprising:
  • a process in accordance with claim 5 wherein the sodium carboxymethyl cellulose comprises from 6% to 18% of the polymer solids.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Paper (AREA)
US369225A 1964-05-21 1964-05-21 Process for preparing synthetic fibers for paper products Expired - Lifetime US3402231A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US369225A US3402231A (en) 1964-05-21 1964-05-21 Process for preparing synthetic fibers for paper products
US385177A US3309734A (en) 1964-05-21 1964-07-27 Spinnerette
BE664276A BE664276A (de) 1964-05-21 1965-05-21
IL23579A IL23579A (en) 1964-05-21 1965-05-21 Process and apparatus for preparing synthetic fibers
LU48651A LU48651A1 (de) 1964-05-21 1965-05-21
CH713265A CH489625A (de) 1964-05-21 1965-05-21 Endlose synthetische Filamente aus Acrylnitrilpolymeren und kontinuierliches Verfahren zu ihrer Herstellung sowie Vorrichtung zur Ausführung des Verfahrens und Verwendung der Filamente zur Herstellung von nicht textilen Flächengebilden
NL6506516A NL6506516A (de) 1964-05-21 1965-05-21
GB21641/65A GB1090478A (en) 1964-05-21 1965-05-21 Process and apparatus for preparing synthetic filamentary structures
FR18013A FR1464605A (fr) 1964-05-21 1965-05-21 Procédé et appareil de fabrication de fibres synthétiques
DE1965M0065325 DE1494690A1 (de) 1964-05-21 1965-05-21 Synthetische Endlosfaeden zur Herstellung von Papier und anderen Vliesprodukten,sowie Verfahren und Vorrichtung zur Herstellung dieser Faeden

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US369225A US3402231A (en) 1964-05-21 1964-05-21 Process for preparing synthetic fibers for paper products
US385177A US3309734A (en) 1964-05-21 1964-07-27 Spinnerette

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US3402231A true US3402231A (en) 1968-09-17

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US369225A Expired - Lifetime US3402231A (en) 1964-05-21 1964-05-21 Process for preparing synthetic fibers for paper products
US385177A Expired - Lifetime US3309734A (en) 1964-05-21 1964-07-27 Spinnerette

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US385177A Expired - Lifetime US3309734A (en) 1964-05-21 1964-07-27 Spinnerette

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US (2) US3402231A (de)
BE (1) BE664276A (de)
CH (1) CH489625A (de)
DE (1) DE1494690A1 (de)
GB (1) GB1090478A (de)
IL (1) IL23579A (de)
LU (1) LU48651A1 (de)
NL (1) NL6506516A (de)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3885014A (en) * 1971-06-01 1975-05-20 Oji Yuka Goseishi Kk Production of fine fiber mass
US3907633A (en) * 1973-06-18 1975-09-23 Crown Zellerbach Corp Process of making polyolefin fibers
US3914354A (en) * 1970-09-25 1975-10-21 Oki Yuka Goeishi Kenkyujo Kk Process for producing fine fibrous structures
US3920508A (en) * 1971-10-12 1975-11-18 Crown Zellerbach Corp Polyolefin pulp and process for producing same
US3920507A (en) * 1972-10-05 1975-11-18 Crown Zellerbach Corp Process of making polyolefin fibers
US3997647A (en) * 1973-10-01 1976-12-14 Kimberly-Clark Corporation Method of making filaments and webs of chemically modified cellulose fibers
US4054625A (en) * 1972-08-30 1977-10-18 Crown Zellerbach Corporation Process for making fibers
US4256111A (en) * 1973-10-01 1981-03-17 Kimberly-Clark Corporation Filaments of chemically modified cellulose fibers and webs and products formed therefrom
US4271056A (en) * 1979-09-17 1981-06-02 American Cyanamid Company Hydrophilic acrylonitrile polymers for melt-spinning
US4392861A (en) * 1980-10-14 1983-07-12 Johnson & Johnson Baby Products Company Two-ply fibrous facing material
US4425126A (en) 1979-12-28 1984-01-10 Johnson & Johnson Baby Products Company Fibrous material and method of making the same using thermoplastic synthetic wood pulp fibers
EP0265762A1 (de) * 1986-10-14 1988-05-04 American Cyanamid Company Fibrillierte Fasern und daraus hergestellte Artikel
US5219501A (en) * 1990-07-11 1993-06-15 Korea Institute Of Science And Technology Process for the production of acrylic short fibers without spinning
US5589264A (en) * 1992-10-01 1996-12-31 Korea Institute Of Science And Technology Unspun acrylic staple fibers
GB2359043A (en) * 1999-12-10 2001-08-15 Seitzschenk Filtersystems Gmbh Production of filtration-active fibres
GB2370248A (en) * 1999-12-10 2002-06-26 Seitzschenk Filtersystems Gmbh Production of filtration-active fibres

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1469501A1 (de) * 1964-12-24 1969-01-23 Glanzstoff Ag Verfahren zur Herstellung von filzartigen Flaechengebilden
US3417426A (en) * 1965-09-17 1968-12-24 Petro Tex Chem Corp Apparatus for separating a polymer from a solvent
US3543332A (en) * 1966-09-21 1970-12-01 Celanese Corp Apparatus for producing fibrous structures
US3774387A (en) * 1970-09-11 1973-11-27 Du Pont Hydrophilic textile products
BE787033A (de) * 1971-08-06 1973-02-01 Solvay
BE790107A (fr) * 1971-10-14 1973-04-13 Du Pont Compositions de polymeres d'acrylonitrile faconnables a l'etat fondu, procede pour leur preparation, et filaments et pellicules produits a partir d'elles
DE2254898C3 (de) * 1971-11-22 1985-08-29 Mitsubishi Chemical Industries Ltd., Tokio/Tokyo Verfahren zur Herstellung von Fasern und Verwendung dieser Fasern
US4094948A (en) * 1972-10-02 1978-06-13 E. I. Du Pont De Nemours And Company Improved acrylonitrile polymer spinning process
NL171825C (nl) * 1973-01-22 1983-05-16 Stamicarbon Werkwijze voor het bereiden van polymeervezels.
IT1001664B (it) * 1973-11-08 1976-04-30 Sir Soc Italiana Resine Spa Prodotto microfibroso adatto ad es sere impiegato nella produzione di carte sintetiche e relativo procedi mento di ppreparazione
US3942921A (en) * 1974-06-12 1976-03-09 The Quaker Oats Company Die and air nozzle
US4582473A (en) * 1984-06-25 1986-04-15 Usm Corporation Polymer pelletizer
US4692965A (en) * 1985-03-25 1987-09-15 Stephenson Fred W Shrimp processing method and device
CN103290500B (zh) * 2013-07-04 2016-02-24 苏州祺尚纺织有限公司 一种熔融纺织结构
ES2547755B1 (es) * 2015-06-25 2016-06-16 Manuel Torres Martínez Cabezal de extrusión para la generación de filamentos, instalación y procedimiento de extrusión que emplean dicho cabezal de extrusión
EP3600856B1 (de) * 2017-03-24 2023-06-07 British American Tobacco (Investments) Limited Verfahren und vorrichtung zur herstellung von rohren aus fasermaterial
CN108103593B (zh) * 2018-02-09 2020-07-24 陕西天策新材料科技有限公司 一种制备中间相沥青基碳纤维原丝的喷丝板及方法
CN116024673A (zh) * 2022-11-28 2023-04-28 江苏诚业化纤科技有限公司 一种新型细旦多孔纤维锦纶生产工艺

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2140921A (en) * 1934-12-08 1938-12-20 Ig Farbenindustrie Ag Manufacture of solutions of a polymerized vinyl compound
US2437263A (en) * 1948-03-09 Fred w
US2585499A (en) * 1948-07-29 1952-02-12 Du Pont Production of shaped articles from acrylonitrile polymers
US2585444A (en) * 1948-07-29 1952-02-12 Du Pont Preparation of shaped articles from acrylonitrile polymers
US2626214A (en) * 1949-06-14 1953-01-20 C H Dexter & Sons Inc Paper from long synthetic fibers and partially water soluble sodium carboxymethylcellulose and method
US2689199A (en) * 1950-06-27 1954-09-14 Mario R Pesce Nonwoven fabrics
US2810646A (en) * 1953-09-17 1957-10-22 American Cyanamid Co Water-laid webs comprising water-fibrillated, wet-spun filaments of an acrylonitrile polymer and method of producing them
US2840447A (en) * 1954-04-28 1958-06-24 Du Pont Process for preparing filaments from dispersions containing graft polymers obtained from ethylenically unsaturated monomers
US2875473A (en) * 1955-08-10 1959-03-03 Rayonier Inc Process of forming solid particulate hydroxyethoxycellulose
US2999789A (en) * 1957-04-02 1961-09-12 W S Hodgkinson & Company Ltd Paper making
US3042970A (en) * 1961-08-14 1962-07-10 American Cyanamid Co Particulation of polymer by extruding a solution thereof into a liquid stream of fluid
US3047456A (en) * 1959-08-10 1962-07-31 Monsanto Chemicals Manufacture of paper products from fibers wet spun from polymer blends
US3081519A (en) * 1962-01-31 1963-03-19 Fibrillated strand
US3110642A (en) * 1960-09-09 1963-11-12 Eastman Kodak Co Method of producing a fibrous product from extruded organic thermoplastic filaments
US3242120A (en) * 1960-03-22 1966-03-22 Du Pont Self-supporting gel shaped structures
US3287304A (en) * 1963-01-03 1966-11-22 Asahi Chemical Ind Acrylonitrile copolymers and compositions

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US204227A (en) * 1878-05-28 John w
US1419090A (en) * 1921-08-12 1922-06-06 Western Electric Co Covering machine
BE374102A (de) * 1929-11-07
US2075867A (en) * 1935-01-16 1937-04-06 Sampel Henri Cement gun nozzle
US2286922A (en) * 1939-04-08 1942-06-16 Us Rubber Co Extrusion machine
US2776119A (en) * 1953-04-22 1957-01-01 Emulsol Egg Products Corp Apparatus for producing dressing
US3208829A (en) * 1960-09-28 1965-09-28 American Cyanamid Co Apparatus for the segmentation of polymer solutions
US3147955A (en) * 1960-08-15 1964-09-08 Union Carbide Corp Apparatus for dispersing finely-divided solids in liquids
US3152362A (en) * 1962-08-22 1964-10-13 Monsanto Co Spinning apparatus

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2437263A (en) * 1948-03-09 Fred w
US2140921A (en) * 1934-12-08 1938-12-20 Ig Farbenindustrie Ag Manufacture of solutions of a polymerized vinyl compound
US2585499A (en) * 1948-07-29 1952-02-12 Du Pont Production of shaped articles from acrylonitrile polymers
US2585444A (en) * 1948-07-29 1952-02-12 Du Pont Preparation of shaped articles from acrylonitrile polymers
US2626214A (en) * 1949-06-14 1953-01-20 C H Dexter & Sons Inc Paper from long synthetic fibers and partially water soluble sodium carboxymethylcellulose and method
US2689199A (en) * 1950-06-27 1954-09-14 Mario R Pesce Nonwoven fabrics
US2810646A (en) * 1953-09-17 1957-10-22 American Cyanamid Co Water-laid webs comprising water-fibrillated, wet-spun filaments of an acrylonitrile polymer and method of producing them
US2840447A (en) * 1954-04-28 1958-06-24 Du Pont Process for preparing filaments from dispersions containing graft polymers obtained from ethylenically unsaturated monomers
US2875473A (en) * 1955-08-10 1959-03-03 Rayonier Inc Process of forming solid particulate hydroxyethoxycellulose
US2999789A (en) * 1957-04-02 1961-09-12 W S Hodgkinson & Company Ltd Paper making
US3047456A (en) * 1959-08-10 1962-07-31 Monsanto Chemicals Manufacture of paper products from fibers wet spun from polymer blends
US3242120A (en) * 1960-03-22 1966-03-22 Du Pont Self-supporting gel shaped structures
US3110642A (en) * 1960-09-09 1963-11-12 Eastman Kodak Co Method of producing a fibrous product from extruded organic thermoplastic filaments
US3042970A (en) * 1961-08-14 1962-07-10 American Cyanamid Co Particulation of polymer by extruding a solution thereof into a liquid stream of fluid
US3081519A (en) * 1962-01-31 1963-03-19 Fibrillated strand
US3287304A (en) * 1963-01-03 1966-11-22 Asahi Chemical Ind Acrylonitrile copolymers and compositions

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3914354A (en) * 1970-09-25 1975-10-21 Oki Yuka Goeishi Kenkyujo Kk Process for producing fine fibrous structures
US3885014A (en) * 1971-06-01 1975-05-20 Oji Yuka Goseishi Kk Production of fine fiber mass
US3920508A (en) * 1971-10-12 1975-11-18 Crown Zellerbach Corp Polyolefin pulp and process for producing same
US4054625A (en) * 1972-08-30 1977-10-18 Crown Zellerbach Corporation Process for making fibers
US3920507A (en) * 1972-10-05 1975-11-18 Crown Zellerbach Corp Process of making polyolefin fibers
US3907633A (en) * 1973-06-18 1975-09-23 Crown Zellerbach Corp Process of making polyolefin fibers
US3997647A (en) * 1973-10-01 1976-12-14 Kimberly-Clark Corporation Method of making filaments and webs of chemically modified cellulose fibers
US4256111A (en) * 1973-10-01 1981-03-17 Kimberly-Clark Corporation Filaments of chemically modified cellulose fibers and webs and products formed therefrom
US4271056A (en) * 1979-09-17 1981-06-02 American Cyanamid Company Hydrophilic acrylonitrile polymers for melt-spinning
US4425126A (en) 1979-12-28 1984-01-10 Johnson & Johnson Baby Products Company Fibrous material and method of making the same using thermoplastic synthetic wood pulp fibers
US4392861A (en) * 1980-10-14 1983-07-12 Johnson & Johnson Baby Products Company Two-ply fibrous facing material
EP0265762A1 (de) * 1986-10-14 1988-05-04 American Cyanamid Company Fibrillierte Fasern und daraus hergestellte Artikel
US5219501A (en) * 1990-07-11 1993-06-15 Korea Institute Of Science And Technology Process for the production of acrylic short fibers without spinning
US5589264A (en) * 1992-10-01 1996-12-31 Korea Institute Of Science And Technology Unspun acrylic staple fibers
GB2359043A (en) * 1999-12-10 2001-08-15 Seitzschenk Filtersystems Gmbh Production of filtration-active fibres
DE19959532C1 (de) * 1999-12-10 2001-10-04 Seitz Schenk Filtersystems Gmb Verfahren und Vorrichtung zur Herstellung von filtrationsaktiven Fasern
GB2370248A (en) * 1999-12-10 2002-06-26 Seitzschenk Filtersystems Gmbh Production of filtration-active fibres
GB2359043B (en) * 1999-12-10 2002-12-18 Seitzschenk Filtersystems Gmbh Process for producing filtration-active fibers

Also Published As

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DE1494690A1 (de) 1970-03-26
LU48651A1 (de) 1965-11-22
US3309734A (en) 1967-03-21
BE664276A (de) 1965-11-22
GB1090478A (en) 1967-11-08
NL6506516A (de) 1965-11-22
CH489625A (de) 1970-04-30
IL23579A (en) 1969-01-29

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