EP0310800A1 - Procédé pour la fabrication de fils d'alcool polyvinylique - Google Patents

Procédé pour la fabrication de fils d'alcool polyvinylique Download PDF

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Publication number
EP0310800A1
EP0310800A1 EP88113740A EP88113740A EP0310800A1 EP 0310800 A1 EP0310800 A1 EP 0310800A1 EP 88113740 A EP88113740 A EP 88113740A EP 88113740 A EP88113740 A EP 88113740A EP 0310800 A1 EP0310800 A1 EP 0310800A1
Authority
EP
European Patent Office
Prior art keywords
spinneret
polyvinyl alcohol
chosen
length
spinning
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.)
Granted
Application number
EP88113740A
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German (de)
English (en)
Other versions
EP0310800B1 (fr
Inventor
Jan Dr. Smook
Gerardus Johannes Hendricus Vos
Johannes Anthony Dr. Juijn
Theodorus Johannes Van Hees
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.)
Akzo NV
Original Assignee
Akzo NV
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Filing date
Publication date
Priority claimed from DE19883826621 external-priority patent/DE3826621A1/de
Application filed by Akzo NV filed Critical Akzo NV
Priority to AT88113740T priority Critical patent/ATE69271T1/de
Publication of EP0310800A1 publication Critical patent/EP0310800A1/fr
Application granted granted Critical
Publication of EP0310800B1 publication Critical patent/EP0310800B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • D01F6/08—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 halogenated hydrocarbons
    • D01F6/10—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 halogenated hydrocarbons from polyvinyl chloride or polyvinylidene chloride
    • 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
    • D01F6/14—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 alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • 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

Definitions

  • the invention relates to a method for producing polyvinyl alcohol yarns with a viscometric average molecular weight M v between 105 and 4.105, in which a solution of polyvinyl alcohol in an organic solvent is spun from a spinneret through an air gap or a gap with an inert gas into a coagulation bath and then stretched.
  • a solution of polyvinyl alcohol in an organic solvent is spun from a spinneret through an air gap or a gap with an inert gas into a coagulation bath and then stretched.
  • the present invention now provides a method whereby yarns of polyvinyl alcohol with high tensile strength and other favorable physical properties can be obtained from polymer solutions with a much higher concentration of polyvinyl alcohol.
  • the invention consists in that, in a procedure of the known type mentioned at the outset, the length of the spinneret channels in the direction of the spinning solution flow is at least five times as large as their diameter and the concentration C in% by weight of the polymer solution is chosen such that C ⁇ 30 - 5.10 ⁇ 5 M v is.
  • the yarns produced using this method of operation not only show high tensile strength, but also high water resistance.
  • the mechanical properties also largely correspond to the properties specified in the aforementioned European patent application, but are already obtained at lower stretching ratios than are mentioned therein.
  • spinnerets in which the length of the spinneret channels is at least five times as large as their diameter.
  • a preferred embodiment is that a spinneret is selected, the spinneret channels of which have a constant diameter over the entire length.
  • the length / diameter ratio of the spinneret channels is chosen to be greater than 5
  • the length / diameter ratio of the spinneret channels is between 5 and 50.
  • the best results are obtained if the length / diameter ratio is chosen between 20 and 40.
  • the nozzle plates can consist of polyether ether ketone or polyphenylene sulfide, each of which contains e.g. 30 wt .-% carbon fibers are reinforced.
  • nozzle capillaries with the claimed large length / diameter ratio can be drilled particularly easily. The gel is unable to adhere to the surface of such spinnerets, so that a particularly good spinning behavior can be observed.
  • a method of operation is preferred in which, on the outlet side of the spinneret, the adjoining spinning mass flows leave the spinneret channels with respect to the intermediate surface of the spinneret plate at different levels.
  • Such a mode of operation can only be realized through a special design of the spinneret.
  • Possible constructions include both an embodiment in which the spinneret channels protrude from the surface of the spinneret plate, i.e. form projections, and an embodiment in which the spinneret ends are at the same or almost the same level as the surface of the spinneret plate, with the proviso that around a recess is provided around the spinneret channel ends.
  • the spinneret channel ends are preferably frustoconical. This prevents the spinning mass flows from coming into contact with the surface of the spinneret plate after leaving the spinneret channels.
  • various, preferably organic, solvents can be used to dissolve the polyvinyl alcohol.
  • suitable polyhydric alcohols are ethylene glycol, glycerin and / or 1,3-propanediol.
  • DMSO dimethyl sulfoxide
  • N-methylpyrrolidone N-methylpyrrolidone
  • the temperature at which the solution of polyvinyl alcohol can be spun is generally between 20 and 250 ° C and depends in part on the type of solvent used or the mixture of solvents. If a polyhydric alcohol is used as the solvent, the spinning temperature is generally chosen between 175 and 190 ° C or higher. When using dimethyl sulfoxide, the spinning temperature is usually not more than 80 ° C, although temperatures of 120 to 150 ° C can be used. The temperature of the coagulation bath will usually set to ambient temperature or lower.
  • the solution of polyvinyl alcohol passes through an air gap or a gap with an inert gas before it is coagulated in the coagulation bath.
  • the distance between the outlet openings of the spinneret and the coagulation bath is generally chosen between 2 and 200 mm and preferably between 3 and 20 mm. With a shorter distance than 2 mm, the process control is extremely complicated, while with a larger distance than 200 mm, thread breaks can occur.
  • the coagulation bath usually contains a lower alcohol or an organic solvent such as acetone, benzene or toluene. Mixtures with a solvent for polyvinyl alcohol can also be used. It is also possible to use a saturated aqueous solution of an inorganic salt. However, acetone or a lower alcohol, such as ethanol, butanol and in particular methanol, are preferred. After coagulation, the filaments are wound up with e.g. Extracted methanol and dried.
  • the stretching process can be carried out in one or more process steps at a temperature between the glass transition temperature and the decomposition temperature and preferably between 190 and 250 ° C. In the context of the present invention, a procedure is preferred in which the stretching ratio is chosen between 10 and 35 and preferably between 15 and 30.
  • the spinneret channels shown in FIG. 1 have a diameter of 250 ⁇ m.
  • the spinneret channels indicated by broken lines in FIG. 2 are 9.5 mm long.
  • the height of the truncated cone is 0.5 mm.
  • the spinneret When producing a polyvinyl alcohol yarn on an industrial scale, the spinneret is provided with a large number, for example with 250 spinneret channels, instead of the six specified.
  • the mechanical properties of the yarns are determined on an Instron universal testing machine at 20 ° C. and 65% relative humidity.
  • the filament clamping length was 10 cm and the drawing speed was 100% per minute.
  • Use was made of Instron 2712-001 Fiber clamps that were provided with copolyetherester clamping surfaces of 1X1 cm2.
  • the tensile strength at break ⁇ b was determined from the end point of the tensile force-elongation curve and is given in cN / tex;
  • the maximum module E max was determined numerically from the tensile force-length change curve and is given in N / tex;
  • the elongation at break values ⁇ b represent the percentages with which the original clamping length was increased by the filament draw.
  • Average polyvinyl alcohol viscometric molecular weight M v of the PVA ⁇ 295,000, degree of saponification 99.9%) was dissolved at 140 ° C. for three hours under a nitrogen atmosphere in dried N-methylpyrrolidone (NMP) until a 20% by weight PVA solution was obtained.
  • NMP N-methylpyrrolidone
  • the solution thus obtained was introduced into a cylinder belonging to a mini-plunger spinning apparatus in the absence of air.
  • the filaments were spun at a speed of 2.6 m / min and passed into a methanol coagulation bath via an air gap of approximately 2 cm. After the coagulation bath, the yarn was wound up at a speed of 2.85 m / min. The filaments were then extracted into methanol for 24 hours and then air dried for one hour. Hot stretching was then carried out in two process steps. During the first drawing, the filaments were passed over a hot plate at 205 ° C. with a feed speed of 14.5 cm / min and a winding speed of 231 cm / min, which corresponds to a draw ratio of 15.9. In the second process step immediately following this, the filaments were passed through a hot tube through which nitrogen flowed at 235 ° C. at a winding speed of 246 cm / min, which corresponds to a total draw ratio of 17.0.
  • the polyvinyl alcohol used had an average molecular weight viscometric M v ⁇ 200,000.
  • the test conditions were identical to those of Example 1, with the proviso that the spinneret contained only a single spinneret channel with a diameter of 200 ⁇ m, which corresponds to a length / diameter ratio of 25 given the otherwise identical length of the spinneret channel.
  • Table 1 example solvent Spinning temperature (° C) ⁇ ⁇ b (cN / tex) E max (N / tex) ⁇ b (%) 2nd Glycol 175 19th 125 44.5 3.7 3rd Glycerin 190 20th 143 44.5 4.0 4th 1,3-propanediol 190 18th 113 35.0 4.1 5 DMSO 80 25th 162 43.0 4.8 6 NMP 100 24th 144 35.0 4.9
  • Example 5 The experiment of Example 5 was repeated with the proviso that the spinning concentration was varied from 12.5 to 20% by weight of PVA in DMSO.
  • the spinning temperature varied from 25 to 55 ° C and the draw ratio from 19 to 29.
  • Example 2 The experiment from Example 1 was carried out using a polyvinyl alcohol M v ⁇ 200,000, DMSO as solvent, a spinning speed of approximately 1 to 2 m / min and a stretching temperature of approximately 225 ° C.
  • Example 2 The experiment from Example 1 was carried out using a polyvinyl alcohol M v ⁇ 200,000, a spinning speed of approximately 1 to 2 m / min and a stretching temperature of approximately 225 ° C.
  • the spinning temperature was always 140 ° C and the solvent used was N-methylpyrrolidone (NMP).
  • Example 5 The experiment from Example 1 was repeated with DMSO or NMP as the solvent, with polyvinyl alcohol of a different average molecular weight, with different spinning concentrations and stretching ratios.
  • the molecular weight of the polyvinyl alcohol used, the degree of saponification of the polyvinyl alcohol, the solvent, the spinning concentration, the draw ratio, and the properties measured on the filaments are listed in Table 5.
  • Table 5 example M v x10 ⁇ 5 Degree of saponification solvent Spinning conc.
  • Example 2 The experiment from Example 1 was carried out using a polyvinyl alcohol M v ⁇ 200,000, DMSO as solvent, repeated with spinning concentrations between 15 and 30 wt .-% and spinning temperatures between 25 and 150 ° C, with the proviso that now a wet spinneret with 30 spinneret channels was used, which has a length / diameter ratio of 1 with a diameter of 70 microns.
  • a piston spinning machine with a 6 hole spinneret was used.
  • the nozzle plate consisted of 30 wt .-% carbon fiber reinforced polyphenylene sulfide.
  • a 25% by weight solution of polyvinyl alcohol in N-methylpyrrolidone was used for spinning.
  • the polyvinyl alcohol had a molecular weight of 210,000.
  • the filaments were spun at a speed of 3.0 m / min. After the coagulation bath, the yarn is wound up at a speed of 3.6 m / min.
  • the bobbin was then extracted with the yarn in methanol for 24 hours. After air drying the filaments were over three hot plates, each having a temperature of 90 ° C, 230 ° C and 245 ° C, at a feed rate of 1 mm / sec. stretched with an aspect ratio of 16.
  • the drawn filaments had the following properties: Tensile strength: 135.3 cN / tex Elongation at break: 6.3% E max : 35.1 N / tex
  • a 23% by weight solution of polyvinyl alcohol in N-methylpyrrolidone with a molecular weight of 210,000 was pressed through an extruder and spinning pump through a die plate made of 30% by weight carbon fiber reinforced polyphenylene sulfide.
  • the filaments were spun at a speed of 4 m / min and wound up at a speed of 8 m / min.
  • the bobbin was then extracted with the yarn in methanol for 24 hours.
  • the filaments were drawn over two hot plates, each at 100 ° C and 230 ° C, at a feed rate of 32 cm / min.
  • the draw ratio over the first plate was 7.3 and that over the second was 1.8.
  • the total stretch ratio was 13.5.
  • the drawn filaments had the following properties: Tensile strength: 127.4 cN / tex Elongation at break: 6.2% E max : 33.1 N / tex

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP88113740A 1987-08-31 1988-08-24 Procédé pour la fabrication de fils d'alcool polyvinylique Expired - Lifetime EP0310800B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88113740T ATE69271T1 (de) 1987-08-31 1988-08-24 Verfahren zur herstellung von polyvinylalkoholgarnen.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
NL8702038 1987-08-31
NL8702038 1987-08-31
DE3826621 1988-08-05
DE19883826621 DE3826621A1 (de) 1988-08-05 1988-08-05 Spinnduesenplatte

Publications (2)

Publication Number Publication Date
EP0310800A1 true EP0310800A1 (fr) 1989-04-12
EP0310800B1 EP0310800B1 (fr) 1991-11-06

Family

ID=25870845

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88113740A Expired - Lifetime EP0310800B1 (fr) 1987-08-31 1988-08-24 Procédé pour la fabrication de fils d'alcool polyvinylique

Country Status (10)

Country Link
US (1) US4927586A (fr)
EP (1) EP0310800B1 (fr)
JP (1) JPS6477617A (fr)
KR (1) KR890004000A (fr)
AT (1) ATE69271T1 (fr)
BR (1) BR8804407A (fr)
CA (1) CA1301418C (fr)
DE (1) DE3866078D1 (fr)
ES (1) ES2025748T3 (fr)
GR (1) GR3003728T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0399528A2 (fr) * 1989-05-24 1990-11-28 Unitika Ltd. Fils de monofilaments d'alcool polyvinylique et leur procédé de fabrication
AU617025B2 (en) * 1988-12-28 1991-11-14 Dow Corning Corporation Novel polyvinyl alcohol compositions and products prepared therefrom

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5851936A (en) * 1996-08-19 1998-12-22 E. I. Du Pont De Nemours And Company Elongation for flash spun products
US6020425A (en) * 1998-06-01 2000-02-01 Kimberly-Clark Worldwide, Inc. Unmodified polyvinyl alcohol films and fibers and methods of making the same
KR102344856B1 (ko) * 2018-03-29 2021-12-28 코오롱인더스트리 주식회사 고강도 원사를 제조하기 위한 방사팩, 이를 포함하는 원사의 제조장치 및 그 제조방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1102340B (de) * 1956-10-03 1961-03-16 Bayer Ag Verfahren zum Abgleichen der Durchflussmengen von Kapillaren
GB1033627A (en) * 1963-09-18 1966-06-22 Fiberfil Inc Filament die
EP0105169A2 (fr) * 1982-09-30 1984-04-11 Allied Corporation Fibres d'alcool polyvinylique à haute résistance et à haut module et méthode pour leur préparation
EP0146084A2 (fr) * 1983-12-12 1985-06-26 Toray Industries, Inc. Fibre d'alcool polyvinylique à ténacité ultra élevée et procédé pour sa fabrication

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2322976A (en) * 1939-11-03 1943-06-29 Schmitz Hilger Peter Method of producing thin threads from polyvinyl alcohol and its water-soluble derivatives
US2447140A (en) * 1943-04-10 1948-08-17 Johnson & Johnson Method of treating polyvinyl alcohol filaments and treated filament
US3066999A (en) * 1958-08-19 1962-12-04 Kurashiki Rayon Co Polyvinyl alcohol fiber and method of making the same
US3278282A (en) * 1963-10-11 1966-10-11 Jaray Francis Ferdinand Glass spinning crucible
JPS6163704A (ja) * 1984-08-31 1986-04-01 Unitika Ltd 低分子量重合体の紡糸方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1102340B (de) * 1956-10-03 1961-03-16 Bayer Ag Verfahren zum Abgleichen der Durchflussmengen von Kapillaren
GB1033627A (en) * 1963-09-18 1966-06-22 Fiberfil Inc Filament die
EP0105169A2 (fr) * 1982-09-30 1984-04-11 Allied Corporation Fibres d'alcool polyvinylique à haute résistance et à haut module et méthode pour leur préparation
EP0146084A2 (fr) * 1983-12-12 1985-06-26 Toray Industries, Inc. Fibre d'alcool polyvinylique à ténacité ultra élevée et procédé pour sa fabrication

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU617025B2 (en) * 1988-12-28 1991-11-14 Dow Corning Corporation Novel polyvinyl alcohol compositions and products prepared therefrom
EP0399528A2 (fr) * 1989-05-24 1990-11-28 Unitika Ltd. Fils de monofilaments d'alcool polyvinylique et leur procédé de fabrication
EP0399528A3 (fr) * 1989-05-24 1991-07-03 Unitika Ltd. Fils de monofilaments d'alcool polyvinylique et leur procédé de fabrication

Also Published As

Publication number Publication date
EP0310800B1 (fr) 1991-11-06
KR890004000A (ko) 1989-04-19
ES2025748T3 (es) 1992-04-01
GR3003728T3 (fr) 1993-03-16
ATE69271T1 (de) 1991-11-15
BR8804407A (pt) 1989-03-28
DE3866078D1 (de) 1991-12-12
US4927586A (en) 1990-05-22
CA1301418C (fr) 1992-05-26
JPS6477617A (en) 1989-03-23

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