US2907096A - Shaped polyacrylonitrile structures - Google Patents

Shaped polyacrylonitrile structures Download PDF

Info

Publication number
US2907096A
US2907096A US36368353A US2907096A US 2907096 A US2907096 A US 2907096A US 36368353 A US36368353 A US 36368353A US 2907096 A US2907096 A US 2907096A
Authority
US
United States
Prior art keywords
filament
filaments
temperature
lustrous
coagulating bath
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
Other languages
English (en)
Inventor
Halbig Paul
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.)
Individual
Original Assignee
Individual
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
Application filed by Individual filed Critical Individual
Application granted granted Critical
Publication of US2907096A publication Critical patent/US2907096A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2973—Particular cross section
    • Y10T428/2975—Tubular or cellular
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the invention -relates to the manufacture of shaped structures from polymers and copolymers of acrylonitrile.
  • the critical temperature range is to a certain eXtent a function of the composition of the polymer but is always between 15 and 70 C. If a solution of polyacrylonitrile in nitric acid is spun, and if the coagulating bath has a temperature below l C., the filaments are lustrous and have a silky character. If, however, the temperature is raised above 15 C., the filaments assume with rising temperature more and more a dull and white aspect. Of course, the transitions from a lustrous and clear filament to a dull and white filament, which are produced by raising the temperature of the coagulating bath, are not abrupt but gradual, and the transition temperatures Vary as a function of Vthe composition and type of filament.
  • Some polymers show the described e'fiect already at bath temperatures of 15 to 20 C.
  • the lower temperature limit is generally above 20 C., i.e'. from this temperature on the effect .becomes visible for the naked eye.
  • the upper temperature limit is defined by the spinnability of the filaments.
  • nitric acid solution into warm water a filament is obtained the interior of which presents over the whole length of the filament a very fine regular porous structure; this makes it possible to spin and Stretch the filaments without difliculties. This behavior appears to be typical for nitric acid solutions. So far, it has not been possible to accomplish similar efi'ects with other solvents.
  • the upper temperature limit is controlled by the spinnability and elongation. As distinctly shown in the preparation of films on glass plates, the size of the cavities increases with increasing temperature until the Spinning of a fine filament becomes impossible, Though for coarser deniers it is possible to Work still 'at 70 C., the matting effect is already at 30 to 40 C. a maximum.
  • the critical temperature range in its broadest aspect may, therefore, be defined as lying between 15 to 70 C.; the optimum range is between 25 and 50 C.
  • a filament produced within the critical temperature range has, for the same titer, a larger diameter than a filament spun below said range.
  • the cross section of the filaments are usually circular; whereas, for instance, a filament of 3 denier which had been pro- Vduced at temperatures of the coagulating bath between 5 and 15 C., has a diameter of 19 to 20/t, a similar filament produced otherwise under the same conditions but in a coagulating bath having a temperature of 35 to 40 C., had a diameter of 24 to 29,11..
  • Fig. l is taken from a lustrous filament, wherein the fibrils have a diameter of 19,u, and
  • Fig. 2 is a corresponding cross section taken from a dull filament according to the invention, wherein the fibrils are larger and have, due to the enclosed air bubbles, a diameter of 24/4.
  • the microscopic picture of stretched filaments shows the lustrous filaments clear and transparent, whereas the mat filaments appear even in thin cross sections opaque and dull, though inhomogenities proper, e.g. air bubbles, cannot be made out. But if the filament is examined in unstretched condition, i.e. in the state as it leaves the coagulating bath after rinsing with water and drying, innumerable bubbles can be detected which are just visible. Otherwise, the filament in this unfinished, i.e. unstretched state constitutes the same unstable structure as the lustrous filament. Surprisingly, however, the mechanical properties and the strength of the mat porous filaments in the stretched state are at least not inferior to those of the transparent lustrous filaments.
  • My ,novel method allows of producing instead of lustrous filaments of dense structure dull filaments of porous structure merely by modifying the temperature of the coagulating bath.
  • the degree of porosity can be controlled by adjusting the rise of temperature.
  • the mat filaments produced according to the invention have a better heat retaining capacity than lustrous filaments.
  • Polymers or copolymers of acrylonitrile can be used for carrying out the novel process; if copolymers are used, they must contain at least 80 percent by weight of acrylonitrile, the rest being another polymerizable compound such as vinyl acetate, arcylic or methacrylic acid or esters or amides thereof.
  • the nitric acid content of the coagulating bath depends on the rate of feed and is between 1 and 40 percent by weight. i
  • the following examples illustrate the method and results obtained in controlling the temperature of the coagulating bath, whereby the first example is carried out at a temperature below the critical temperature and the following examples above the critical temperature.
  • Example I 100 g. of polyacrylonitrile having an average molecular Weight of 60,000 and l g. of urea are dissolved at 20 C. in 700 ⁇ g. of 59%l nitric acid. The solution is filtered through a Nichrome Wire net with 50,1l meshes and stored at a temperature of to C. At this temperature, the solution is stable for at least 100 hours, i.e. after said time the polymer can be quantitatively recovered with substantially the same nitrogen content by precipitation with water. The solution has a viscosity of 450 poise at C. It is extruded into a coagulating bath at a rate of 36 cc. per hour through a spinneret having 10 holes of .1 mm. diameter.
  • the coagulating bath has a temperature of 10 to 15 C. and consists of 10% nitric acid.
  • the filament travels through the bath for a distance of 150 mm. and is then rinsed With distilled water in countercurrent in a washing trough having a length of 500 mm.
  • the filament is then wound on a take-up bobbin revolving at a circurnferential speed of 8 m./min. From this bobbin, the filament passes through a water bath of 90 to 95 C., which contains 0.l% of phosphoric acid, 02% of polyvinyl alcohol, and 02% of glycerol; in this bath, the filament gives olf the main amount of its Water content.
  • the filament passes over a guide roller into a drying chamber, where it is dried with air of about 100 C., and then over a bobbin heated to 150 C. and revolving at a circumferential speed of 10'm./min to the collecting bobbin, which revolves at a circumferential speed at 30 m./rnin.
  • a 30 denier fiber consisting of 10 filaments, which has a tensile strength of 120 to 150 g.
  • the fiber is lustrous and colorless; its cross-section is Circular and has a diameter of 19 to ZOM.
  • Example 2 The procedure was exactly the same as in the first example with the sole difference that the temperature in the coagulating bath was maintained at 35 to 40 C. instead of at 10' to 15 C. There was also obtained a 30 denier fiber which consisted of 10'individual ⁇ filaments and. had a tensilestrength of 120 to 150 g. However,
  • the fiber had dull lustre and a snow White color.
  • the cross section was Circular, and the diameter was 22 to 2411..
  • Example 3 As in Example 1, a solution of g. of polyacrylonitrile having an average molecular weight of 65000 and 800 g. of 59% nitric acid is prepared at 20 C. The solution has a viscosity of 400 poisc at 15 C. It is spun as described in Example l, with the following modifications. The spinneret has 10 holes of .2 mm. diameter and is fed With 40 ccm. of solution per hour. The spinning speed is 3 m./min at the spi'nneret and 30 Iin/min on the take-up bobbin. The temperature in the coagulating bath is maintained at 40 to 45 C. The fiber has a total titre of 30 d. and a tensile strength of g. It is dull and white. The cross section of the fiber is circular and has a diameter of 25 to 28.
  • Example 4 Acrylonitfile and Vinyl acetate are polymerized in a known manner to a copolymer containing 5 percent of Vinyl acetate and having a molecular weight of 70,000.
  • the polymer is connninuted to a particle size of less than a diameter.
  • 100 parts of this copolymer are ground to a suspension with 350 parts of a nitric acid containing 53 percent by weight of HNO3. This suspension is degassed at reduced pressure. Then 1 g. of urea and 350 parts of 65% nitric acid are introduced with stirring. Within a few minutes, the suspension changes to a clear solution. Said solution is filtered through a finely porous filter of a polyvinyl chloride fabric and then degassed in vacuo.
  • the Spinning process can be carried out up to' temperatures of 35 to 40 C. in the coagulati'ng bath' Without disturbances; at a further increase of the temperature of the coagulating bath, however, the filament easily tends to break before it is sufliciently strengthen'ed by' stretching.
  • line A indicates the tensile strength in grams'perv 1 denier
  • line B the diameter of the filament in microns
  • line C the aspect of the filament.
  • filaments can be Washed first With Water, and subsequently they can be treated With hot water of more than 70 C. to remove the greater part of the absorbed Water; the Washed filaments are then heated to about 70 to 100 C., for instance in Water, and stretched by at least about 30 percent, and these prestretched filaments are subsequently stretched again at temperatures above 100 C. by to 250%. Or the swollen filaments can be heated to 70 to 100 C., for instance by passing them over a heated support, to remove the greater part of the absorbed water in liquid form, and the recovered hot water may, if desired, be used for treating the freshly spun filaments at temperatur-es of 70 to 100" C.
  • the after-stretching can also be carried out in a water bath Which contains traces of a strong acid, and after the wet stretching, the filament may be subjected to a finishing treatment by which small amounts of a strong acid and a lubricating agent are applied.
  • a delustered filament composed of an acrylonitrile polymer selected from the group consisting of polyacrylonitrile and copolymers containing at least 80 percent by weight of acrylonitrile monomer units, the balance being polymers of compounds copolymerizable With acrylonitrile, said polymer being soluble in nitric acid, the interior of said filament being honeycombed With a great number of small cavities, said filament having throughout a dull to White appearance and being stretchable without impairment of its mechanical and strength properties to the same extent as a corresponding transparent lustrous filament of the same composition.
  • a delustered stretched filamentV composed of an acrylonitrile polymer selected from the group consisting of polyacrylonitrile and copolymers containing at least 80 percent by weight of acrylonitrile monomer units, the balance being polymers of compounds copolymerizable with acrylonitrile, said polymer being soluble in nitric acid, the interior of said filament being honeycombed with a great number of small cavities, said filament having throughout its cross-section a dull to white appearance, the mechanical and strength properties of said delustered filament being at least the same as those of, and the heat retaining capacity of said delustered filament being considerably improved over that of a corresponding transparent lustrous filament of the same composition. 3.
  • a delustered filament composed of an acrylonitrile polymer selected from the group consisting of polyacrylonitrile and copolymers containing at least percent by weight of acrylonitrile monomer units, the balance being polymers of compounds selected from the group consisting of vinyl acetate, acrylic acid, methacrylic acid, and esters and amides of said acids, said polymer being Soluble in nitric acid, the interior of said filament being honeycombed with a great number of small cavities, said filament having throughout its cross-section a dull to White appearance and being stretchable Without impairment of its mechanical and strength properties to the same eXtent as a corresponding transparent lustrous filament of the same composition.
  • a delustered filament composed of polyacrylonitrile soluble in nitric acid, the interior of said filament being honeycombed With a great number of small cavities, said filament having throughout its cross-section a dull to White appearance and being stretchable Without impairment of its mechanical and strength properties to the same extent as a corresponding transparent lustrous filament of the same composition.
  • a delustered stretched filament composed of polyacrylonitrile soluble in nitric acid, the interior of said filament being honeycombed With a great number of small cavities, said filament having throughout its crosssection a dull to white appearance, the mechanical and strength properties of said delustered filament being substantially the same as those of, andthe heat retaining capacity of said delustered filament being considerably improved over that of, a corresponding transparent lustrous filament of the same composition.

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)
US36368353 1952-06-28 1953-06-23 Shaped polyacrylonitrile structures Expired - Lifetime US2907096A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH741847X 1952-06-28

Publications (1)

Publication Number Publication Date
US2907096A true US2907096A (en) 1959-10-06

Family

ID=4533225

Family Applications (1)

Application Number Title Priority Date Filing Date
US36368353 Expired - Lifetime US2907096A (en) 1952-06-28 1953-06-23 Shaped polyacrylonitrile structures

Country Status (5)

Country Link
US (1) US2907096A (de)
BE (1) BE520876A (de)
CH (1) CH308184A (de)
GB (1) GB741847A (de)
NL (2) NL105850C (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3088188A (en) * 1960-01-04 1963-05-07 Monsanto Chemicals Manufacture of shaped objects of acrylonitrile polymer by wet spinning
US3118161A (en) * 1963-03-13 1964-01-21 E B & A C Whiting Company Foamed polypropylene filaments
US3127298A (en) * 1964-03-31 Method and products thereof
US3246067A (en) * 1962-05-14 1966-04-12 Du Pont Wet-spinning of aromatic polyester filament of high opacity
US3322611A (en) * 1962-10-19 1967-05-30 Du Pont Porous fibers and processes of preparing same
US3871950A (en) * 1972-04-28 1975-03-18 Asahi Chemical Ind Hollow fibers of acrylonitrile polymers for ultrafilter and method for producing the same
US3933653A (en) * 1972-04-28 1976-01-20 Asahi Kasei Kogyo Kabushiki Kaisha Membranes of acrylonitrile polymers for ultrafilter and method for producing the same
US4559268A (en) * 1983-07-04 1985-12-17 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Filament for brushmaking
US5032456A (en) * 1987-09-11 1991-07-16 Newell Operating Company Microcellular synthetic paintbrush bristles
US5786087A (en) * 1995-02-22 1998-07-28 Specialty Filaments, Inc. Honeycomb brush bristles and brush made therefrom

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1057285B (de) * 1955-08-18 1959-05-14 Dr Paul Halbig Verfahren zur Herstellung von Faeden oder Fasern aus Polymerisaten

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1427330A (en) * 1922-05-08 1922-08-29 Rousset Jules Manufacture of hollow artificial textile articles
US2268160A (en) * 1939-06-21 1941-12-30 Du Pont Spongy superpolymer
US2385890A (en) * 1943-03-31 1945-10-02 Du Pont Spinning process
US2476293A (en) * 1944-10-03 1949-07-19 American Viscose Corp Artificial fiber
US2530962A (en) * 1948-09-24 1950-11-21 Du Pont Formation of shaped articles from acrylonitrile polymers
US2531409A (en) * 1946-12-13 1950-11-28 Ind Rayon Corp Interiolymers of acrylonitrile and fumarodinitrile
US2531408A (en) * 1946-12-13 1950-11-28 Ind Rayon Corp Interpolymers of acrylonitrile and itaconic acid
US2555300A (en) * 1947-02-13 1951-06-05 Du Pont Wet-spinning process
US2572931A (en) * 1947-11-01 1951-10-30 American Viscose Corp Cellular products comprising acrylonitrile polymers
US2579451A (en) * 1948-12-31 1951-12-18 Du Pont Polymeric materials
US2628945A (en) * 1949-03-24 1953-02-17 Du Pont Process for obtaining cellular polymeric materials

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1427330A (en) * 1922-05-08 1922-08-29 Rousset Jules Manufacture of hollow artificial textile articles
US2268160A (en) * 1939-06-21 1941-12-30 Du Pont Spongy superpolymer
US2385890A (en) * 1943-03-31 1945-10-02 Du Pont Spinning process
US2476293A (en) * 1944-10-03 1949-07-19 American Viscose Corp Artificial fiber
US2531409A (en) * 1946-12-13 1950-11-28 Ind Rayon Corp Interiolymers of acrylonitrile and fumarodinitrile
US2531408A (en) * 1946-12-13 1950-11-28 Ind Rayon Corp Interpolymers of acrylonitrile and itaconic acid
US2555300A (en) * 1947-02-13 1951-06-05 Du Pont Wet-spinning process
US2572931A (en) * 1947-11-01 1951-10-30 American Viscose Corp Cellular products comprising acrylonitrile polymers
US2530962A (en) * 1948-09-24 1950-11-21 Du Pont Formation of shaped articles from acrylonitrile polymers
US2579451A (en) * 1948-12-31 1951-12-18 Du Pont Polymeric materials
US2628945A (en) * 1949-03-24 1953-02-17 Du Pont Process for obtaining cellular polymeric materials

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3127298A (en) * 1964-03-31 Method and products thereof
US3088188A (en) * 1960-01-04 1963-05-07 Monsanto Chemicals Manufacture of shaped objects of acrylonitrile polymer by wet spinning
US3246067A (en) * 1962-05-14 1966-04-12 Du Pont Wet-spinning of aromatic polyester filament of high opacity
US3322611A (en) * 1962-10-19 1967-05-30 Du Pont Porous fibers and processes of preparing same
US3118161A (en) * 1963-03-13 1964-01-21 E B & A C Whiting Company Foamed polypropylene filaments
US3871950A (en) * 1972-04-28 1975-03-18 Asahi Chemical Ind Hollow fibers of acrylonitrile polymers for ultrafilter and method for producing the same
US3933653A (en) * 1972-04-28 1976-01-20 Asahi Kasei Kogyo Kabushiki Kaisha Membranes of acrylonitrile polymers for ultrafilter and method for producing the same
US4559268A (en) * 1983-07-04 1985-12-17 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Filament for brushmaking
US5032456A (en) * 1987-09-11 1991-07-16 Newell Operating Company Microcellular synthetic paintbrush bristles
US5786087A (en) * 1995-02-22 1998-07-28 Specialty Filaments, Inc. Honeycomb brush bristles and brush made therefrom

Also Published As

Publication number Publication date
CH308184A (de) 1955-06-30
GB741847A (en) 1955-12-14
NL179065B (nl)
NL105850C (de) 1900-01-01
BE520876A (de) 1900-01-01

Similar Documents

Publication Publication Date Title
US2907096A (en) Shaped polyacrylonitrile structures
JPH08501356A (ja) セルロースファイバ
US3494121A (en) Hollow reinforced composite fiber and process for producing same
US3376370A (en) Vinylidene fluoride yarns and process for producing them
JPS604284B2 (ja) 親水性フイラメント類又は繊維類の製造法
US2681265A (en) Spinning artificial filaments
US3322611A (en) Porous fibers and processes of preparing same
US2743994A (en) Method of producing shaped articles from polymeric materials
US3676540A (en) Wet-spinning shaped fibers
CN111254506B (zh) 一种高强壳聚糖长丝及其界面光聚合制备方法与装置
US4869856A (en) Method for producing carbon fibers from acrylonitrile fiber strands
US3706828A (en) Wet spinning non-circular polyacrylonitrile fibers by utilizing circular orifices and sequential coagulation
CN111254507B (zh) 一种高强壳聚糖长丝及其界面聚合制备方法与装置
US5496510A (en) Acrylonitrile filament process
US2692185A (en) Wet spinning of acrylonitrile polymers
US2677591A (en) Removal of porosity in wet-spun acrylonitrile filaments by pressing against a hot surface
US3539678A (en) High speed spinning method of viscose rayon filaments having high wet modulus
US2555300A (en) Wet-spinning process
US3657409A (en) Process for the production of acrylic filaments
US3701820A (en) Process for high speed wet spinning of acrylonitrile fibers
US3073670A (en) Process for the wet-spinning of acrylonitrile polymers
US3760053A (en) Wet-spinning process for {37 dog-bone{38 {0 shaped acrylonitrile polymer fibers
EP0372622A2 (de) Acrylvorläufer für Kohlenstoffasern und Verfahren zur Herstellung derselben
JPS5982420A (ja) 炭素繊維の製造方法
KR950002814B1 (ko) 무연신 초극세 아크릴 섬유의 제조 방법