US3388200A - Process for wet spinning elastic fibers - Google Patents

Process for wet spinning elastic fibers Download PDF

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Publication number
US3388200A
US3388200A US419779A US41977964A US3388200A US 3388200 A US3388200 A US 3388200A US 419779 A US419779 A US 419779A US 41977964 A US41977964 A US 41977964A US 3388200 A US3388200 A US 3388200A
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US
United States
Prior art keywords
filaments
wet spinning
spinning
linear
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
US419779A
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English (en)
Inventor
Charles E Jackson
Lloyd T Jenkins
Jr Philip E Slade
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.)
Monsanto Co
Original Assignee
Monsanto Co
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 Monsanto Co filed Critical Monsanto Co
Priority to US419779A priority Critical patent/US3388200A/en
Priority to NL6516600A priority patent/NL6516600A/xx
Priority to GB53912/65A priority patent/GB1111807A/en
Priority to IL24836A priority patent/IL24836A/xx
Priority to CH1757065A priority patent/CH480455A/de
Priority to BE674131D priority patent/BE674131A/xx
Priority to LU50116A priority patent/LU50116A1/xx
Priority to FR43122A priority patent/FR1461054A/fr
Priority to DE19651660468 priority patent/DE1660468A1/de
Application granted granted Critical
Publication of US3388200A publication Critical patent/US3388200A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • D01D5/06—Wet spinning methods
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes

Definitions

  • This invention relates to the preparation of shaped articles from linear, segmented polyurethane compositions and more particularly to an improved wet spinning method for the preparation of elastic fibers and filaments from linear, segmented, polyurethane polymers typified structurally by the presence of low-melting, amorphous segments joined to high-melting, crystalline segments.
  • Certain synthetic elastomers based on linear, segmented polyurethane polymers have been developed as a replacement for rubber, which possesses some disadvantages for textile applications that tend to offset its desirable elastic properties. Fibers from these new synthetic elastomers are highly elastic and also have a higher modulus and better abrasion resistance than rubber. It is desirable therefore, to have available a wet spinning process for the preparation of fibers and filaments from these synthetic elastomers which would have a relatively wide range of tenacities, elongations, moduli and other properties which are easily obtained in a controlled and consistently reproducible manner.
  • Another object of the invention is to provide a wet spinning process for the preparation of elastic fibers and filtments from linear, segmented polyurethane compositions in which the process is characterized by faster production rates, by the fibers remaining in the spin bath a very short period of time, approximately from about 0.025 to 0.2 second, and by the positioning of the spinneret so that the fiber leaves the spin bath at right angles to the surfaces of the spin bath and travels in an essentially vertical path upwardly to the first godet.
  • An additional object of the invention is to provide a wet spinning process which produces elastic polyurethan fibers of improved elongation, tenactiy, modulus and stress retention.
  • Yet another object of the invention is to provide a wet spinning process for the preparation of fibers from linear, segmented polyurethane compositions in which the spinneret is immersed only from about 0.5 to 3.0 inches beneath the surface of the coagulation bath and in which the elimination of substantially all friction points in the bath and on the first godet has taken place.
  • Patents 2,755,266; 2,923,598; 2,955,07; and 2,965,437 teaches the necessity of having to use long coagulation baths and lengthy immersion time with the spinneret positioned for substantially horizontal extrusion or horizontal spinning regardless of whether the polymer is formed prior to spinning or extended in the coagulation bath.
  • the extrusion of the linear, segmented polyurethane polymer solution may be accomplished by employing a suitable extrusion orifice well known in the art and which is suitable for the preparation of the type of end product desired.
  • the solution of the polymer may be prepared by employing any well known prior art solvent which will dissolve a linear, segmented polyurethane polymer in the desired concentration for spinning, usually from 1525% solids concentration.
  • solvents for example, include dimethylformamide, dimethylacetamide, dimethylsulfoxide and hexamethphosphoramide.
  • the preferred solvents are dimethylformamide and dimethylacetamide.
  • the coagulating bath preferably consists primarily of water at a temperature of from about 60 to C.
  • the coagulating bath may contain a percentage of the organic solvent used to prepare the solution, for example from about 1 to 40 percent.
  • the positioning of the spinneret beneath the surface of the coagulting bath and the residence time of the fiber in the bath are critical features of the invention.
  • the improvement obtainable in the wet spinning of linear, segmented polyurethane polymers is achieved by placing the spinneret in a position in the coagulating bath so that the filaments as they are extruded out of the spinneret are conveyed in an essentially vertical upward direction through the coagulating bath liquid for a distance of from about 0.5 to 3.0 inches, preferably 1.5 to 2.0 inches and at a rate of withdrawal which will result in the filaments remaining in the coagulating bath for a period of time of from about 0.025 to 0.2 second and preferably from about 0.075 to 0.1 second.
  • this very short coagulation bath exposure or residence time has been found to be advantageous in effecting coagulation and to do so without void formation.
  • the vertical withdrawal of the filaments reduces solvent drag which is prevalent during normal wet spinning processes wherein a certain amount of the coagulating bath liquid and the spinning solvent is withdrawn partially from the surface of the coagulating bath by the moving filament and then falls back into the coagulating bath. This sets up a certain amount or drag or frictional pull on the filaments as they emerge from the coagulating bath liquid and results in deterioration of critical fiber properties.
  • the first godet or roller around which the filaments are wrapped and removed from the coagulating bath is constructed so as to freely rotate or be driven by motor means extension of the fibers at the breaking point. Stress retention is the percent elasticity retained after 300% extension and 80% recovery of the 2nd cycle stretch.
  • FIGURE 2 is a graph showing the effect of residence formamide to give a spinning dope of percent solids. time and immersion length on elongation, a critical prop- The spinning dope is extruded through a spinneret conerty for elastic fibers. 15 taining 15 holes of 6 mil diameter into a coagulation bath.
  • 075 .do 205 770 030 tion may be extruded through a single orifice or a plural- EXAMPLE II ity of orifices in the spinneret to form a filament or bundle A 3oo p,u t Onion by Wei ht of O] ,(tewrmemykne of filaments.
  • the extruded streams of polymer are directed nlycol) of imolgcular Weight 28600 E g g with 58 5 n g D $21?
  • m P g fg f fgf l i 802mm suitable for use in the improved wet spinning process of 0 glve a spmmng 0 so 1 spmmng 0pc was extruded both houzontally and vertically through a the invention include any and all of the well known linear, S imemt 15 holes of 6 mil diameter into a bqth connim segmented polyurethane polymer compositions of the s water and 25% dimeth rlformqmidg at C prior art Sometimes referred to .spandex P filas' Tl e residence time of the fiber in the spin bath was two $223 ii gi fi gg ggf ggg g seconds when spun horizontally and 0.075 second when 3,097,192 and are generally desciibed as cor npri sinmurea spun Vemcany' Thefiber fi Washed, drld and taken up segments linked to polyester or polvether segments at
  • a wind range of solvents may also be a -Spmnmg This 2 dope 18 then extrudgd used in the process of the invention. using the c0nd1t1ons described in Example 11.
  • the prop- The elastic fibers and filaments of the invention are of these are ,also gwen Tab1e H shcwmfg useful in a variety of applications Such as in fabrics? the improvement in vertlcal short residence over horiwomens lingerie, support hose and similar textile end Zomal long resldence Splnmnguses- EXAMPLE IV
  • the invention is further illustrated by the following examples in which all parts and percents are by weight un- A 4001mm Pomon by welght of a polyester Composed less otherwise indicated.
  • EXAMPLE VI The permanent set of fibers prepared from the polymer composition of Example I is improved when wet spun vertically as shown by the following data.
  • Percent set sample average 2 secs. horizontal, 35;
  • the improvement consisting of advancing the filaments as they are coagulated upwardly through the coagulating bath a distance of up to about 3.0 inches at a rate of withdrawal which will result in the filaments remaining in the coagulating bath for a period of time of up to about 0.2 second.
  • the improvement consisting of advancing the filaments as they are coagulated upwardly polyurethane polymers to produce elastomeric polyurethane fibers and filaments, the improvement consisting of advancing the filaments as they are coagulated upwardly through the coagulating bath so that the filaments will move essentially vertically with respect to the surface of the coagulating bath liquid for a distance of from 1.5 to 2.0 inches at a rate of withdrawal which will result in the filaments remaining in the coagulating bath for a period of time of from about 0.075 to 0.1 second.
  • the improvement consisting of advancing the filaments as they are coagulated upwardly through the coagulating bath consisting essentially of water and from 1 to 40 percent of dimethylformamide so that the filaments will move essentially vertically with respect to the surface of the coagulating bath liquid for a distance of from 1.5 to 2.0 inches at a rate of withdrawal which will result in the filaments remaining in the coagulating bath for a period of time of from about 0.075 to 0.1 second.
  • the improvement consisting of advancing the filaments as they are coagulated upwardly through the coagulating bath consisting essentially of Water and from 1 to 40 percent of dimethylacetamide so that the filaments will move essentially vertically with respect to the surface of the coagulating bath liquid for a distance of from 1.5 to 2.0 inches at a rate of withdrawal which will result in the filaments remaining in the coagulating bath for a period of time of from about 0.075 to 0.1 second.

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)
US419779A 1964-12-21 1964-12-21 Process for wet spinning elastic fibers Expired - Lifetime US3388200A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US419779A US3388200A (en) 1964-12-21 1964-12-21 Process for wet spinning elastic fibers
GB53912/65A GB1111807A (en) 1964-12-21 1965-12-20 Process for wet spinning elastic polyurethane fibers
IL24836A IL24836A (en) 1964-12-21 1965-12-20 Process for wet spinning elastic fibers
NL6516600A NL6516600A (de) 1964-12-21 1965-12-20
CH1757065A CH480455A (de) 1964-12-21 1965-12-21 Verfahren zur Herstellung von elastomeren Polyurethanfilamenten
BE674131D BE674131A (de) 1964-12-21 1965-12-21
LU50116A LU50116A1 (de) 1964-12-21 1965-12-21
FR43122A FR1461054A (fr) 1964-12-21 1965-12-21 Procédé de filage par voie humide de fibres élastiques
DE19651660468 DE1660468A1 (de) 1964-12-21 1965-12-21 Verfahren zur Herstellung von geformten Gegenstaenden aus linearen segmentierten Polyurethanmassen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US419779A US3388200A (en) 1964-12-21 1964-12-21 Process for wet spinning elastic fibers

Publications (1)

Publication Number Publication Date
US3388200A true US3388200A (en) 1968-06-11

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Family Applications (1)

Application Number Title Priority Date Filing Date
US419779A Expired - Lifetime US3388200A (en) 1964-12-21 1964-12-21 Process for wet spinning elastic fibers

Country Status (9)

Country Link
US (1) US3388200A (de)
BE (1) BE674131A (de)
CH (1) CH480455A (de)
DE (1) DE1660468A1 (de)
FR (1) FR1461054A (de)
GB (1) GB1111807A (de)
IL (1) IL24836A (de)
LU (1) LU50116A1 (de)
NL (1) NL6516600A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3548047A (en) * 1967-02-23 1970-12-15 Union Carbide Corp Lubrication of spandex yarns
EP0380344A2 (de) * 1989-01-26 1990-08-01 E.I. Du Pont De Nemours And Company Verfahren zur Herstellung von mit Röntgenstrahlen entdeckbaren Spandexfasern und diese Fasern
US20100025887A1 (en) * 2006-12-19 2010-02-04 Robert Bosch Gmbh Process and apparatus for producing a strand-like extrudate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3036878A (en) * 1959-09-25 1962-05-29 Globe Mfg Company Polyurethanes
US3037240A (en) * 1958-11-24 1962-06-05 Stoy Artur Method and apparatus for manufactureing shaped articles from solutions of acrylonitrile polymers and copolymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037240A (en) * 1958-11-24 1962-06-05 Stoy Artur Method and apparatus for manufactureing shaped articles from solutions of acrylonitrile polymers and copolymers
US3036878A (en) * 1959-09-25 1962-05-29 Globe Mfg Company Polyurethanes

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3548047A (en) * 1967-02-23 1970-12-15 Union Carbide Corp Lubrication of spandex yarns
EP0380344A2 (de) * 1989-01-26 1990-08-01 E.I. Du Pont De Nemours And Company Verfahren zur Herstellung von mit Röntgenstrahlen entdeckbaren Spandexfasern und diese Fasern
US5183614A (en) * 1989-01-26 1993-02-02 E. I. Du Pont De Nemours And Company Method for producing x-ray detectable spandex fibers
EP0380344B1 (de) * 1989-01-26 1993-09-29 E.I. Du Pont De Nemours And Company Verfahren zur Herstellung von mit Röntgenstrahlen entdeckbaren Spandexfasern und diese Fasern
US20100025887A1 (en) * 2006-12-19 2010-02-04 Robert Bosch Gmbh Process and apparatus for producing a strand-like extrudate

Also Published As

Publication number Publication date
FR1461054A (fr) 1966-12-10
CH480455A (de) 1969-10-31
GB1111807A (en) 1968-05-01
LU50116A1 (de) 1966-06-21
BE674131A (de) 1966-06-21
NL6516600A (de) 1966-06-22
IL24836A (en) 1969-07-30
DE1660468A1 (de) 1971-01-14

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