US3492390A - Process for preparing filaments from poly-beta-lactams - Google Patents

Process for preparing filaments from poly-beta-lactams Download PDF

Info

Publication number
US3492390A
US3492390A US691948A US3492390DA US3492390A US 3492390 A US3492390 A US 3492390A US 691948 A US691948 A US 691948A US 3492390D A US3492390D A US 3492390DA US 3492390 A US3492390 A US 3492390A
Authority
US
United States
Prior art keywords
precipitating
poly
filaments
formiates
percent
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
US691948A
Other languages
English (en)
Inventor
Karl Borner
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.)
Hoechst AG
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Application granted granted Critical
Publication of US3492390A publication Critical patent/US3492390A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides

Definitions

  • the present invention relates to a process for preparing filaments from poly-,B-lactams.
  • Filaments and fibers obtained from poly-B-lactams may be employed in many fields. It is known that some poly-18- lactams, in particular the poly-4,4-dimethyl-azetidin-2-one, are soluble in a methanolic calcium thiocyanate solution and may be spun from such a solution into filaments in a precipitating bath of distilled or deionized water (French Patent 1,416,414). However, the spinning process proceeds only with said poly-,B-lactams disubstituted in 4,4- position in an unobjectionable manner for a prolonged period of time and also in this case only under certain conditions, for example while maintaining the temperature of the precipitating bath constant at :1 C.
  • the concentration of the formiates of the alkaline earth metals in the precipitating bath may vary within wide limits up to that concentration at which the precipitating bath is saturated with the formiate of the alkaline earth metal at the respective temperature of the precipitating bath.
  • concentration to be used in each case depends on the nature of the polymer to be coagulated, especially on its viscosity. In general, concentrations of 8 to 15 percent by weight, preferably of 9 to 12 percent by weight, are sufficient.
  • the proportion of the free formic acid in the precipitating baths is 0.5 to 4 percent by weight, preferably 1 to 2 percent by weight.
  • the advantage of the precipitating baths containing formiates of the alkaline earth metals is that the filament is slowly precipiated in these precipitating baths and that the completely coagulated filament remains soft and elastic for a long time and can thus be processed without disturbances.
  • Another advantage of the precipitating baths according to the present invention is that they can easily be prepared and that the salts used can be recovered.
  • the formiates of the alkali earth metals are relative difficultly soluble and can, therefore, already be separated by partial evaporation of the exhausted precipitating baths which is very advantageous for recovering the formic acid from the precipitating bath.
  • the enriched formic acid can be neutralized without difiiculty by conversion with the corresponding oxides or hydroxides of the alkaline earth metals, and the salts formed can be isolated together With the coagulation salts.
  • soft and elastic filaments could be obtained by the process of the present invention when spinning solutions of formic acid of poly-fi-lactams in precipitating baths containing formiates of the alkaline earth metals, especially in view of the fact that there is only required a relatively low concentration of the formiates of the alkaline earth metals in the precipitating bath, for the coagulating effect of sodium chloride, zinc chloride, zinc sulfate or sodium sulfate is considerably lower than that of the formiates of the alkaline earth metals.
  • alkali metal formiates for example MgCl MgSO CaCl NaCl or Na SO especially alkali metal formiates.
  • concentration of these additionally employed salts should not exceed 18 percent by weight and should amount preferably to 5 to 10 percent by Weight.
  • Such salt combinations are preferably used for spinning poly-fi-lactams whose relative viscosity only amounts to 3.2 to 3.6.
  • magnesium sulfate for example 12 percent by weight of magnesium formiate and 10 percent by weight of magnesium sulfate
  • Precipitating baths of a corresponding composition for example 2 percent by weight of formic acid, 11.2 percent by weight of magnesium formiate and 8.9 percent by weight of sodium formiate, remained entirely clear in spinning tests conducted over long periods of time.
  • the advantages of the process according to the present invention are not limited to the non-occurrence of turbidity phenomena in the precipitating baths used according to the present invention or to the prevention of the fluffiness resulting therefrom. Since the precipitation of the filament takes place gradually and, for this reason, the filament remains elastic in the precipitating bath, it can be drawn off more rapidly without breaking. In this manner it is possible to increase the final draw-01f rate to m./minute and thereby to raise the production. For the reasons stated above also the drawability of the spun filaments is distinctly improved. High strength values can be obtained at suflicieutly high elongations.
  • the filaments or fibers obtained by the process of the present invention find many applications in the textile industries.
  • the filaments have a pleasant, silk-like feel and, with a relative atmospheric moisture of 65 percent, absorb 9 percent of Water which is 3 percent more than in the case of poly-e-caprolactam.
  • Knitted or woven fabrics may be produced from the continuous filaments, said fabrics withstanding a boiling wash. Staple fibers produced from the spun filaments are employed in the Worsted yarn industries.
  • the following examples serve to illustrate the invention.
  • the relative viscosity was measured in a solution of 1 percent concentration by weight of the polymer in 98 percent sulfuric acid at 20 C.
  • the viscosity of the spinning solution was measured at 20 C. according to the falling ball test by means of a steel ball (diameter 3 millimeters) with a vertical falling distance of 20 cm.
  • This spinning solution was spun at the rate of 0.33 ml./ minute by means of a gear pump through a tantalum spinneret having 40 openings of a diameter of 0.2 mm. each into an aqueous precipitating bath which had a length of 105 cm., a temperature of 23 C. and which contained 2.6% by weight of formic acid, 109% by weight of magnesium formiate and 6.2% by weight of magnesi um sulfate.
  • the coagulated filament was drawn off at the rate of 6.6 m./ minute by means of a trio-roller and drawn in a ratio of 1:4.4 in a Water bath which had a temperature of 24 C. and a length of 35 cm.
  • the filament obtained had a total titer of 40 deniers and an individual titer of 1.0 denier.
  • the ultimate tensile strength of the filament was 2.60 g./denier at an elongation of break of 17%.
  • ning solution of 25.8% concentration by weight was obtained which had a falling ball viscosity of 700 seconds.
  • this spinning solution was spun, at a rate of 0.493 ml./ minute, into an aqueous precipitating bath which had a length of 120 cm., a temperature of 27 C. and which contained 2.8% by weight of formic acid and 11.7% by Weight of magnesium formiate.
  • EXAMPLE 3 A spinning solution which corresponded to that used in Example 2 was spun by means of a spinneret having openings each having a diameter of 0.3 mm. and processed in the manner described in Example 1.
  • the filament obtained had a total titer of 60 deniers and an individual titer of 4.0 deniers; its ultimate tensile strength was 3.08 g./ den. at an elongation of break of 26%
  • EXAMPLES 4 to 10 In the manner described in Example 1, poly-4-methylazetidin-2-one having a relative viscosity of 8.0 was spun at a rate of 0.465 ml./minute in the form of a spinning solution of 21% concentration by weight in formic acid with a falling ball viscosity of 222 seconds.
  • the following table shows the precipitating baths used, none of I claim:
  • lactam is poly-4-rnethyl-azetidin-2-one.
  • the bath contains up to 18 percent by Weight of another salt selected from the group consisting of inorganic salts of the alkaline earth metals, inorganic alkali metal salts and alkali metal formiates.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US691948A 1966-12-21 1967-12-20 Process for preparing filaments from poly-beta-lactams Expired - Lifetime US3492390A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF0051029 1966-12-21

Publications (1)

Publication Number Publication Date
US3492390A true US3492390A (en) 1970-01-27

Family

ID=7104275

Family Applications (1)

Application Number Title Priority Date Filing Date
US691948A Expired - Lifetime US3492390A (en) 1966-12-21 1967-12-20 Process for preparing filaments from poly-beta-lactams

Country Status (5)

Country Link
US (1) US3492390A (cg-RX-API-DMAC10.html)
BE (1) BE708343A (cg-RX-API-DMAC10.html)
DE (1) DE1669419A1 (cg-RX-API-DMAC10.html)
FR (1) FR1551307A (cg-RX-API-DMAC10.html)
GB (1) GB1145790A (cg-RX-API-DMAC10.html)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379773A (en) * 1980-06-04 1983-04-12 Chevron Research Company Process for wet spinning nylon 4

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2130948A (en) * 1937-04-09 1938-09-20 Du Pont Synthetic fiber
US2360406A (en) * 1940-06-21 1944-10-17 Celanese Corp Manufacture of artificial filaments, films, and like materials
US3093618A (en) * 1958-06-14 1963-06-11 Hoechst Ag Polyamides from beta-amino carboxylic acids
BE640198A (cg-RX-API-DMAC10.html) * 1962-11-20 1964-05-20
US3231539A (en) * 1961-06-02 1966-01-25 Hoechst Ag Process for the manufacture of spinning solutions of poly-beta-lactams by dissolving in an alcoholic solution of calcium thiocyanate
US3269970A (en) * 1962-03-29 1966-08-30 Celanese Corp Spinning filaments from solution in concentrated sulfuric acid of a polyamide and salt
US3360503A (en) * 1963-04-09 1967-12-26 Du Pont Process for preparing poly(alpha, alpha-disubstituted beta-lactams)

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2130948A (en) * 1937-04-09 1938-09-20 Du Pont Synthetic fiber
US2360406A (en) * 1940-06-21 1944-10-17 Celanese Corp Manufacture of artificial filaments, films, and like materials
US3093618A (en) * 1958-06-14 1963-06-11 Hoechst Ag Polyamides from beta-amino carboxylic acids
US3231539A (en) * 1961-06-02 1966-01-25 Hoechst Ag Process for the manufacture of spinning solutions of poly-beta-lactams by dissolving in an alcoholic solution of calcium thiocyanate
US3269970A (en) * 1962-03-29 1966-08-30 Celanese Corp Spinning filaments from solution in concentrated sulfuric acid of a polyamide and salt
BE640198A (cg-RX-API-DMAC10.html) * 1962-11-20 1964-05-20
US3360503A (en) * 1963-04-09 1967-12-26 Du Pont Process for preparing poly(alpha, alpha-disubstituted beta-lactams)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379773A (en) * 1980-06-04 1983-04-12 Chevron Research Company Process for wet spinning nylon 4

Also Published As

Publication number Publication date
BE708343A (cg-RX-API-DMAC10.html) 1968-06-21
FR1551307A (cg-RX-API-DMAC10.html) 1968-12-27
GB1145790A (en) 1969-03-19
DE1669419A1 (de) 1971-03-18

Similar Documents

Publication Publication Date Title
US2130948A (en) Synthetic fiber
DE808922T1 (de) Verfahren zum Nassspinnen von Aramid-Polymer welches Salze enthält sowie damit hergestellte Faser
US3720743A (en) Process for producing high performance crimped rayon staple fiber
US2385890A (en) Spinning process
US4409289A (en) Cellulose-acrylonitrile polymer solutions, articles, and methods of making same
US3492390A (en) Process for preparing filaments from poly-beta-lactams
US3454534A (en) Preparation of nylon with polyalkylene glycol diamine as additive
US4242411A (en) High crimp, high strength, hollow rayon fibers
EP0000740A1 (de) Verfahren zur Herstellung von hydrophilen Fäden und Fasern nach dem Trocken-Düsen-Nassspinnverfahren
US3838562A (en) Acrylonitrile yarn
US3018158A (en) Viscose process
US3549306A (en) Surface modified nylon fibers produced by photocatalyzed halogenation
US5069847A (en) Improvements in process for preparing spun yarns
US3532526A (en) Flame - retardant rayon containing mercapto-phosphonitrilate polymer
US3697637A (en) Method for producing highly crimped regenerated cellulose fibers by steam stretching
US2341586A (en) Wet spinning of cellulose acetate
US2315560A (en) Method for producing high strength and crimped staple fibers from viscose
US3109699A (en) Method for making rayon filaments
US5264282A (en) Polyamide filament, process for producing it and its use
US3445557A (en) Process for preparing filaments from beta-polyamides
US2339316A (en) Wet spinning of cellulose acetate
US4182735A (en) Production of high crimp, high strength, hollow rayon fibers
US3194861A (en) Viscose spinning process and bath
US3364290A (en) High tenacity rayon yarn production
US2930671A (en) Process of producing cuprammonium cellulose articles