US3253074A - Process for the manufacture of filaments of poly-beta-methyl-beta-butyrolactam - Google Patents

Process for the manufacture of filaments of poly-beta-methyl-beta-butyrolactam Download PDF

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US3253074A
US3253074A US415186A US41518664A US3253074A US 3253074 A US3253074 A US 3253074A US 415186 A US415186 A US 415186A US 41518664 A US41518664 A US 41518664A US 3253074 A US3253074 A US 3253074A
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water
filaments
spinning
weight
filament
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US415186A
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Borner Karl
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Hoechst AG
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Hoechst AG
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    • 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 the manufacture of filaments of poly-fi-methyl-fibutyrolactam.
  • the concentration of the spinning solution of calcium thiocyanate should preferably be 23 to 26 percent by weight, in which case the proportion by weight of polymer to (anhydrous) calcium thiocyanate can vary within
  • the calcium thiocyanate is generally used with 4 moles of water so that the spinning solutions generally contain 9 to 11 percent of water.
  • the water content of the solvent methyl alcohol/ calcium thiocyanate should not exceed 13 percent because otherwise the solvent would not dissolve the polymer to a sufiicient extent.
  • the very high salt content of the spinning solution of about 23 to 26 percent by weight promotes sticking of the capillary filaments of the freshly spun filament after leaving the precipitating bath, above all during the drawing process which follows immediately.
  • the textile usefulness of such sticky filaments is, of course, substantially impaired so that they cannot be processed at all or with great difficulties only.
  • composition of the spinning solutions may vary to a considerable extent.
  • Their viscosity should lie within the range of from 40 to 800 seconds at C. (measured by the falling ball test with a steel ball having a diameter of 3 mm).
  • the viscosity of the spinning solution depends, in addition to its composition, essentially also on the internal viscosity of the polymer used.
  • the relative viscosity of the polymers used can vary Within the range of from 7.5 to 34, measured as a solution of 1 percent strength by weight in sulfuric acid of 96 percent strength by weight at 20 C.
  • the calcium thiocyanate is preferably used as a salt containing crystal water with 4 moles of water per mole of calcium thiocyanate. The desired water content is easily attained with this salt.
  • the water which is used as precipitating bath may not "ice contain sulfate ions or carbonate ions because these ions would form difiicultly soluble salts with the calcium ion of the spinning solution.
  • the presence of small amounts of chlorides, for example potassiumor sodium chloride, or nitrates does not disturb the spinning process. On the contrary, these salts contribute towards diminishing the sticking tendency of the single filaments of the filament bundle. Since even with the use of boiler feed water owing to the low content of alkali bicarbonatesdeposits of calcium carbonate at the Walls of the container used for the coagulation bath and at the nozzles cannot be avoided, it is necessary to use distilled water or desalted Water for the preparation of the coagulation bath.
  • the temperature of the precipitating bath must be maintained within the limits indicated above. At a temperature exceeding 19 C., filaments are obtained which have a pronounced tendency of stick and are, therefore, entirely useless. At a temperature of the precipitating bath of below 12 C., filaments are obtained which do not stick but which cannot be drawn to a sufiicient extent and whose ultimate tensile strength is entirely insufficient.
  • the temperature constant of the precipitating bath can also be of importance.
  • the preferred temperature of the spinning bath depends on several factors:
  • the admissible temperature range of the precipitating bath, within which fibers are obtained that do not stick, is the broader the higher the relative viscosity of the polymer and the more uniform the structure of the polymer.
  • the chosen temperature of the spinning bath is the higher the less calcium thiocyanate is used in proportion to the polymer.
  • Spinning solutions with a veryhi h falling ball viscosity are generally spun at a temperature of the precipitating bath of from 20 to C., in particular in those cases in which simultaneously a polymer of a high relative viscosity is used.
  • the temperatures of the spinning bath should be the lower the higher the individual titer of the filament.
  • the coagulation bath should advantageously flow countercurrently to the drawing direction of the spinning filament in order that the filament leaves the coagulation bath in as salt-free a state as possible.
  • the coagulated bundle of filaments is drawn off through the spinning bath at a rate of 1 to 6 m./min.
  • the filaments are drawn on trio rollers to 6 to 11 times their original length.
  • the drawing of the still moist filaments can take place in air or in a water bath.
  • the temperatures during the drawing process can vary within wide limits up to the temperature of boiling water. However, the best strength values are obtained when the filaments are drawn at temperatures within the range of from 15 to 25 C.
  • shrinkage spools drying on so-called shrinkage spools is preferred, with an admitted shrinkage of 7 to 10%.
  • the filaments After the first drying-shrinking process, the filaments still have a boil shrinkage of to 64% on an average. To eliminate this boil shrinkage, the filament is still subjected to a hot water fixation at temperatures within a the range of from 68 to 100 C. The hot water fixation can take place while maintaining the length of the filament or while drawing the filament. Drawing degrees of from 5 to of the original length are preferred. Owing to this heat treatment, the crystalline structure of the filament is rearranged while the high boil shrinkage of the filament, which has been freshly spun, drawn and dried with simultaneous shrinkage, is substantially reduced.
  • the application of the process according to the invention has, in addition to the fact that sticking of the capillary filaments is eliminated, still other advantages.
  • the filaments obtained are swollen to a small extent.
  • the spinning/swelling value is the lower the lower the temperature of the spinning bath within the range applied according to the invention. Under these spinning conditions the highest values of ultimate tensile strength and elongation are simultaneously obtained.
  • the swelling value (i.e. the amount of water which is squeezed off) of the freshly spun and drawn filaments lies within the range of from 80 to 140 percent before the first drying. It is reduced to- 40 to 50 percent after the first drying. By the hot water fixation according to the process of the invention the swelling value is reduced to 20 to 30 percent.
  • Example 1 A solution of poly-[i-rnethyl-fl-butyrolactam with a viscosity number according to Staudinger of 5.1 (c.f., for example, Ullmann Encyclopadie der ischen Chemie, vol.
  • the distance of the spinning bath was 165 cm. and the spinning solution was forced into the coagulation bath at a rate of 0.95 g./min., which corresponds to a spinning rate of 8.2 m./min.
  • the temperature of the coagulation bath was maintained at 17.5 C. by means of a thermostat.
  • the filament leaving the spinning bath at a rate of 2.5 m./min., which was squeezed ofi but was still moist (residence time in the spinning bath about 39 seconds), was then drawn between two trio rollers to 8 times its length in water having a temperature of 20 C.
  • the drawn filament was passed through wash water by means of two drawing trio rollers at a rate of 20 m./min. without further drawing, to completely remove possibly adhering traces of calcium thiocyanate. Then the filament was passed under low tension at a drawing rate of 20.5 m./min. through a preparation bath consisting of 4 g./l.
  • the residual shrinkage only amounted to 0.5 to 1%.
  • the filament was interduced into the fixing bath generally by means of a trio roller at a rate of 18 m./min. and was drawn off from the fixing bath by another trio roller at a rate of 20 m./min. Thus a slight drawing took place in the fixing bath.
  • the ultimate tensile strength of the filament was 295 g./100 den. at an elongation of break of 26%.
  • the individual titer of a single filament was 2 deniers, while the total titer of the bundle was deniers.
  • the boil shrinkage could be reduced to 0.5 to 1%.
  • Example 2 A solution of poly-fi-methyl-B-butyrolactam with a viscosity number according to S-taudinger of 3.1, which corresponds to a relative viscosity of 7.5 (measured as a solution of 1% strength by weight in sulfuric acid of 96% strength by weight at 20 C.) in methanolic calcium thiocyanate having a composition of 17% polymer, 23.2% calcium thiocyanate, 11.2% water and 48.6% methyl alcohol, was spun into distilled water by means of a tantalum nozzle having 60 bores of a diameter of 0.07 mm. each, as described in Example 1. The viscosity of the spinning solution, determined according to the falling ball test, was 110 seconds at 20 C.
  • the spinning solution was forced into the coagulation bath at a rate of 1.18 g./min. which corresponds to a spinning rate of 5.1 m./min.
  • the temperature of the spinning bath was 16 C.
  • the filament was processed as described in Example 1.
  • the ultimate tensile strength of the filament was 290 g./ den. at an elongation of 25.7%.
  • the individual titer was 1.6 den.
  • the total titer of the strand was 95.5 den.
  • the viscosity of the spinning solution was 122 seconds at 20 C. (diameter of the steel ball: 3 mm.).
  • the spinning solution was forced into the coagulation bath at a rate of 2.54 g./min. which corresponds to a spinning rate of 10.8 ITL/mll'l.
  • the temperature of the spinning bath was 14.5 C.
  • the filament leaving the spinning bath at a rate of 2.5 rm/min. was drawn in water having a temperature of 20 C. to 7 times its length, washed with water and wound on a shrinkage spool at a rate of 17.5 m./min., the filament being allowed to shrink by 7%.
  • the filament After drying at 35 C., the filament was fixed in water having a temperature of 82 C. The filament obtained had a boil shrinkage of 15%. The individual titer of the filament was 3.0 den. It had an ultimate tensile strength of 240 g./100 den. and an elongation at break of 40%.
  • a process for the manufacture of filaments of polyfi-methyl-fi butyrolactam which comprises spinning a methanolic solution which contains 10.5 to 18 percent by weight of poly-flamethyl-fl-bu'tyrolactam, 19 to 25 percent by weight of calcium thiocyanate and 9 to 11 percent by weight of water, the percentages by weight being calculated on the total solution, into desalted water having a temperature within the range of from 11 to 25 C., drawing the coagulated filaments after they have left the water to 6 to 11 times their original length, drying them with simultaneous shrinkage by 3% to 15% of their length and subjecting them to a hot water fixation within the range of from 68 to 100 C.

Description

the limits of 1:12 to 1:1.9.
United States Patent ,49 6 Claims. (Cl. 264-203) The present invention relates to a process for the manufacture of filaments of poly-fi-methyl-fibutyrolactam.
For the manufacture of spinning solutions capable of being readily filtered it has been proposed in US. patent application SN. 198,446, filed on May 29, 1962, now Patent No. 3,231,539, in the name of Hans Hoyer et al., for Process for the Manufacture of Spinning Solutions of Polyamides to dissolve poly-B-lactams, especially poly-fi-methyl-[i-butyrolactam, in a methanolic solution of calcium thiocyanate.
In order to achieve that the aforesaid polymer dissolves readily, the concentration of the spinning solution of calcium thiocyanate should preferably be 23 to 26 percent by weight, in which case the proportion by weight of polymer to (anhydrous) calcium thiocyanate can vary within The calcium thiocyanate is generally used with 4 moles of water so that the spinning solutions generally contain 9 to 11 percent of water. The water content of the solvent methyl alcohol/ calcium thiocyanate should not exceed 13 percent because otherwise the solvent would not dissolve the polymer to a sufiicient extent.
The very high salt content of the spinning solution of about 23 to 26 percent by weight promotes sticking of the capillary filaments of the freshly spun filament after leaving the precipitating bath, above all during the drawing process which follows immediately. The textile usefulness of such sticky filaments is, of course, substantially impaired so that they cannot be processed at all or with great difficulties only.
Now I have found that sticking of the capillary filaments can be avoided by spinning a methanolic solution, which contains 19.5 to 18 percent by weight of poly-B- methyl-fi-butyrolactam, 19 to 25 percent by weight of calcium thiocyanate and 9 to 11 percent by weight of water, the percentages by weight being calculated on the total solution, into desalted water having a temperature Within the range of from 11 to 25 C., drawing the coagulated filaments, after they have left the water, to 6 to 11 times their original length, drying them with simultaneous longitudinal shrinkage by 3 to percent and subjecting them to a hot water fixation at a temperature within the range of from 68 to 160 C.
Thus the composition of the spinning solutions may vary to a considerable extent. Their viscosity should lie within the range of from 40 to 800 seconds at C. (measured by the falling ball test with a steel ball having a diameter of 3 mm). The viscosity of the spinning solution depends, in addition to its composition, essentially also on the internal viscosity of the polymer used. The relative viscosity of the polymers used can vary Within the range of from 7.5 to 34, measured as a solution of 1 percent strength by weight in sulfuric acid of 96 percent strength by weight at 20 C.
The calcium thiocyanate is preferably used as a salt containing crystal water with 4 moles of water per mole of calcium thiocyanate. The desired water content is easily attained with this salt.
The water which is used as precipitating bath may not "ice contain sulfate ions or carbonate ions because these ions would form difiicultly soluble salts with the calcium ion of the spinning solution. The presence of small amounts of chlorides, for example potassiumor sodium chloride, or nitrates does not disturb the spinning process. On the contrary, these salts contribute towards diminishing the sticking tendency of the single filaments of the filament bundle. Since even with the use of boiler feed water owing to the low content of alkali bicarbonatesdeposits of calcium carbonate at the Walls of the container used for the coagulation bath and at the nozzles cannot be avoided, it is necessary to use distilled water or desalted Water for the preparation of the coagulation bath.
The temperature of the precipitating bath must be maintained within the limits indicated above. At a temperature exceeding 19 C., filaments are obtained which have a pronounced tendency of stick and are, therefore, entirely useless. At a temperature of the precipitating bath of below 12 C., filaments are obtained which do not stick but which cannot be drawn to a sufiicient extent and whose ultimate tensile strength is entirely insufficient. The temperature constant of the precipitating bath can also be of importance. Especially with the use of polymers of low and medium relative viscosities of 7 to 11 (measured as a solution of 1 percent by weight in sulfuric acid of 96 to 97 percent by weight), there are obtained, depending on the composition of the spinning solution used in each case, filaments which do not stick only in case the chosen spinning temperature is maintained at :*:1.5 C.
The preferred temperature of the spinning bath depends on several factors:
The admissible temperature range of the precipitating bath, within which fibers are obtained that do not stick, is the broader the higher the relative viscosity of the polymer and the more uniform the structure of the polymer.
The chosen temperature of the spinning bath is the higher the less calcium thiocyanate is used in proportion to the polymer.
Spinning solutions with a veryhi h falling ball viscosity are generally spun at a temperature of the precipitating bath of from 20 to C., in particular in those cases in which simultaneously a polymer of a high relative viscosity is used.
The temperatures of the spinning bath should be the lower the higher the individual titer of the filament.
Calcium thiocyanate and methyl alcohol are of necesstiy entrained into the precipitating bath due to the precipitating process. The coagulation bath should advantageously flow countercurrently to the drawing direction of the spinning filament in order that the filament leaves the coagulation bath in as salt-free a state as possible. The coagulated bundle of filaments is drawn off through the spinning bath at a rate of 1 to 6 m./min.
On leaving the spinning bath, the filaments are drawn on trio rollers to 6 to 11 times their original length. The drawing of the still moist filaments can take place in air or in a water bath. The temperatures during the drawing process can vary within wide limits up to the temperature of boiling water. However, the best strength values are obtained when the filaments are drawn at temperatures within the range of from 15 to 25 C.
To ensure a good quality of the filaments, it is important that during the first drying process a shrinkage of about 3% to 15% sets in. Drying on so-called shrinkage spools is preferred, with an admitted shrinkage of 7 to 10%.
After the first drying-shrinking process, the filaments still have a boil shrinkage of to 64% on an average. To eliminate this boil shrinkage, the filament is still subjected to a hot water fixation at temperatures within a the range of from 68 to 100 C. The hot water fixation can take place while maintaining the length of the filament or while drawing the filament. Drawing degrees of from 5 to of the original length are preferred. Owing to this heat treatment, the crystalline structure of the filament is rearranged while the high boil shrinkage of the filament, which has been freshly spun, drawn and dried with simultaneous shrinkage, is substantially reduced. It is especially advantageous to carry out the hot water fixation in two stages with an intermediate drying whereby the boil shrinkage is first reduced to 5 to 20% by an initial hot water fixation and, after an intermediate drying, the boil shrinkage of the filament is finally reduced to a value below 1 percent by renewed fixation of the filaments with boiling water.
The application of the process according to the invention has, in addition to the fact that sticking of the capillary filaments is eliminated, still other advantages. The filaments obtained are swollen to a small extent. The spinning/swelling value is the lower the lower the temperature of the spinning bath within the range applied according to the invention. Under these spinning conditions the highest values of ultimate tensile strength and elongation are simultaneously obtained. The swelling value (i.e. the amount of water which is squeezed off) of the freshly spun and drawn filaments lies within the range of from 80 to 140 percent before the first drying. It is reduced to- 40 to 50 percent after the first drying. By the hot water fixation according to the process of the invention the swelling value is reduced to 20 to 30 percent.
The following examples serve to illustrate the invention but they are not intended to limit it thereto, the percentages being by weight:
Example 1 A solution of poly-[i-rnethyl-fl-butyrolactam with a viscosity number according to Staudinger of 5.1 (c.f., for example, Ullmann Encyclopadie der technischen Chemie, vol. 211, page 779), which corresponds to a relative viscosity of 16.4 (determined as a solution of 1% strength by weight in sulfuric acid of 96% by weight at 20 C.) in methanolic calcium thiocyanate having a composition of 13.9% polymer, 22.3% calcium thiocyanate, 10.4% water (the calcium thiocyanate contains about 4 moles crystal water) and 53.4% methyl alcohol, was spun by means of a tantalum nozzle having 30 bores of a diameter of 0.07 mm. each into distilled water or into water that had been completely desalted by means of an exchanger. The viscosity of the spinning solution was 126 seconds at 20 C. (according to the falling ball test carried out with a steel ball of a diameter of 3 mm.). The distance of the spinning bath was 165 cm. and the spinning solution was forced into the coagulation bath at a rate of 0.95 g./min., which corresponds to a spinning rate of 8.2 m./min. The spinning rate was computed from the number of -bores=n, the radius of the nozzle orifice=r, the weight of the solution conveyed per minute=V and the length of the computed cylinder or the desired spinning rate=h according to the formula T 1r-TL-lL=V; h= T 1r-77,
The temperature of the coagulation bath was maintained at 17.5 C. by means of a thermostat. The filament leaving the spinning bath at a rate of 2.5 m./min., which was squeezed ofi but was still moist (residence time in the spinning bath about 39 seconds), was then drawn between two trio rollers to 8 times its length in water having a temperature of 20 C. The drawn filament was passed through wash water by means of two drawing trio rollers at a rate of 20 m./min. without further drawing, to completely remove possibly adhering traces of calcium thiocyanate. Then the filament was passed under low tension at a drawing rate of 20.5 m./min. through a preparation bath consisting of 4 g./l. of a reaction product of coconut oil amine +20 moles of ethylene oxide, and was wound without tension on a shrinkage spool turning at a rate of 20 m./min. During the subsequent drying process on a shrinkage spool, the filament was allowed to shrink by 7 to 10%. The dried filament still had a boil shrinkage of It was, therefore, subjected to a fixing process in hot water of a temperature of, for example, 72 C. or 81 C. The higher the fixing temperature, the lower the residual shrinkage of the finished filament. At 72 C. the residual shrinkage amounted, for example, to 20%, at a fixing temperature of 81 C. it amounted to only 6%. When the fixation was carried out with boiling water, the residual shrinkage only amounted to 0.5 to 1%. The filament was interduced into the fixing bath generally by means of a trio roller at a rate of 18 m./min. and was drawn off from the fixing bath by another trio roller at a rate of 20 m./min. Thus a slight drawing took place in the fixing bath.
The ultimate tensile strength of the filament was 295 g./100 den. at an elongation of break of 26%. The individual titer of a single filament was 2 deniers, while the total titer of the bundle was deniers.
By fixing the filament subsequently in boiling water, the boil shrinkage could be reduced to 0.5 to 1%.
Example 2 A solution of poly-fi-methyl-B-butyrolactam with a viscosity number according to S-taudinger of 3.1, which corresponds to a relative viscosity of 7.5 (measured as a solution of 1% strength by weight in sulfuric acid of 96% strength by weight at 20 C.) in methanolic calcium thiocyanate having a composition of 17% polymer, 23.2% calcium thiocyanate, 11.2% water and 48.6% methyl alcohol, was spun into distilled water by means of a tantalum nozzle having 60 bores of a diameter of 0.07 mm. each, as described in Example 1. The viscosity of the spinning solution, determined according to the falling ball test, was 110 seconds at 20 C. (diameter of the steel ball: 3 mm.). The spinning solution was forced into the coagulation bath at a rate of 1.18 g./min. which corresponds to a spinning rate of 5.1 m./min. The temperature of the spinning bath was 16 C. The filament was processed as described in Example 1.
The ultimate tensile strength of the filament was 290 g./ den. at an elongation of 25.7%. The individual titer was 1.6 den., the total titer of the strand was 95.5 den.
Example 3 A solution of poly-fi=methyl-,B-butyrolactam with a viscosity number according to Staudinger of 5.1, which cor responds to a relative viscosity of 16.4 (measured as a solution of 1% strength by weight in sulfuric acid of 96% strength by weight at 20 C.) in methanolic calcium thiocyanate having the composition of 13.8% polymer, 22.3% calcium thiocyanate (anhydrous), 10.5% water and 53.4% methyl alcohol, was spun into distilled water by means of a tantalum nozzle having 60 bores of a diameter of 0.07 mm. each, as described in Example 1.
The viscosity of the spinning solution, determined according to the falling bal'l test, was 122 seconds at 20 C. (diameter of the steel ball: 3 mm.). The spinning solution was forced into the coagulation bath at a rate of 2.54 g./min. which corresponds to a spinning rate of 10.8 ITL/mll'l. The temperature of the spinning bath was 14.5 C. The filament leaving the spinning bath at a rate of 2.5 rm/min. was drawn in water having a temperature of 20 C. to 7 times its length, washed with water and wound on a shrinkage spool at a rate of 17.5 m./min., the filament being allowed to shrink by 7%. After drying at 35 C., the filament was fixed in water having a temperature of 82 C. The filament obtained had a boil shrinkage of 15%. The individual titer of the filament was 3.0 den. It had an ultimate tensile strength of 240 g./100 den. and an elongation at break of 40%.
I claim:
1. A process for the manufacture of filaments of polyfi-methyl-fi butyrolactam, which comprises spinning a methanolic solution which contains 10.5 to 18 percent by weight of poly-flamethyl-fl-bu'tyrolactam, 19 to 25 percent by weight of calcium thiocyanate and 9 to 11 percent by weight of water, the percentages by weight being calculated on the total solution, into desalted water having a temperature within the range of from 11 to 25 C., drawing the coagulated filaments after they have left the water to 6 to 11 times their original length, drying them with simultaneous shrinkage by 3% to 15% of their length and subjecting them to a hot water fixation within the range of from 68 to 100 C.
2. The process as claimed in claim 1, wherein the coagulated filaments are drawn in a water bath having a temperature of 15 to 25 C.
3. The process as claimed in claim 1, wherein the coagulated and drawn filaments are caused to shrink on a shrinkage pool by 7% to 10% of their length.
4. The process as claimed in claim 1, wherein the hot water fixation is carried out in such a manner that the length of the filament is preserved. 1
5. The process as claimed in claim 1, wherein the filaments are subjected during the hot water fixation to a drawing of from 5% to 20%.
6. The process as claimed in claim 1, wherein the hot water fixation is carried out in two stages by using first a water bath having a temperature of from 68 to 82 C. and then another water bath with boiling water and drying the filaments between the two baths.
No references cited.
ALFRED L. LEAVITT, Primary Examiner.

Claims (1)

1. A PROCESS FOR THE MANUFACTURE OF FILAMENTS OF POLYB-METHYL-B-BUTYROLACTAM, WHICH COMPRISES SPINNING A METHANOLIC SOLUTION WHICH CONTAINS 10.5 TO 18 PERCENT BY WEIGHT OF POLY-B-METHYL-B-BUTYROLACTAM, 19 TO 25 PERCENT BY WEIGHT OF CALCIUM THIOCYANATE AND 9 TO 11 PERCENT BY WEIGHT OF WATER, THE PERCENTAGES BY WEIGHT BEING CALCULATED ON THE TOTAL SOLUTION, INTO DESALTED WATER HAVING A TEMPERATURE WITHIN THE RANGE OF FROM 11* TO 25*C., DRAWING THE COAGULATED FILAMENTS AFTER THEY HAVE LEFT THE WATER TO 6 TO 11 TIMES THEIR ORIGINAL LENGTH, DRYING THEM WITH SIMULTANEOUS SHRINKAGE BY 3% TO 15% OF THEIR LENGTH AND SUBJECTING THEM TO A HOT WATER FIXATION WITHIN THE RANGE OF FROM 68* TO 100*C.
US415186A 1963-12-07 1964-12-01 Process for the manufacture of filaments of poly-beta-methyl-beta-butyrolactam Expired - Lifetime US3253074A (en)

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DEF41498A DE1238613B (en) 1963-12-07 1963-12-07 Process for the production of threads from poly-4,4-dimethylazetidin-2-one

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Publication number Priority date Publication date Assignee Title
CN102142343B (en) * 2010-01-28 2013-01-30 北大方正集团有限公司 Filament renewing method and device

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US3588338A (en) * 1969-03-21 1971-06-28 Rca Corp Gamma correction and shading modulation circuitry for a television camera

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US2177637A (en) * 1938-09-14 1939-10-31 Du Pont Polymeric material
BE447540A (en) * 1941-11-15
DE971078C (en) * 1949-10-09 1959-01-15 Hoechst Ag Process for the production of crimped fibers from a tow made of polymeric ªŠ-caprolactam

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CN102142343B (en) * 2010-01-28 2013-01-30 北大方正集团有限公司 Filament renewing method and device

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