US3122412A - Production of fibres of acrylonitrile polymers - Google Patents
Production of fibres of acrylonitrile polymers Download PDFInfo
- Publication number
- US3122412A US3122412A US45558A US4555860A US3122412A US 3122412 A US3122412 A US 3122412A US 45558 A US45558 A US 45558A US 4555860 A US4555860 A US 4555860A US 3122412 A US3122412 A US 3122412A
- Authority
- US
- United States
- Prior art keywords
- yarn
- filaments
- ketone
- treated
- drawn
- 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
Links
- 229920002239 polyacrylonitrile Polymers 0.000 title description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000009987 spinning Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 26
- 150000002576 ketones Chemical class 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000011282 treatment Methods 0.000 description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 10
- 208000012886 Vertigo Diseases 0.000 description 8
- 238000000578 dry spinning Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- -1 fatty acid ester Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 2
- 239000008041 oiling agent Substances 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/221—Preliminary treatments
-
- 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
Definitions
- acrylonitrile polymers are meant acrylonitrile homopolymer as well as copolymers and grafted polymers containing from 85% to 100% of acrylonitrile and up to 15 of one or more copolymerisable ethylenic compounds, and mixtures of such polymers.
- undrawn filaments filaments made by dry or wet spinning before they have undergone their complete drawing. They may have undergone a treatment for the extraction of the solvent employed in their spinning, for example by washing, and/or a preliminary drawing. Depending upon the subsequent use for which they are intended, these filaments are combined in groups to form either yarns of relatively low count, which will be employed as continuous yarns, or tows of higher count which will thereafter be cut or cracked to obtain staple fibre. it is these filaments combined in groups of variable size which are treated in accordance with the invention and then drawn.
- the treatment or treatments of the invention can be carried out at any desired instant between the extrusion of the filaments and their final drawing.
- the filaments may be passed through a bath containing a ketone immediately after they leave the spinning zone, or the spinning solvent can be extracted by one or more washings with a ketone, or one or more immersions in a ketone may be effected before or after elimination of the solvent by known means, or a number of these treaments may be carried out in conjunction.
- the treatment or treatments according to the invention may be effected either continuously or discontinuously, if desired after a preliminary drawing.
- the duration of the treatment or treatments of the invention may vary within wide limits. In any case, it must be suiiicient to ensure good contact of the filaments with the ketone. For example, in the case of the discontinuous immersion of a larger or compact wound package of filaments, the duration of the immersion must be sufficient to ensure contact of the ketone with all the filaments as far as the centre of the package. An immersion duration of from to 30 minutes is then generally preferred. If the filaments are continuously passed through the bath containing the ketone, a virtually instantaneous contact may be sufiicient in the case of a gr up of filaments of relatively low count.
- an oiling agent soluble in the ketone such as a condensation product of ethylene oxide with a fatty alcohol, an alkyl higher fatty acid ester such as butyl stearate, etc.
- the final drawing may be carried out by known means.
- One of the main advantages of the present invention resides in the fact that owing to the greatly improved drawing properties of the treated yarns it is possible to increase the extent of the drawing, and therefore the tenacity of the drawn yarn, while maintaining its flexibility and elongation.
- the maximum degree of drawing i.e. the degree of drawing above which breakage of the yarn occurs, is considerably higher than in the case of an untreated yarn.
- the laws governing the tension during drawing are fundamentally modified.
- the tension necessary for the drawing is substantially independent of the extent of the drawing, while in the case of the untreated yarn the tension necessary increases with the extent of drawing.
- an undrawn yarn treated entirely with a ketone, such for example as acetone, from the time of its extrusion, and thus in a completely dry state possesses before drawing a high elongation at ambient temerature, as also great flexibility, while an untreated yarn has very low elongation and has no flexibility, so that it is rendered brittle in the course of the manipulations.
- Another advantage of the process is that it makes it possible to draw a treated yarn to the same extent as an untreated yarn but with greater safety, i.e. without the risk or" the formation of hairs on the yarn as a result of the rupture of a number of filaments during the drawing.
- Example I A polyacrylonitrile yarn obtained by dry spinning a solution of polyacrylonitrile in dimethylfcrmamide is washed with water in order to remove the residual solvent and then immersed at room temperature for 10 minutes in a bath of diethylketone containing 1% of a condensation product of ethylene oxide with a fatty alcohol, calculated on the weignt of yarn immersed. It is thereafter drawn in steam at a temperature of 98 C.
- This yarn can be readily drawn to twelve times its origi nal length, wln'le a comparison specimen not washed with diethylketone cannot easily be drawn beyond 6.5 times its original length.
- the final tenacity of the yarn treated with diethylketone is considerably greater than that of the comparison specimen, though its elongation is substantially the same.
- Example 11 A copolymer yarn containing by wei ht of acrylontirlle and 10% by weight of vinyl dimethylaminoethyl eti er obtained by dry spinning is treated just bei is first twice washed with water.
- Example IV A yarn obtained by dry spinning a mixture of 85% by weight of polyacrylonitrile and 15% by weight of polyvinyl acetate is treated just before it leaves the spinning cell with an aqueous liquid in accordance wtih the aforesaid French Patent 1,052,539.
- the yarn obtained has a Water content of 100% of its dry weight. It is successively treated in three acetone baths at room temperature.
- the water content of the yarn varies as follows:
- the third bath contains 1% of a condensation prodnot of ethylene oxide with a fatty alcohol, calculated on the weight of the treated yarn.
- the yarn thus obatined can readily be drawn to 12 times its original length, while a yarn treated in the same way, but with Water instead of acetone, can only with difficulty be drawn to more than 8 times its original length.
- Example V A tow of polyacrylonitrile obtained by wet spinning It is pre-drawn by 10% of its initial length, whereafter it is immersed for minutes at room temperature in a methylethylketone bath containing 1% of butyl stearate calculated on the weight of the tow treated. It is thereafter readily drawn by a factor of 10, while a similar tow, treated only with water, can be drawn only with difficulty by more than 7 times its original length.
- Example VI A polyacrylonitrile yarn obtained by dry spinning is treated with acetone just before it leaves the spinning cell. t is collected in a perforated pot, which is thereafter successively immersed in three acetone baths for 10 minutes in each bath, the last bath containing 0.8% of a condensation product of ethylene oxide with a fatty alcohol, calculated on the weight of the treated yarn.
- the yarn is thereafter readily drawn at elevated tem* perature to 11 times its initial length, while an identical yarn, which has undergone treatments with water instead of acetone, can only with difiiculty be drawn to more than 7 times its original length. Even in the cold state before the drawing, the yarn treated with acetone possesses a drawing capacity higher than 3, while that of a comparison yarn treated with water is only 1.5 under the same conditions.
- Example VII A polyacrylonitrile yarn obtained by dry spinning is first washed in counter-current with water in order to remove the residual solvent. It is collected in a perforated pot, which is thereafter successively immersed in two baths containing of acetone and 30% of water for 10 minutes in each bath.
- the yarn thus treated can be readily drawn at elevated temperature to 11.5 times its original length, while a comparison yarn only washed with water and not treated with the acetone-water bath can only with difilculty be drawn to more than 6.8 times its original length.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR801528A FR1240653A (fr) | 1959-07-30 | 1959-07-30 | Perfectionnement à l'obtention de fibres en polymères à base d'acrylonitrile |
Publications (1)
Publication Number | Publication Date |
---|---|
US3122412A true US3122412A (en) | 1964-02-25 |
Family
ID=8717738
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US45558A Expired - Lifetime US3122412A (en) | 1959-07-30 | 1960-07-27 | Production of fibres of acrylonitrile polymers |
Country Status (7)
Country | Link |
---|---|
US (1) | US3122412A (es) |
CH (1) | CH386617A (es) |
DE (1) | DE1186977B (es) |
ES (1) | ES259995A1 (es) |
FR (1) | FR1240653A (es) |
GB (1) | GB954553A (es) |
NL (1) | NL254391A (es) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3491179A (en) * | 1967-01-03 | 1970-01-20 | American Cyanamid Co | Preparation of acrylonitrile polymer fibers |
US3925524A (en) * | 1972-06-22 | 1975-12-09 | Celanese Corp | Process for the production of carbon filaments |
US4013753A (en) * | 1973-10-09 | 1977-03-22 | Bayer Aktiengesellschaft | Process for the production of spontaneously crimping polyacrylonitrile composite fibres with improved crimp properties |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2579451A (en) * | 1948-12-31 | 1951-12-18 | Du Pont | Polymeric materials |
US2589294A (en) * | 1948-02-26 | 1952-03-18 | Goodrich Co B F | Vinylidene cyanide polymers and polymer products |
US2768868A (en) * | 1953-03-27 | 1956-10-30 | Du Pont | Improving the dyeing uniformity and thermostability of undrawn acrylonitrile polymer filaments by applying steam under pressure |
US2916348A (en) * | 1956-08-21 | 1959-12-08 | American Cyanamid Co | Production of polyacrylonitrile filaments |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB720380A (en) * | 1952-01-10 | 1954-12-15 | British Celanese | Improvements in the manufacture of filamentary material from copolymers of acrylonitrile and vinylidene chloride |
DE961288C (de) * | 1953-08-03 | 1957-04-04 | Glanzstoff Ag | Verfahren zum Aufrauhen und Mattieren von Faeden aus Polyaethylenterephthalaten |
-
0
- NL NL254391D patent/NL254391A/xx unknown
-
1959
- 1959-07-30 FR FR801528A patent/FR1240653A/fr not_active Expired
-
1960
- 1960-07-27 US US45558A patent/US3122412A/en not_active Expired - Lifetime
- 1960-07-29 ES ES0259995A patent/ES259995A1/es not_active Expired
- 1960-07-29 DE DEC22035A patent/DE1186977B/de active Pending
- 1960-07-29 CH CH870160A patent/CH386617A/fr unknown
- 1960-07-29 GB GB26571/60A patent/GB954553A/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2589294A (en) * | 1948-02-26 | 1952-03-18 | Goodrich Co B F | Vinylidene cyanide polymers and polymer products |
US2579451A (en) * | 1948-12-31 | 1951-12-18 | Du Pont | Polymeric materials |
US2768868A (en) * | 1953-03-27 | 1956-10-30 | Du Pont | Improving the dyeing uniformity and thermostability of undrawn acrylonitrile polymer filaments by applying steam under pressure |
US2916348A (en) * | 1956-08-21 | 1959-12-08 | American Cyanamid Co | Production of polyacrylonitrile filaments |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3491179A (en) * | 1967-01-03 | 1970-01-20 | American Cyanamid Co | Preparation of acrylonitrile polymer fibers |
US3925524A (en) * | 1972-06-22 | 1975-12-09 | Celanese Corp | Process for the production of carbon filaments |
US4013753A (en) * | 1973-10-09 | 1977-03-22 | Bayer Aktiengesellschaft | Process for the production of spontaneously crimping polyacrylonitrile composite fibres with improved crimp properties |
Also Published As
Publication number | Publication date |
---|---|
NL254391A (es) | |
CH386617A (fr) | 1965-01-15 |
GB954553A (en) | 1964-04-08 |
ES259995A1 (es) | 1960-12-01 |
DE1186977B (de) | 1965-02-11 |
FR1240653A (fr) | 1960-09-09 |
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