GB2039827A - Method of Producing Hydrophilic Threads or Fibres - Google Patents
Method of Producing Hydrophilic Threads or Fibres Download PDFInfo
- Publication number
- GB2039827A GB2039827A GB8001243A GB8001243A GB2039827A GB 2039827 A GB2039827 A GB 2039827A GB 8001243 A GB8001243 A GB 8001243A GB 8001243 A GB8001243 A GB 8001243A GB 2039827 A GB2039827 A GB 2039827A
- Authority
- GB
- United Kingdom
- Prior art keywords
- water
- threads
- organic liquid
- organic
- mixable
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000578 dry spinning Methods 0.000 claims abstract description 7
- 230000015271 coagulation Effects 0.000 claims abstract description 5
- 238000005345 coagulation Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 3
- 238000009987 spinning Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 238000002166 wet spinning Methods 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000001891 gel spinning Methods 0.000 abstract 1
- 150000002576 ketones Chemical class 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 9
- 229920002239 polyacrylonitrile Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- -1 aminomethylol groups Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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
Landscapes
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
In a method of producing hydrophilic threads or fibres from an acrylonitrile homopolymerisate or an acrylonitrile copolymerisate by dry- spinning or wet-spinning of a solution of the polymerisate in a non-aqueous organic solvent, coagulation of the threads and subsequent drawing, washing and drying, the water contained in the threads is replaced by organic liquids that do not dissolve the polymerisate, prior to drying of the threads. Preferably the organic liquids are water soluble mono- or polyhydric alcohols, ketones or cyclic ethers optionally mixed with water-insoluble organic liquids.
Description
SPECIFICATION
Improvements in or Relating to a Method of
Producing Hydrophilic Threads or Fibres
The invention relates to a method of producing hydrophilic threads or fibres from an acrylonitrile homopolymerisate or an acrylonitrile copolymerisate having a content of at least 50% by weight of acrylonitrile units that exhibit a water retention capacity of at least 20%, a resistance to tearing of at least 20 cN/tex and an elongation at tear of at least 25%, by dry or wet spinning of a solution of the polymerisate in a non-aqueous organic solvent, coagulation of the threads by evaporation of the organic solvent in a spinning shaft or by precipitation in a spin bath containing precipitating agents, as well as subsequent drawing, washing and drying.
Methods have been known for producing hydrophilic threads or fibres from polymers consisting of or containing acrylonitrile units, by dry or wet spinning. Thus, for instance according to German Offenlegungsschrift No. 20 61 213, hydrophilic fibres are produced by incorporating by polymerisation hydrophilic functional groups, such as carboxyl groups, amino groups, aminomethylol groups or hydroxyl groups, into polyacrylonitrile and wet spinning the mixed polymerisate. For increasing the hydrophilic behaviour of the threads or fibres, also other polymers, such as polyethylene oxide methacrylate, can be incorporated into the polyacrylonitrile, or the polyacrylonitrile can be impregnated with such polymers (cf. Japanese
Patent No. 73 01 322). Furthermore, it has been known to treat wet-spun polyacrylonitrile fibres in the swollen state with aldehyde and acid, as disclosed in U.S.Patent No. 3,733,386, in order to improve the hydrophility.
A further method of producing hydrophilic threads or fibres according to the wet-spinning method according to German Offenlegungsschrift
No. 26 07 996 consists in that low-molecular substances are admixed to the spinning solution which are easily mixable with the spinning solvent and with water and which are washed out of the threads or fibres after coagulation and drawing.
The cavity volume remaining in the threads or fibres in this manner, confers an appropriate water retention capacity to the same.
Finally, in Japanese Patent No. 72 1 5 901 a method is disclosed according to which a pore structure and a water absorption capacity based thereupon are achieved in that wet-spun threads, after drawing, are dried at low temperatures (less than 600 C). the formation of a microporous structure in this case is effected by the fact that the loose polymer structure present in the wetcoagulated gel threads to a great extent is preserved at low drying temperatures. As a result of the low drying temperature, threads are however obtained that have poor textiletechnological properties, in particular a poor elongation.
Dry-spinning methods in which, as disclosed in
German Offenlegungsschriften Nos. 22 54 124 and 26 07 654, either liquid substances being mixable with the spinning solvent and water, or
solid compounds being mixable with the spinning
solvent and a washing liquid, are admixed to the spinning solution and washed out again after
drawing also belong to the prior art.
The known methods have the disadvantage that, on the one hand, the application of the usual
drying temperatures leads to a collapsing of the
cavity structure as a result of the plastifying effect of the water present in the thread, on the other
hand, however, low drying temperatures deteriorate the textile-technological properties, in
particular the elongation.
The invention aims at avoiding these disadvantages and has as its object to provide a method of the initially defined kind with which threads or fibres are obtained in which the pore structure present after spinning is being fixed and collapsing of the pore cavities is prevented by applying drying temperatures above the glass temperature.
This object is achieved according to the invention in that the water contained in the threads is substituted by organic liquids that do not dissolve the polymerisate, prior to drying of the threads.
The threads obtained according to the invention besides the microporous structure, which is essential for the desired water retention capacity, possess also good textile properties, e.g.
a resistance to tearing of at least 20 cN/tex and an elongation at tear of at least 25%.
Preferred embodiments of the invention consist in that organic liquids that are completely or partly mixable with water, and water-soluble organic liquids that form an azeotropic mixture with water, respectively, are used.
According to a special embodiment, an organic liquid that is mixable with water and consists of an organic liquid being unmixable with water and an organic liquid being mixable with water is used as a solubiliser.
The substitution of the water contained in the threads by the organic liquid may take place also in two steps, wherein in the first step a watersoluble organic liquid and in the second step a water-insoluble organic liquid being mixable with the organic liquid used in the first step, are used.
As water-soluble organic liquids mono- or polyvalent alcohols, ketons or cyclic ethers can be used. Alcohols including up to four carbon atoms have proved particularly suitable.
As water-insoluble organic liquids alcohols, esters, ethers and aliphatic, aromatic, if desired halogenated, hydrocarbons can be used.
Advantageously, the substitution of the water by the organic liquid takes place during or after drawing of the threads.
The fixation of the loose pore structure effected by the water substitution results from the fact that the organic liquids replacing the water have no plastifying properties. Therefore, the danger of collapsing of the pore cavities no longer exists with the drying temperatures to be applied, which may amount to 140 to 1500C.
With wet-spun threads and fibres a water retention capacity of up to 100%, with dry-spun threads or fibres a water retention capacity of up to about 25%, can be reached according to the invention.
When carrying out the spinning process as a dry-spinning process, for instance a 26 to 30% solution is pressed through a nozzle into a dryspinning shaft, and the spinning solvent, preferably dimethyl formamide or dimethyl acetamide, is driven off, the threads still exhibiting a residual solvent content of at least 25% when leaving the shaft. The cables thus obtained are stored in cans or are spooled up. Then the cables of several cans or spools are combined into a common ribbon, if desired conducted through a swell bath containing in an aqueous solution either the spinning solvent itself or another
solvent or swelling agent in order to further loosen the polymer structure, then drawn in baths containing the same solvent or swelling agent,
and finally washed in hot water.
The water adhering to the fibre and contained
in the pores, according to the invention is
substituted by the organic solvent.
When carrying out the spinning process as a
wet-spinning process, an 1 8 to 23% spinning
solution is conducted into a precipitation bath, a
swollen gel structure being obtained by the wet
coagulation. The threads are drawn and washed,
the substitution according to the invention of the
water by an organic liquid being effected prior to
drying.
The method of the invention will now be
explained in more detail in the following
examples:
The water retention capacity, which is
essential for the hydrophility of the threads, has
been determined according to DIN 53 814.
Example 1
A 20% polyacrylonitrile solution in dimethyl
formamide (DMF) is pressed through a 200-hole
nozzle into a spin bath of 1 50C consisting of a
solution of 50% DMF in water. The threads are
drawn off, drawn 7-fold in a boiling solution of 16% DMF in water, washed in boiling water and
finally conducted through two troughs filled with
i-propanol at 200C for the extraction of water, the
second containing an avivage admixture. At last,
drying takes place at 1 400C followed by crushing
in the conventional manner, and cutting.
The fibres obtained, in the light microscope,
show a kidney-shaped to circular cross-section
with an even pore structure.
The following textile data have been obtained
at a titre of 3.3 dtex:
Water retention capacity 30%
Strength 21 cN/tex
Elongation 28%
Example 2
An 18% polyacrylonitrile solution in DMF is pressed through a 200-hole nozzle into a spin bath consisting of 60% DMF in water and having a temperature of 1 50C. The threads are drawn off, drawn 8-fold in a boiling solution of 20% DMF in water, washed in boiling water and then conducted through two troughs filled with ethanol at 200C for the extraction of water, the second containing an avivage admixture. At last, drying takes place at 1 1 OOC followed by crushing in the conventional manner and cutting.
The fibres obtained, in the light microscope, show a bean-shaped to kidney-shaped crosssection with an even pore structure.
The following textile data have been obtained at a titer of 3.3 dtex:
Water retention capacity 70%
Strength 25 cN/tex
Elongation 25%
Example 3
A 30% polyacrylonitrile solution in DMF is pressed through a 240-hole nozzle into a spinning shaft, the spin gas amount and temperature being chosen such that the threads drawn off at the shaft end have a residual DMF content of about 30%. The cables, which have been collected on twenty spools, are then combined into a ribbon of 50,640 dtex, conducted through a swell bath consisting of 80% DMF in water and having a temperature of 200C, drawn 4-fold in 600C hot 75% DMF, washed with water at 300C and finally conducted through two troughs filled with propanol for the extraction of water, the second containing an avivage admixture. At last, drying takes place at 1 300C followed by crushing in the conventional manner, and cutting.
The fibres obtained, in the light microscope, show a dump-bell-shaped cross-section with an even pore structure.
The following textile data have been obtained at a titer of 3.3 dtex:
Water retention capacity 20%
Strength 25 cN/tex
Elongation 30%
Claims (9)
1. A method of producing hydrophilic threads or fibres from an acrylonitrile homopolymerisate or an acrylonitrile copolymerisate having a content of at least 50% by weight of acrylonitrile units that exhibit a water retention capacity of at least 20%, a resistance to tearing of at least 20 cN/tex and an elongation at tear of at least 25%, by dry or wet spinning of a solution of the polymerisate in a non-aqueous organic solvent, coagulation of the threads by evaporation of the organic solvent in a spinning shaft or by precipitation in a spin bath containing precipitating agents, as well as subsequent drawing, washing and drying, characterised in that the water contained in the threads is replaced by organic liquids that do not dissolve the polymerisate, prior to drying of the threads.
2. A method according to claim 1, wherein organic liquids are used that are totally or partly mixable with water.
3. A method according to claim 1 or 2, wherein water-soluble organic liquids are used which form an azeotropic mixture with water.
4. A method according to claim 1, wherein an organic liquid that is mixable with water is used as a solubiliser, consisting of a mixture of an organic liquid that is unmixable with water and an organic liquid that is mixable with water.
5. A method according to claim 1, wherein the substitution of the water contained in the threads by the organic liquid is effected in two steps, a water-soluble organic liquid being used in the first step and a water-insoluble organic liquid that is mixable with the organic liquid used in the first step being used in the second step.
6. A method according to claims 1 to 5, wherein as water-soluble organic liquids mono- or polyvalent alcohols, ketons or cyclic ethers are used.
7. A method according to claims 1,4 and 5, wherein as water-insoluble organic liquids alcohols, esters, ethers and aliphatic, aromatic, if desired halogenated, hydrocarbons are used.
8. A method according to claim 1, wherein the substitution of the water by the organic liquid takes place during or after drawing of the threads.
9. A method substantially as hereinbefore described with reference to the accompanying examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT30879A AT357260B (en) | 1979-01-16 | 1979-01-16 | METHOD FOR PRODUCING HYDROPHILIC FIBERS OR FIBERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2039827A true GB2039827A (en) | 1980-08-20 |
Family
ID=3487108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8001243A Withdrawn GB2039827A (en) | 1979-01-16 | 1980-01-15 | Method of Producing Hydrophilic Threads or Fibres |
Country Status (5)
| Country | Link |
|---|---|
| AT (1) | AT357260B (en) |
| DE (1) | DE3001422A1 (en) |
| FR (1) | FR2446875A1 (en) |
| GB (1) | GB2039827A (en) |
| IT (1) | IT1145651B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19544097C1 (en) | 1995-11-27 | 1997-07-10 | Thueringisches Inst Textil | Moulding solution of cellulose and more water-soluble polysaccharide component |
-
1979
- 1979-01-16 AT AT30879A patent/AT357260B/en not_active IP Right Cessation
-
1980
- 1980-01-15 GB GB8001243A patent/GB2039827A/en not_active Withdrawn
- 1980-01-16 DE DE19803001422 patent/DE3001422A1/en not_active Withdrawn
- 1980-01-16 IT IT47606/80A patent/IT1145651B/en active
- 1980-01-16 FR FR8000932A patent/FR2446875A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| IT8047606A0 (en) | 1980-01-16 |
| DE3001422A1 (en) | 1980-07-24 |
| AT357260B (en) | 1980-06-25 |
| IT1145651B (en) | 1986-11-05 |
| FR2446875A1 (en) | 1980-08-14 |
| ATA30879A (en) | 1979-11-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |