US3121765A - Process for the manufacture of acrylic synthetic fiber - Google Patents
Process for the manufacture of acrylic synthetic fiber Download PDFInfo
- Publication number
- US3121765A US3121765A US138581A US13858161A US3121765A US 3121765 A US3121765 A US 3121765A US 138581 A US138581 A US 138581A US 13858161 A US13858161 A US 13858161A US 3121765 A US3121765 A US 3121765A
- Authority
- US
- United States
- Prior art keywords
- tow
- chloride
- aqueous solution
- solution
- 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
Links
- 238000000034 method Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920002994 synthetic fiber Polymers 0.000 title claims description 5
- 239000012209 synthetic fiber Substances 0.000 title claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 235000002639 sodium chloride Nutrition 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 235000005074 zinc chloride Nutrition 0.000 claims description 15
- 239000011592 zinc chloride Substances 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 235000013877 carbamide Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 10
- 239000000835 fiber Substances 0.000 description 8
- 238000011033 desalting Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000002040 relaxant effect Effects 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
-
- 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
- This invention relates to a process for the manufacture of a synthetic acrylic fiber by spinning a spinning solution comprising zinc chloride solution and polymer containing acrylonitrile as a principal constituent, and then treating .the coagulated tow with an aqueous solution of a compound so as to produce a zinc complex ion with the object of avoiding the degradation of fiber quali ty due to remaining salts.
- the present invention has been reached by our new knowledge on the effect of compounds, forming complex ion with zinc ion, such as ammonium, amine or chlorine, and the process is industrially useful and practicable.
- Desalting agents are sodium chloride, potassium chloride, ammonium chloride, urea, thiourea and others, that is, election donor compounds which coordinate to cation forming complex ion.
- These compounds which have chloride, ammonium ion, or amino group can form complex ions with the zinc ion as in the following.
- Halides, such as NaCl, KCl, NH Cl form complex ions, some of which are [ZnCld and [ZnCl 0H and in the case of NH Cl occur, moreover, amine complexes, such as and so on.
- urea and thiourea occur [ZH(NHQCONHQ)4]++ and [ZI1(NH2CSNH2)4]++ respectively. All of these complex ions have tetrahedral 4-coordinated structure.
- the salt removal treatment based on the above discovery may be applied to a dried fiber, but from the point of easiness in removing the salt and of simplification in industrial fiber process, it is effected during or after the washing process of coagulated tow with water which has been coagulated from a spinning solution as is a common practice, and then the coagulated tow is treated with an aqueous solution of above mentioned compounds.
- zinc compounds which remained in the tow as hydroxide or hydrated oxide of zinc, can diffuse and dissolve out into the solution as water soluble complex ions.
- the tow which is formed by extruding a polymer solu- 3,121,765 Patented Feb. 18, 1964 tion into a coagulating bath comprised of a more dilute aqueous salt solution of the same or similar salt system as employed in the solvent of the polymer solution, may be stretched at moderate temperature in water, or stretched under moderate temperature and humidity after water washing. Thereafter, it may go through required aftertreatments, such as oiling, heat stretching and relaxing processes that are in common practice.
- the salt removing treatment is accomplished, according to this invention, by using 1 to 20 percent aqueous solution of desalting agent, preferably 5 to 15 percent, at 70 C. to boiling temperature, preferably over C.
- Tow B is composed of 52.6% polymer, 45.1% water and 2.3% zinc chloride, and, when squeezed and dried in air, it contains 0.39% residual zinc.
- T he tow B treated with various salt removal treatments (I, II, III, IV and V) and dried in air to 1 percent moisture content was analyzed and found to include residual zinc chloride as follows:
- Example 1 A solution was prepared consisting of 9% by weight of copolymer containing mole percent of acrylonitrile and 5 mole percent of methyl acrylate having a Standinger molecular weight of 82,000, 50.9% by weight of zinc chloride and 41% of water. This solution, having a viscosity of 360 poises at 30 C., was extruded through a -hole spinneret having openings respectively 0.08 mm. in diameter, into an aqueous solution of 15% by weight of zinc chloride at 15 C. The so-coagulated tow of filament was stretched 1.6 times its original length during washing with water (the sample here called A), and then stretched in boiling water three times its cold stretched length (sample B).
- This tow B of stretched fibers was washed with water and, when dried in air to 1% moisture content, had 0.39% of zinc chloride.
- This tow was boiled in an aqueous solution of 5% by weight of ammonium chloride for 2 minutes, then washed with water and, when dried, had 0.024% of zinc chloride.
- Example 2 The tow A in Example 1 was stretched in boiling water containing 7% of sodium chloride two times its original length and then in boiling water 5 times its original length, and when dried, had only 0.034% of zinc chloride in it.
- Example 3 The other portion of tow A was treated with aqueous solution of 10% of urea, washed with water and, when dried, had 0.039% of zinc chloride.
- the other portion of tow B was treated similarly as A and had had only 0.029% of zinc chloride.
- a method for manufacturing acrylic synthetic fibers comprising spinning into a coagulated tow a solution of a polymer containing acrylonitrile and a solvent of aqueous zinc chloride, contacting the coagulated toW with an aqueous solution containing 1 to 20 percent of a desalting agent chosen from the group consisting of ammonium chloride, sodium chloride, potassium chloride, urea and thiourea, and maintaining the aqueous solution in a temperature range of from 70 to 100 C.
- a desalting agent chosen from the group consisting of ammonium chloride, sodium chloride, potassium chloride, urea and thiourea
- a method for manufacturing acrylic synthetic fibers comprising spinning into a coagulated tow a solution of a polymer containing acrylonitrile and a solvent of aqueous zinc chloride, contacting the coagulated tow With an aqueous solution containing 1 to percent of a desalting agent chosen from the group consisting of ammonium chloride, sodium chloride, potassium chloride, urea and thiourea, and maintaining the aqueous solution in a temperature range of from to C.
- a desalting agent chosen from the group consisting of ammonium chloride, sodium chloride, potassium chloride, urea and thiourea
Description
United States Patent 3,121,765 PROCESS FOR THE MANUFACTURE OF ACRYLIC SYNTHETIC FIBER Ichiro Kanda, Miciliaiti Nakaiima, and Makoto Amiya,
all of Kitaiima-machi, Itano-gun, Tokushima Prefecture, .Iapan, assignors to Tolio Rayon Kahushiki Kaisha, Tokyo, Japan, a corporation of Japan No Drawing. Filed Sept. 18, 1961,. Ser. No. 138,581 Claims priority, application Japan Sept. 24, 1960 4- Claims. (Cl. 264-182) This invention relates to a process for the manufacture of a synthetic acrylic fiber by spinning a spinning solution comprising zinc chloride solution and polymer containing acrylonitrile as a principal constituent, and then treating .the coagulated tow with an aqueous solution of a compound so as to produce a zinc complex ion with the object of avoiding the degradation of fiber quali ty due to remaining salts.
It has been reported that in fiber products obtained from an acrylic polymer solution using concentrated aqueous inorganic salt solution containing zinc chloride as a principal constituent, inorganic salts particularly zinc compound in the form of hydroxide or oxide remained in the fibers and that such residual salts caused the quality of the products to be unfavorably reduced. For instance, fiber containing a residual salt of more than 1 percent by weight is brittle and dyed in dull color, and upon heating it becomes yellowish and weak. To improve on the above disadvantages, it has been proposed to apply an ion-exchange resin method of Japanese Pat. Publn. No. 2,369/ 56, or a zinc chloride method by treating the fiber with compounds such as sodium ethylenediamine tetraacetate according to the Japanese Pat. Publn. No. 8,444/57. But these methods are too expensive for industrial practice.
The present invention has been reached by our new knowledge on the effect of compounds, forming complex ion with zinc ion, such as ammonium, amine or chlorine, and the process is industrially useful and practicable.
Desalting agents, in the present invention, are sodium chloride, potassium chloride, ammonium chloride, urea, thiourea and others, that is, election donor compounds which coordinate to cation forming complex ion. These compounds which have chloride, ammonium ion, or amino group can form complex ions with the zinc ion as in the following. Halides, such as NaCl, KCl, NH Cl form complex ions, some of which are [ZnCld and [ZnCl 0H and in the case of NH Cl occur, moreover, amine complexes, such as and so on. In the case of urea and thiourea occur [ZH(NHQCONHQ)4]++ and [ZI1(NH2CSNH2)4]++ respectively. All of these complex ions have tetrahedral 4-coordinated structure.
The salt removal treatment based on the above discovery may be applied to a dried fiber, but from the point of easiness in removing the salt and of simplification in industrial fiber process, it is effected during or after the washing process of coagulated tow with water which has been coagulated from a spinning solution as is a common practice, and then the coagulated tow is treated with an aqueous solution of above mentioned compounds.
According to this invention, by immersing tow after being passed through the coagulating bath in an aqueous solution of desalting agents, zinc compounds, which remained in the tow as hydroxide or hydrated oxide of zinc, can diffuse and dissolve out into the solution as water soluble complex ions.
The tow which is formed by extruding a polymer solu- 3,121,765 Patented Feb. 18, 1964 tion into a coagulating bath comprised of a more dilute aqueous salt solution of the same or similar salt system as employed in the solvent of the polymer solution, may be stretched at moderate temperature in water, or stretched under moderate temperature and humidity after water washing. Thereafter, it may go through required aftertreatments, such as oiling, heat stretching and relaxing processes that are in common practice.
The salt removing treatment is accomplished, according to this invention, by using 1 to 20 percent aqueous solution of desalting agent, preferably 5 to 15 percent, at 70 C. to boiling temperature, preferably over C.
Results according to a few examples of salt removal treatment are shown in the following Table 1, using coagulated tow B in the following Example 1. Tow B is composed of 52.6% polymer, 45.1% water and 2.3% zinc chloride, and, when squeezed and dried in air, it contains 0.39% residual zinc.
T he tow B treated with various salt removal treatments (I, II, III, IV and V) and dried in air to 1 percent moisture content was analyzed and found to include residual zinc chloride as follows:
TABLE 1 Method I II III IV V Residual ZnCl Percent 0.173 0.150 0.024 0.026 0.029
invention, but are not to be construedas limiting.
Example 1 A solution was prepared consisting of 9% by weight of copolymer containing mole percent of acrylonitrile and 5 mole percent of methyl acrylate having a Standinger molecular weight of 82,000, 50.9% by weight of zinc chloride and 41% of water. This solution, having a viscosity of 360 poises at 30 C., was extruded through a -hole spinneret having openings respectively 0.08 mm. in diameter, into an aqueous solution of 15% by weight of zinc chloride at 15 C. The so-coagulated tow of filament was stretched 1.6 times its original length during washing with water (the sample here called A), and then stretched in boiling water three times its cold stretched length (sample B). This tow B of stretched fibers was washed with water and, when dried in air to 1% moisture content, had 0.39% of zinc chloride. This tow was boiled in an aqueous solution of 5% by weight of ammonium chloride for 2 minutes, then washed with water and, when dried, had 0.024% of zinc chloride.
Example 2 The tow A in Example 1 was stretched in boiling water containing 7% of sodium chloride two times its original length and then in boiling water 5 times its original length, and when dried, had only 0.034% of zinc chloride in it.
Example 3 The other portion of tow A was treated with aqueous solution of 10% of urea, washed with water and, when dried, had 0.039% of zinc chloride. The other portion of tow B was treated similarly as A and had had only 0.029% of zinc chloride.
What we claim is:
1. A method for manufacturing acrylic synthetic fibers comprising spinning into a coagulated tow a solution of a polymer containing acrylonitrile and a solvent of aqueous zinc chloride, contacting the coagulated toW with an aqueous solution containing 1 to 20 percent of a desalting agent chosen from the group consisting of ammonium chloride, sodium chloride, potassium chloride, urea and thiourea, and maintaining the aqueous solution in a temperature range of from 70 to 100 C.
2. The method as recited in claim 1, wherein the aqueous solution contains 5 to percent of the desalting agent.
3. A method for manufacturing acrylic synthetic fibers comprising spinning into a coagulated tow a solution of a polymer containing acrylonitrile and a solvent of aqueous zinc chloride, contacting the coagulated tow With an aqueous solution containing 1 to percent of a desalting agent chosen from the group consisting of ammonium chloride, sodium chloride, potassium chloride, urea and thiourea, and maintaining the aqueous solution in a temperature range of from to C.
4. The method as recited in claim 3, wherein the aqueous solution contains 5 to 15 percent of the desalting agent.
References Cited in the file of this patent
Claims (1)
1. A METHOD FOR MANUFACTURING ACRYLIC SYNTHETIC FIBERS COMPRISING SPINNING INTO A COAGULATED TOW A SOLUTION OF A POLYMER CONTAINING ACRYLONITRILE AND A SOLVENT OF AQUEOUS ZINC CHLORIDE, CONTACTING THE COAGULATED TOW WITH AN AQUEOUS SOLUTION CONTAINING 1 TO 20 PERCENT OF A DISALTING AGENT CHOSEN FROM THE GROUP CONSISTING OF AMMONIUM CHLORIDE, SODIUM CHLORIDE, POTASSIUM CHLORIDE, UREA AND THIOUREA, AND MAINTAINING THE AQUEOUS SOLUTION IN A TEMPERATURE RANGE OF FROM 70* TO 100*C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3974560 | 1960-09-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3121765A true US3121765A (en) | 1964-02-18 |
Family
ID=12561486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US138581A Expired - Lifetime US3121765A (en) | 1960-09-24 | 1961-09-18 | Process for the manufacture of acrylic synthetic fiber |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3121765A (en) |
| BE (1) | BE608206A (en) |
| DE (1) | DE1267783B (en) |
| FI (1) | FI40194B (en) |
| GB (1) | GB954860A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3622658A (en) * | 1969-09-11 | 1971-11-23 | Japan Exlan Co Ltd | Method of treating acrylonitrile synthetic fiber |
| US4925604A (en) * | 1984-10-16 | 1990-05-15 | Nikkiso Co., Ltd. | Process for preparing a carbon fiber of high strength |
| CN112645653A (en) * | 2020-12-17 | 2021-04-13 | 江苏长路交通工程有限公司 | Fiber-toughened anti-crack cement-stabilized macadam, preparation method and construction method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB636476A (en) * | 1949-02-02 | 1950-05-03 | Edgar Bertie Johnson | Improvements in or relating to the production of textile materials having a basis ofpolyacrylonitrile |
| US2558730A (en) * | 1947-09-04 | 1951-07-03 | American Cyanamid Co | Method of preparing shaped products from polymers and copolymers of acrylonitrile |
| US2558781A (en) * | 1947-09-04 | 1951-07-03 | American Cyanamid Co | Method of treating water-swollen polymers |
| US2648592A (en) * | 1951-05-28 | 1953-08-11 | Dow Chemical Co | Removing salts from polyacrylonitrile |
| CA564327A (en) * | 1958-10-07 | B. Bates Emile | Wet heat treatment of material of poor electrical conductivity |
-
1961
- 1961-09-12 GB GB32636/61A patent/GB954860A/en not_active Expired
- 1961-09-15 BE BE608206A patent/BE608206A/en unknown
- 1961-09-18 US US138581A patent/US3121765A/en not_active Expired - Lifetime
- 1961-09-20 FI FI1650/61A patent/FI40194B/fi active
- 1961-09-22 DE DEP1267A patent/DE1267783B/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA564327A (en) * | 1958-10-07 | B. Bates Emile | Wet heat treatment of material of poor electrical conductivity | |
| US2558730A (en) * | 1947-09-04 | 1951-07-03 | American Cyanamid Co | Method of preparing shaped products from polymers and copolymers of acrylonitrile |
| US2558781A (en) * | 1947-09-04 | 1951-07-03 | American Cyanamid Co | Method of treating water-swollen polymers |
| GB636476A (en) * | 1949-02-02 | 1950-05-03 | Edgar Bertie Johnson | Improvements in or relating to the production of textile materials having a basis ofpolyacrylonitrile |
| US2648592A (en) * | 1951-05-28 | 1953-08-11 | Dow Chemical Co | Removing salts from polyacrylonitrile |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3622658A (en) * | 1969-09-11 | 1971-11-23 | Japan Exlan Co Ltd | Method of treating acrylonitrile synthetic fiber |
| US4925604A (en) * | 1984-10-16 | 1990-05-15 | Nikkiso Co., Ltd. | Process for preparing a carbon fiber of high strength |
| CN112645653A (en) * | 2020-12-17 | 2021-04-13 | 江苏长路交通工程有限公司 | Fiber-toughened anti-crack cement-stabilized macadam, preparation method and construction method |
Also Published As
| Publication number | Publication date |
|---|---|
| BE608206A (en) | 1962-01-02 |
| GB954860A (en) | 1964-04-08 |
| DE1267783B (en) | 1968-05-09 |
| FI40194B (en) | 1968-07-31 |
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