US2648592A - Removing salts from polyacrylonitrile - Google Patents
Removing salts from polyacrylonitrile Download PDFInfo
- Publication number
- US2648592A US2648592A US228759A US22875951A US2648592A US 2648592 A US2648592 A US 2648592A US 228759 A US228759 A US 228759A US 22875951 A US22875951 A US 22875951A US 2648592 A US2648592 A US 2648592A
- Authority
- US
- United States
- Prior art keywords
- salt
- per cent
- fibers
- article
- salts
- 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
- 150000003839 salts Chemical class 0.000 title claims description 34
- 229920002239 polyacrylonitrile Polymers 0.000 title description 8
- 238000000034 method Methods 0.000 claims description 11
- -1 ALKALI METAL SALT Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 238000005345 coagulation Methods 0.000 claims description 5
- 230000015271 coagulation Effects 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000003352 sequestering agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- 239000002904 solvent Substances 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- MNQDKWZEUULFPX-UHFFFAOYSA-M dithiazanine iodide Chemical compound [I-].S1C2=CC=CC=C2[N+](CC)=C1C=CC=CC=C1N(CC)C2=CC=CC=C2S1 MNQDKWZEUULFPX-UHFFFAOYSA-M 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000037307 sensitive skin Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D05—SEWING; EMBROIDERING; TUFTING
- D05B—SEWING
- D05B1/00—General types of sewing apparatus or machines without mechanism for lateral movement of the needle or the work or both
- D05B1/08—General types of sewing apparatus or machines without mechanism for lateral movement of the needle or the work or both for making multi-thread seams
- D05B1/18—Seams for protecting or securing edges
- D05B1/20—Overedge seams
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/06—Chelate
Definitions
- This invention relates to a method for removing metal salts from polymeric films or filaments composed chiefly of acrylonitrile. It is concerned particularly with such a method for minimizing the salt content of fibers of polyacrylonitrile which have been spun from aqueous saline solutions of the polymer.
- the desired salt removal is effected after the fibers have been coagulated and stretched in the desired manner.
- the fiber forming process may entail coagulation of the polymer solution as it is extruded into water, acid or dilute brine, followed by cold stretching or hot stretching, or both, with following or in tervening treatments of the fiber with water or other coagulant to reduce the salt content to a value usually between 2 and 5 per cent.
- Such an amount of residual salt is not detrimental during a subsequent drying operation, though the presence of over 5 per cent salt usually causes the fibers to fuse when heated to C. or so during drying.
- a much lower salt content is required when the fibers are to be used in making woven or knit goods which may be worn in contact with sensitive skins.
- an agent capable of forming a complex with the metal ion or ions of the salt or salts in the fibers include chelating agents and other metal sequestering agents.
- the preferred agents include the alkali metal salts of ethylene diamine tetraacetic acid and the alkali metal salts of the polyphosphoric acids.
- the commoner polyvalent metal ions which may be present in the fibers, including those of zinc, calcium, magnesium, tin, aluminum, antimony, arsenic, bismuth, and others.
- the treatment is carried out while the fibers are still wet from a prior step in the process, as it has been found that dried fibers containing salt lose it very slowly to a solution of one of the complex-forming or sequestering agents, as they do to plain water.
- a solution was prepared consisting of 7 per cent by weight of polyacrylonitrile, having a Staudinger molecular weight of 76,100, 31.6 per cent zinc chloride, 23.2 per cent calcium chloride and 38.2 per cent water.
- This solution having a viscosity of 300 poises,-was extruded through a 100-hole spinneret, having openings 0.0025 inch in diameter, into Water at C.
- the socoagulated tow of filaments was cold-stretched in air 1.8 times its initial length, and was hotstretched in wet steam 2.4 times its cold-stretched length.
- the tow of stretched fibers was washed for 10 seconds with water. Analysis of the product at various stages in the process to this point showed the following values:
- the tow was dried to l per cent moisture content, and had 2.9 per cent zinc chloride and 1.7 per cent calcium chloride. Another portion of the wet tow was soaked in water for one minute, and, when dried, had 0.35 per cent zinc chloride and 0.22 per cent calcium chloride. When, however, the wet tow was led through a 10 per cent solution in water at pH 8 of the tetrasodium salt of ethylene diamine tetracetic acid for one minute, the subsequently dried fibers had 0.04 per cent zinc chloride and 0.08 per cent calcium chloride. By way of contrast, if the tow was dried before being exposed to the solution of sequestering or chelating agent, soaking in such a solution for 18 hours still left over 1 per cent total salt in the redried fibers.
- the invention has been illustrated with respect to the treatment of fibers produced by wet spinning of aqueous saline solutions of polyacrylonitrile. It is applicable as well to the removal of salts from such other products as films made by extrusion and coagulation of such saline solutions.
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)
Description
Patented Aug. 11, 1953 REMOVING SALTS FROM POLY- ACRYLONITRILE George W. Stanton, Walnut Creek, and Theodore B. Lefierdink, Concord, Calif., assignors to The Dow Chemical Company, Midland, Mich.,- a corporation of Delaware N Drawing. Application May 28,1951, Serial N0. 228,759
3 Claims.
This invention relates to a method for removing metal salts from polymeric films or filaments composed chiefly of acrylonitrile. It is concerned particularly with such a method for minimizing the salt content of fibers of polyacrylonitrile which have been spun from aqueous saline solutions of the polymer.
It is taught by Rein in U. S. 2,140,921 and by Kropa in U. S. 2,356,767 that polyacrylonitrile is soluble in concentrated aqueous solutions of certain highly hydrated metal salts, such as zinc chloride, and that such solutions can be spun to make fibers. Such fibers have been criticised in numerous patents as being weak, brittle and full of voids. Such brittleness or weakness may be due in some cases to the voids resulting from too rapid extraction of the salt during coagulation of the filamentary extruded product, but in others it is due to the presence of some of the salt in the final spun product.
In a group of applications filed concurrently herewith by one or both of the present inventors and others, Serial Nos. 228,751 to 228,758 inclusive, it is disclosed that improved spun products can be made from polyacrylonitrile when the latter is first dissolved in an aqueous solution of at least 30 per cent, and usually not over 50 per cent, of a solvent salt and a lesser amount, from 5 to 25 per cent of a non-solvent salt, in proportions such that the aggregate amount of the two salts is at least 55 per cent, by weight. The solvent salts are those whose anions are at least as high in the following table as their cations, and the non-solvent salts are those whose anions are lower in the table than their cations. To be useful, both types of salts employed must be mutually soluble in water.
Anions in Decreasing Order of Efiectlveness Cations in Increasing Order of Effectiveness SCN" While fibers spun from solutions in such mixed salts are superior to those made from solutions in single solvent salts, it is desirable for most purposes that the amount of salt or salts left in the finished fiber be reduced to a minimum. It has been found that the rate of extraction of the last few percent ofsalts from the fibers by water is 'very slow, and often may be considered impractical for use in a continuous fiber spinning process.
It is a principal object of the present invention to provide a practical and rapid method for reducing the salt content of articles such as films or filaments which have been formed from aqueous saline solutions of the polymer of acrylonitrile or of copolymers of at least per cent acrylonitrile with another monoethylenically unsaturated compond.
In accordance with the present invention, which will be described with reference to polyacrylonitrile fibers, the desired salt removal is effected after the fibers have been coagulated and stretched in the desired manner. The fiber forming process may entail coagulation of the polymer solution as it is extruded into water, acid or dilute brine, followed by cold stretching or hot stretching, or both, with following or in tervening treatments of the fiber with water or other coagulant to reduce the salt content to a value usually between 2 and 5 per cent. Such an amount of residual salt is not detrimental during a subsequent drying operation, though the presence of over 5 per cent salt usually causes the fibers to fuse when heated to C. or so during drying. A much lower salt content is required when the fibers are to be used in making woven or knit goods which may be worn in contact with sensitive skins. Hence after the final wet stretching treatment, and before the fibers are dried, they are conducted through an aqueous solution of an agent capable of forming a complex with the metal ion or ions of the salt or salts in the fibers. Such agents include chelating agents and other metal sequestering agents. The preferred agents include the alkali metal salts of ethylene diamine tetraacetic acid and the alkali metal salts of the polyphosphoric acids. These are capable of forming complexes with, and of removing rapidly from solution, the commoner polyvalent metal ions which may be present in the fibers, including those of zinc, calcium, magnesium, tin, aluminum, antimony, arsenic, bismuth, and others. The treatment is carried out while the fibers are still wet from a prior step in the process, as it has been found that dried fibers containing salt lose it very slowly to a solution of one of the complex-forming or sequestering agents, as they do to plain water.
The following example illustrates the mac-- tice of the invention, but is not to be construed as limiting:
A solution was prepared consisting of 7 per cent by weight of polyacrylonitrile, having a Staudinger molecular weight of 76,100, 31.6 per cent zinc chloride, 23.2 per cent calcium chloride and 38.2 per cent water. This solution, having a viscosity of 300 poises,-was extruded through a 100-hole spinneret, having openings 0.0025 inch in diameter, into Water at C. The socoagulated tow of filaments was cold-stretched in air 1.8 times its initial length, and was hotstretched in wet steam 2.4 times its cold-stretched length. The tow of stretched fibers was washed for 10 seconds with water. Analysis of the product at various stages in the process to this point showed the following values:
One portion of the tow was dried to l per cent moisture content, and had 2.9 per cent zinc chloride and 1.7 per cent calcium chloride. Another portion of the wet tow was soaked in water for one minute, and, when dried, had 0.35 per cent zinc chloride and 0.22 per cent calcium chloride. When, however, the wet tow was led through a 10 per cent solution in water at pH 8 of the tetrasodium salt of ethylene diamine tetracetic acid for one minute, the subsequently dried fibers had 0.04 per cent zinc chloride and 0.08 per cent calcium chloride. By way of contrast, if the tow was dried before being exposed to the solution of sequestering or chelating agent, soaking in such a solution for 18 hours still left over 1 per cent total salt in the redried fibers.
In other tests, when the coagulated and stretched product was immersed in aqueous solutions of metal complexing agents while the product was still wet from a prior step in the process, the alkali metal salts of ethylene diamine tetraacetic acid and of polyphosphoric acids removed the polyvalent metal salts effectively from the product. Thus when the treated product has been digested with nitric acid, burned to constant weight, and the ash analyzed photometrically for calcium and colorimetrically with dithiazine for zinc, values as low as nil for both elements have been obtained, and total values for the two are seldom found to exceed 0.2 per cent. The complexing agents have been found to be most effective when their solutions are adjusted to a pH value near 8, as their normally alkaline condition, pH 11 or higher, tends to discolor the fibers.
The invention has been illustrated with respect to the treatment of fibers produced by wet spinning of aqueous saline solutions of polyacrylonitrile. It is applicable as well to the removal of salts from such other products as films made by extrusion and coagulation of such saline solutions.
We claim:
1. The method as claimed in claim 3, wherein the solution of said alkali metal salt is employed at a pH of about 8.
2. The method as claimed in claim 3, wherein the shaped article is a wet-spun fiber of polyacrylonitrile.
3. In a method for making shaped articles by coagulation of an aqueous polyvalent metal saltcontaining saline solution of a polymer containing at least per cent acrylonitrile in the polymer molecule, the improvement which consists in immersing the article, before it has been dried, in an aqueous solution of a water-soluble alkali metal salt of ethylene diamine tetraacetic acid as a sequestering agent for the polyvalent metal ions in the salt contained in the coagulated article, until the salt content is reduced to a negligible value, and then drying the article.
Martell et al., Properties and Uses of Ethylenediamine Tetra Acetic Acid and Its Salts, Beersworth Chemical Co. 194.8Frarningham, Mass, page '7.
Number
Claims (1)
- 3. IN A METHOD FOR MAKING SHAPED ARTICLES BY COAGULATION OF AN AQUEOUS POLYVALENT METAL SALTCONTAINING SALINE SOLUTION OF A POLYMER CONTAINING AT LEAST 85 PER CENT ACRYLONITRILE IN THE POLYMER MOLECULE, THE IMPROVEMENT WHICH CONSISTS IN IMMERSING THE ARTICLE, BEFORE IT HAS BEEN DRIED, IN AN AQUEOUS SOLUTION OF A WATER-SOLUBLE ALKALI METAL SALT OF ETHYLENE DIAMINE TETRAACETIC ACID AS A SEQUESTERING AGENT FOR THE POLYVALENT METAL IONS IN THE SALT CONTAINED IN THE COAGULATED ARTICLE, UNTIL THE SALT CONTENT IS REDUCED TO A NEGLIGIBLE VALUE, AND THEN DRYING THE ARTICLE.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US228759A US2648592A (en) | 1951-05-28 | 1951-05-28 | Removing salts from polyacrylonitrile |
| US319182A US2648593A (en) | 1951-05-28 | 1952-10-27 | Removing salts from polyacrylonitrile |
| DED15083A DE1044346B (en) | 1951-05-28 | 1953-05-18 | Process for the production of structures from polyacrylonitrile |
| FR1082729D FR1082729A (en) | 1951-05-28 | 1953-05-18 | Improvements relating to the manufacturing process for shaped articles |
| NL178428A NL81838C (en) | 1951-05-28 | 1953-05-19 | |
| CH326492D CH326492A (en) | 1951-05-28 | 1953-05-19 | Process for the manufacture of shaped articles such as threads or films from acrylonitrile polymers |
| GB15167/53A GB732008A (en) | 1951-05-28 | 1953-06-01 | Improvements in or relating to the purification of polyacrylonitrile filaments and films |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US228759A US2648592A (en) | 1951-05-28 | 1951-05-28 | Removing salts from polyacrylonitrile |
| US319182A US2648593A (en) | 1951-05-28 | 1952-10-27 | Removing salts from polyacrylonitrile |
| GB15167/53A GB732008A (en) | 1951-05-28 | 1953-06-01 | Improvements in or relating to the purification of polyacrylonitrile filaments and films |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2648592A true US2648592A (en) | 1953-08-11 |
Family
ID=32303003
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US228759A Expired - Lifetime US2648592A (en) | 1951-05-28 | 1951-05-28 | Removing salts from polyacrylonitrile |
| US319182A Expired - Lifetime US2648593A (en) | 1951-05-28 | 1952-10-27 | Removing salts from polyacrylonitrile |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US319182A Expired - Lifetime US2648593A (en) | 1951-05-28 | 1952-10-27 | Removing salts from polyacrylonitrile |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US2648592A (en) |
| CH (1) | CH326492A (en) |
| DE (1) | DE1044346B (en) |
| FR (1) | FR1082729A (en) |
| GB (1) | GB732008A (en) |
| NL (1) | NL81838C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2879203A (en) * | 1956-05-09 | 1959-03-24 | Roussel Uclaf | Recovery of vitamin b12 from diluted solutions |
| US2879204A (en) * | 1956-05-05 | 1959-03-24 | Roussel Uclaf | Vitamin b12 recovery process |
| US2904391A (en) * | 1956-09-10 | 1959-09-15 | Courtaulds Ltd | Production of polyacrylonitrile threads, fibres, filaments and the like |
| US2916348A (en) * | 1956-08-21 | 1959-12-08 | American Cyanamid Co | Production of polyacrylonitrile filaments |
| US3003993A (en) * | 1959-10-19 | 1961-10-10 | Eastman Kodak Co | Process for color stabilizing acrylonitrile polymers by washing with ethylene diamine tetraacetic acid |
| US3056169A (en) * | 1959-09-28 | 1962-10-02 | Du Pont | Process of preparing shaped articles of acrylonitrile polymer containing silver insoluble particles |
| US3057811A (en) * | 1958-04-25 | 1962-10-09 | American Cyanamid Co | Self-insolubilizing mineral pigment coating compositions for paper comprising a water-soluble anionic polymer adhesive and a water-soluble alum-sequestering agent complex |
| US3081273A (en) * | 1960-07-13 | 1963-03-12 | Celanese Corp | Solution of terephthalamide polymer in solvent comprising antimony trichloride and process for preparing same |
| US3121765A (en) * | 1960-09-24 | 1964-02-18 | Toho Rayon Kk | Process for the manufacture of acrylic synthetic fiber |
| US3154509A (en) * | 1960-07-13 | 1964-10-27 | Celanese Corp | Solutions of polymers in solvent comprising antimony trichloride and process for preparing same |
| US3415611A (en) * | 1965-10-28 | 1968-12-10 | Dow Chemical Co | Method of improving heat stability of acrylonitrile polymer fibers |
| US4650624A (en) * | 1984-05-22 | 1987-03-17 | Bayer Aktiengesellschaft | Process for the production of filaments and fibres from acrylonitrile polymers |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2878200A (en) * | 1956-05-23 | 1959-03-17 | Chemstrand Corp | Stabilized acrylonitrile polymer composition and method of preparing same |
| US2878204A (en) * | 1956-05-23 | 1959-03-17 | Chemstrand Corp | Acrylonitrile polymer composition stabilized with metal formaldehyde sulfoxylate, ethylenediamine tetra-acetic acid and sodium salts thereof, and an inorganic acid, and method of making same |
| US2878208A (en) * | 1956-05-23 | 1959-03-17 | Chemstrand Corp | Acrylonitrile polymer composition stabilized with formaldehyde, ethylenediamine tetraacetic acid and sodium salts thereof, and an inorganic acid, and method of making same |
| US3030235A (en) * | 1958-03-13 | 1962-04-17 | American Viscose Corp | Discoloration-resistant regenerated cellulose articles |
| US3079213A (en) * | 1958-06-02 | 1963-02-26 | Yardney International Corp | Antimicrobial treatment of organic materials and composition therefor |
| DE1181367B (en) * | 1960-06-08 | 1964-11-12 | Toho Rayon Kabushiki Kaisha | Process for the production of threads from acrylonitrile polymers or copolymers with at least 85% acrylonitrile by wet spinning |
| CS148810B1 (en) * | 1969-06-13 | 1973-05-24 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2425191A (en) * | 1944-07-13 | 1947-08-05 | American Cyanamid Co | Polymerization of acrylates, methacrylates alone or in mixtures, and products thereof |
-
1951
- 1951-05-28 US US228759A patent/US2648592A/en not_active Expired - Lifetime
-
1952
- 1952-10-27 US US319182A patent/US2648593A/en not_active Expired - Lifetime
-
1953
- 1953-05-18 FR FR1082729D patent/FR1082729A/en not_active Expired
- 1953-05-18 DE DED15083A patent/DE1044346B/en active Pending
- 1953-05-19 NL NL178428A patent/NL81838C/xx active
- 1953-05-19 CH CH326492D patent/CH326492A/en unknown
- 1953-06-01 GB GB15167/53A patent/GB732008A/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2425191A (en) * | 1944-07-13 | 1947-08-05 | American Cyanamid Co | Polymerization of acrylates, methacrylates alone or in mixtures, and products thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2879204A (en) * | 1956-05-05 | 1959-03-24 | Roussel Uclaf | Vitamin b12 recovery process |
| US2879203A (en) * | 1956-05-09 | 1959-03-24 | Roussel Uclaf | Recovery of vitamin b12 from diluted solutions |
| US2916348A (en) * | 1956-08-21 | 1959-12-08 | American Cyanamid Co | Production of polyacrylonitrile filaments |
| US2904391A (en) * | 1956-09-10 | 1959-09-15 | Courtaulds Ltd | Production of polyacrylonitrile threads, fibres, filaments and the like |
| US3057811A (en) * | 1958-04-25 | 1962-10-09 | American Cyanamid Co | Self-insolubilizing mineral pigment coating compositions for paper comprising a water-soluble anionic polymer adhesive and a water-soluble alum-sequestering agent complex |
| US3056169A (en) * | 1959-09-28 | 1962-10-02 | Du Pont | Process of preparing shaped articles of acrylonitrile polymer containing silver insoluble particles |
| US3003993A (en) * | 1959-10-19 | 1961-10-10 | Eastman Kodak Co | Process for color stabilizing acrylonitrile polymers by washing with ethylene diamine tetraacetic acid |
| US3081273A (en) * | 1960-07-13 | 1963-03-12 | Celanese Corp | Solution of terephthalamide polymer in solvent comprising antimony trichloride and process for preparing same |
| US3154509A (en) * | 1960-07-13 | 1964-10-27 | Celanese Corp | Solutions of polymers in solvent comprising antimony trichloride and process for preparing same |
| US3121765A (en) * | 1960-09-24 | 1964-02-18 | Toho Rayon Kk | Process for the manufacture of acrylic synthetic fiber |
| DE1267783B (en) * | 1960-09-24 | 1968-05-09 | Toho Rayon Kabushiki Kaisha Co | Process for the production of fibers from an acrylonitrile polymer |
| US3415611A (en) * | 1965-10-28 | 1968-12-10 | Dow Chemical Co | Method of improving heat stability of acrylonitrile polymer fibers |
| US4650624A (en) * | 1984-05-22 | 1987-03-17 | Bayer Aktiengesellschaft | Process for the production of filaments and fibres from acrylonitrile polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| CH326492A (en) | 1957-12-31 |
| US2648593A (en) | 1953-08-11 |
| NL81838C (en) | 1956-06-15 |
| GB732008A (en) | 1955-06-15 |
| FR1082729A (en) | 1954-12-31 |
| DE1044346B (en) | 1958-11-20 |
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