US3681004A - Polyacrylonitrile fibres - Google Patents
Polyacrylonitrile fibres Download PDFInfo
- Publication number
- US3681004A US3681004A US2423A US3681004DA US3681004A US 3681004 A US3681004 A US 3681004A US 2423 A US2423 A US 2423A US 3681004D A US3681004D A US 3681004DA US 3681004 A US3681004 A US 3681004A
- Authority
- US
- United States
- Prior art keywords
- fibre
- salt
- carboxylate
- acrylic
- fibres
- 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 2
- 150000003839 salts Chemical class 0.000 abstract description 23
- 150000007942 carboxylates Chemical class 0.000 abstract description 21
- 239000000835 fiber Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 13
- 229920002972 Acrylic fiber Polymers 0.000 abstract description 12
- 230000000737 periodic effect Effects 0.000 abstract description 3
- 230000000717 retained effect Effects 0.000 abstract description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 6
- 239000013522 chelant Substances 0.000 description 6
- -1 alkali metal salts Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000009971 piece dyeing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
-
- 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
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/927—Polyacrylonitrile fiber
Definitions
- carboxylate acrylic fibres are of copolymers containing at least 85 percent by weight of acrylonitrile and at least 0.5 percent by weight of an ethylenically unsaturated carboxylic acid, for example acrylic acid, an a-alkyl acrylic acid such as methacrylic acid and an Ot-SllbStlIlltCd alkyl acrylic acid, such as itaconic acid.
- an ethylenically unsaturated carboxylic acid for example acrylic acid, an a-alkyl acrylic acid such as methacrylic acid and an Ot-SllbStlIlltCd alkyl acrylic acid, such as itaconic acid.
- ethylenically unsaturated monomers for example styrene, vinyl acetate, or an ester of acrylic or methacrylic acid for example methyl methacrylate or methyl acrylate.
- a wet-spun, gelstate carboxylate acrylic fibre is impregnated with a solution of a salt of a metal from Group II of the Periodic Table, and the fibre is dried.
- the preferred salts are those of Ca, Mg, Ba, Sr and Zn.
- the salt is preferably a sulphonate such as p-toluene sulphonate or benzene sulphonateor an inorganic salt, for example sulphate, chloride or nitrate; the carboxylate salts,
- Patented Aug. 1, 1972 for example acetate and benzoate, improve the resistance of the carboxylate acrylic fibre to a lesser extent.
- the resistance to heat-discolouration is significantly increased even when only a proportion of the carboxylate groups in the carboxylate acrylic copolymer are incorporated in chelate groups.
- the maximum resist ance is developed when all the available carboxylate groups (free acid groups and alkali metal salt groups) are deactivated.
- the salt retained by the fibre should be from one half to twice that stoichiometrically required to form the chelate with the available carboxylate groups. Larger proportions are acceptable but do not significantly affect the outcome, except perhaps to accelerate the formation of the chelate.
- the deactivation of the carboxylate groups as degradation catalysts following the impregnation of the gel-state fibre with the salt also reactivates the carboxylate groups as dye sites for basic dyes.
- the gel state fibre is first dyed and then impregnated with the salt of the Group II metal.
- Carboxylate groups already occupied by dye molecules are not significantly susceptible to reaction with the salt so that these groups are not available as they were before dyeing.
- the reaction of the dyed fibre with the salt therefore involves only the supernumerary carboxylate groups, and the stoichiometric proportions of the salt should be calculated on this basis.
- EXAMPLE 1 20 grams of never-dried carboxylate acrylic fibre con taining 2 percent by weight of acrylic acid on the dry fibre weight was immersed for 30 seconds in a 2 percent by weight zinc sulphate solution at 20 C. The fibres, after washing in demineralised water and drying in air at a temperature of 80 C., were 0.5 gm. heavier than another 20 gm. sample of untreated fibers which had been dried in the same way. The treated and untreated fibres were subjected to the heat stability test referred to above. The
- Example 2 The procedure of Example 1 was followed, substituting other salt solutions for the zinc sulphate solution. The solutions are identified in the following table, together with the difference in temperatures at which the treated and untreated samples discoloured to the same extent and in the same time.
- a method of improving the resistance to discolouration by heat of a wet-spun acrylic fibre containing carboxylic acid groups comprising impregnating the gel-state fibre with a solution of an uncolored, non-reducing salt of a metal of Group II of the Periodic Table.
- a method as claimed in claim 1 comprising dyeing the gel-state fibre before impregnating it with the salt solution.
- a method as claimed in claim 1 in which the salt retained by the fibre is from half to twice that stoichiometrically required to react with the available carboxylic acid groups of the fibre.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
A METHOD OF IMPROVING THE RESISTANCE TO DISCOLOURATION BY HEAT OF A WET-SPUN CARBOXYLATE ACRYLIC FIBRE, COMPRISING IMPREGNATING THE GEL-STATE FIBRE WITH A SOLUTION OF A SALT OF A METAL OF GROUP II OF THE PERIODIC TABLE. THE PREFERRED SALTS ARE THOSE OF CA, MG, BA, SR AND ZN. THE SALT RETAINED BY THE FIBRE MAY BE FROM HALF TO TWICE THAT STOICHIOMETRICALLY REQUIRED TO REACT WITH THE AVAILABLE CARBOXYLATE GROUPS OF THE FIBRE.
Description
United States Patent 3,681,004 POLYACRYLONITRILE FIBRES Brian J. D. Torrance, Coventry, England, assignor' to Courtaulds Limited, London, England No Drawing. Filed Jan. 12, 1970, Ser. No. 2,423 Claims priority, application Great Britain, Jan. 20, 1969, 3,067/69 Int. Cl. D06p /00 US. Cl. 8-17 5 Claims ABSTRACT OF THE DISCLOSURE This invention is concerned with improving the resistance to discolouration by heat of acrylic fibres containing covalently bound carboxylic acid groups or alkali metal salts thereof. Such fibres are referred to hereinafter as carboxylate acrylic fibres.
carboxylate acrylic fibres are of copolymers containing at least 85 percent by weight of acrylonitrile and at least 0.5 percent by weight of an ethylenically unsaturated carboxylic acid, for example acrylic acid, an a-alkyl acrylic acid such as methacrylic acid and an Ot-SllbStlIlltCd alkyl acrylic acid, such as itaconic acid. Optionally there may be included in the copolymer one or more ethylenically unsaturated monomers, for example styrene, vinyl acetate, or an ester of acrylic or methacrylic acid for example methyl methacrylate or methyl acrylate.
It is known that carboxylate acrylic fibres are prone to discolour on being heated above 130 C., and as several textile finishing treatments now require that the textiles be heated to above this temperature, methods of increasing the resistance to discolouration by heat of the carboxylate acrylic fibres are of interest.
We have found such a method.
According to the present invention, a wet-spun, gelstate carboxylate acrylic fibre is impregnated with a solution of a salt of a metal from Group II of the Periodic Table, and the fibre is dried. v
The preferred salts are those of Ca, Mg, Ba, Sr and Zn.
We understand the process to involve the chelation of the divalent cation of the salt on the carboxylic acid groups of the carboxylate acrylic compolymer, the chelate being less active as a catalyst to the intramolecular degradation of the copolymer by heat, than is the free carboxyl group or alkali metal carboxylate group of the original polymer, so that the salt impregnated copolymer is more resistant to discolouration by heat.
The formation of the chelate by a double decomposition reaction between the copolymer and the salt leads to the liberation of the anion of the salt as the free acid or alkali metal salt and this by-product is not permanent in the fibre; it is largely washed from the fibre during the impregnation and subsequent wet-processing. However there is evidence that the resistance to discolouration by heat is greater when the impregnant salt is that of a strong acid (having a dissociation constant (K) of at least 1 10- rather than a carboxylic acid. Thus the salt is preferably a sulphonate such as p-toluene sulphonate or benzene sulphonateor an inorganic salt, for example sulphate, chloride or nitrate; the carboxylate salts,
Patented Aug. 1, 1972 for example acetate and benzoate, improve the resistance of the carboxylate acrylic fibre to a lesser extent.
The resistance to heat-discolouration is significantly increased even when only a proportion of the carboxylate groups in the carboxylate acrylic copolymer are incorporated in chelate groups. However the maximum resist ance is developed when all the available carboxylate groups (free acid groups and alkali metal salt groups) are deactivated.
It is preferred that the salt retained by the fibre should be from one half to twice that stoichiometrically required to form the chelate with the available carboxylate groups. Larger proportions are acceptable but do not significantly affect the outcome, except perhaps to accelerate the formation of the chelate.
The deactivation of the carboxylate groups as degradation catalysts following the impregnation of the gel-state fibre with the salt, also reactivates the carboxylate groups as dye sites for basic dyes. In a preferred modification of this process, therefore, the gel state fibre is first dyed and then impregnated with the salt of the Group II metal. Carboxylate groups already occupied by dye molecules are not significantly susceptible to reaction with the salt so that these groups are not available as they were before dyeing. The reaction of the dyed fibre with the salt therefore involves only the supernumerary carboxylate groups, and the stoichiometric proportions of the salt should be calculated on this basis.
It is also possible to partially deactivate the carboxylate groups of the fibre by reaction with the salt and to dye the fibre at some later stage, not necessarily the gel state fibre, but after it has been dried-but ideally this process requires a knowledge of the intended dyeing and the required content of dyeable carboxylate groups-facts not easily ascertained at the fibre-making stage.
Attendant benefits of the process are that certain dyes which change shade on carboxylate acrylic fibres subjected to heat, are no longer so unstable on the salt impregnated fibres. The salt impregnated fibres are also resistant to dyeing to a degree depending on the proportion of carboxylate groups incorporated in the chelate groups and this property may be employed to obtain parti-coloured yarns and fabrics by piece dyeing, when the dye resistant fibres are blended with dyeable fibres.
The effectiveness of the treatment was demonstrated in a series of tests in which multifilament yarns treated in accordance with this invention, and comparable untreated yarns, were mounted together on a rotor in an oven heated to a selected temperature in the range of to C. Samples of both yarns were removed at five minute intervals from the oven, the first at five minutes and the last at 30 minutes. This procedure was repeated at other oven temperatures within the stated range. From the spectrum of results is was possible to select samples of untreated yarn which had discoloured to the same extent within similar dwell times in the oven. In all such cases the temperature required to discolour the treated sample was higher than that which discoloured the untreated sample and this difference in temperature is exemplified in the following examples which identify the impregnating salt.
EXAMPLE 1 20 grams of never-dried carboxylate acrylic fibre con taining 2 percent by weight of acrylic acid on the dry fibre weight was immersed for 30 seconds in a 2 percent by weight zinc sulphate solution at 20 C. The fibres, after washing in demineralised water and drying in air at a temperature of 80 C., were 0.5 gm. heavier than another 20 gm. sample of untreated fibers which had been dried in the same way. The treated and untreated fibres were subjected to the heat stability test referred to above. The
treated fibres required to be heated at a temperature twenty centigrade degrees above that which discoloured the untreated fibre to the same extent in the same time. EMMPLE 2 The procedure of Example 1 was followed, substituting other salt solutions for the zinc sulphate solution. The solutions are identified in the following table, together with the difference in temperatures at which the treated and untreated samples discoloured to the same extent and in the same time.
What is claimed is:
1. A method of improving the resistance to discolouration by heat of a wet-spun acrylic fibre containing carboxylic acid groups comprising impregnating the gel-state fibre with a solution of an uncolored, non-reducing salt of a metal of Group II of the Periodic Table.
2. A method as claimed in claim 1 in which the salt has a cation chosen from the group C-a++, Mg++, Ba++, Sr++ and Zn++ and :an anion derived from an acid having a dissociation constant (K) of at least 1 10- 3. A method as claimed in claim 1 comprising dyeing the gel-state fibre before impregnating it with the salt solution.
4. A method as claimed in claim 1 in which the salt retained by the fibre is from half to twice that stoichiometrically required to react with the available carboxylic acid groups of the fibre.
5. An acrylic fibre containing carboxylic acid groups and Group II metal cations in a proportion equal to onehalf the stoichiometric equivalent of said carboxylic acid groups.
References Cited UNITED STATES PATENTS 3,297,471 1/1967 Traumann 117-62.1 3,410,647 11/1968 Hirshfield s-97 3,091,552 5/1963 Furness 117 13s.s
DONALD LEVY, Primary Examiner U.S. Cl. X.R.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB306769 | 1969-01-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3681004A true US3681004A (en) | 1972-08-01 |
Family
ID=9751377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2423A Expired - Lifetime US3681004A (en) | 1969-01-20 | 1970-01-12 | Polyacrylonitrile fibres |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3681004A (en) |
| AU (1) | AU1025470A (en) |
| BE (1) | BE744681A (en) |
| CH (1) | CH522049A (en) |
| DE (1) | DE2002400A1 (en) |
| FR (1) | FR2028740A1 (en) |
| GB (1) | GB1288563A (en) |
| NL (1) | NL7000345A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3917776A (en) * | 1970-12-12 | 1975-11-04 | Mitsubishi Rayon Co | Process for producing carbon fiber |
| US4001382A (en) * | 1974-02-04 | 1977-01-04 | Japan Exlan Company Limited | Process for producing carbon fibers having excellent physical properties |
| US4060650A (en) * | 1975-06-24 | 1977-11-29 | Kureha Kagaku Kogyo Kabushiki Kaisha | Method for preventing or eliminating water-absorption whitening of a molded article containing an acrylonitrile polymer or copolymer |
| US4507257A (en) * | 1982-03-18 | 1985-03-26 | Hoechst Aktiengesellschaft | Process for preparing acrylic filaments and fibers |
| US4524041A (en) * | 1982-03-18 | 1985-06-18 | Hoechst Aktiengesellschaft | Processes for preparing thermostable fibers and filaments |
-
1969
- 1969-01-20 GB GB306769A patent/GB1288563A/en not_active Expired
-
1970
- 1970-01-12 NL NL7000345A patent/NL7000345A/xx unknown
- 1970-01-12 US US2423A patent/US3681004A/en not_active Expired - Lifetime
- 1970-01-13 AU AU10254/70A patent/AU1025470A/en not_active Expired
- 1970-01-20 FR FR7001898A patent/FR2028740A1/fr active Pending
- 1970-01-20 CH CH74470A patent/CH522049A/en not_active IP Right Cessation
- 1970-01-20 BE BE744681D patent/BE744681A/en unknown
- 1970-01-20 DE DE19702002400 patent/DE2002400A1/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3917776A (en) * | 1970-12-12 | 1975-11-04 | Mitsubishi Rayon Co | Process for producing carbon fiber |
| US4001382A (en) * | 1974-02-04 | 1977-01-04 | Japan Exlan Company Limited | Process for producing carbon fibers having excellent physical properties |
| US4060650A (en) * | 1975-06-24 | 1977-11-29 | Kureha Kagaku Kogyo Kabushiki Kaisha | Method for preventing or eliminating water-absorption whitening of a molded article containing an acrylonitrile polymer or copolymer |
| US4507257A (en) * | 1982-03-18 | 1985-03-26 | Hoechst Aktiengesellschaft | Process for preparing acrylic filaments and fibers |
| US4524041A (en) * | 1982-03-18 | 1985-06-18 | Hoechst Aktiengesellschaft | Processes for preparing thermostable fibers and filaments |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7000345A (en) | 1970-07-22 |
| DE2002400A1 (en) | 1970-07-23 |
| BE744681A (en) | 1970-07-01 |
| CH522049A (en) | 1972-04-30 |
| AU1025470A (en) | 1971-07-15 |
| GB1288563A (en) | 1972-09-13 |
| FR2028740A1 (en) | 1970-10-16 |
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