US2978439A - Process for the purification of polyamides - Google Patents
Process for the purification of polyamides Download PDFInfo
- Publication number
- US2978439A US2978439A US721108A US72110858A US2978439A US 2978439 A US2978439 A US 2978439A US 721108 A US721108 A US 721108A US 72110858 A US72110858 A US 72110858A US 2978439 A US2978439 A US 2978439A
- Authority
- US
- United States
- Prior art keywords
- polyamides
- hydrazine
- polyamide
- chips
- molecular weight
- 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
- 239000004952 Polyamide Substances 0.000 title claims description 29
- 229920002647 polyamide Polymers 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 8
- 230000008569 process Effects 0.000 title claims description 8
- 238000000746 purification Methods 0.000 title claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 20
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000007859 condensation product Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000012505 colouration Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- KNIUHBNRWZGIQQ-UHFFFAOYSA-N 7-diethoxyphosphinothioyloxy-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 KNIUHBNRWZGIQQ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/46—Post-polymerisation treatment
Definitions
- the polyamides are usually converted into chip form and boiled in water or the chips are washed for several hours with a stream of boiling hot water.
- the water in both cases, possibly contains a small amount of a reducing agent such as hydrogen sulphite or sulphur dioxide. Nevertheless, a yellow colouration or even a deterioration of the polyamide can easily occur which not only efiects the appearance of the polyamide but also reduces the mechanical properties of objects produced therefrom.
- the water be heated up for a short time to temperatures of, for example, between about 50 and about 80 C. after the addition of the hydrazine but before it is used for treating the polyamides.
- the process according to the invention also permits the production of polyamides of the highest quality.
- Example Chips of a polyamide which has been obtained in a known manner from caprolactam are placed in a container in which a stream of water heated to C. can be introduced from below.
- the container is provided with a heating device which heats the water to boiling point while it flows through the container. The water then runs away through an overflow.
- a period of treatment of about 20 to 30 hours is necessary. If in this treatment of the polyamide, water is used without a special additive then the polyamide chips become yellow during the course of the treatment. This is especially true in the case of those chips lying in the proximity of the point of entry of the stream of water.
- polyamide treated according to the invention can be much more easily spun to a thread than a corresponding polyamide which has been treated with water without the addition of hydrazine. Furthermore, fibres made from a polyamide treated according to the invention have improved properties.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent PROCESS FOR THE PURIFICATION OF POLYAMIDES Adolf Kersting, Krefeld-Bockum, Germany, assignor to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Mar. 13, 1958, Ser. No. 721,108 Claims priority, application Italy Mar. 20, 1957 4 Claims. (Cl. 260-78) This invention relates to a process for the purification of polyamides and more particularly to the removal of monomeric and low molecular weight compounds from polyamides by treatment with aqueous solutions of hydrazine.
Polyamides from w-amino-carboxylic acids or their polyamide-forming derivatives, such as lactams, alone and from mixtures of these materials with other polyamide-forming materials, such as diamines and dicarboxylic acids, usually contain a certain amount of unchanged amino-carboxylic acids or low molecular weight condensation products which exude during storage or during working up, for example, during the spinning of melts to thin threads thereby giving the polyamides an undesirable appearance. This can have an extremely deleterious efiect due to the formation of vapours, especially of lactam vapours, and in the case of rather high content of vapourizable materials, can make the working up practically impossible.
In order to reduce the content of these monomeric and low molecular weight products in the polyamides to a suitably low amount, the polyamides are usually converted into chip form and boiled in water or the chips are washed for several hours with a stream of boiling hot water. The water, in both cases, possibly contains a small amount of a reducing agent such as hydrogen sulphite or sulphur dioxide. Nevertheless, a yellow colouration or even a deterioration of the polyamide can easily occur which not only efiects the appearance of the polyamide but also reduces the mechanical properties of objects produced therefrom.
I have now found that such colouration or deterioration of polyamides by their treatment with hot water can be prevented in a technically simple and advantageous manner if small amounts, such as for example, about to about 100 milligrams per litre of hydrazine or hydrazine hydrate are added to the water before it comes into contact with the polyamide.
If cold water is initially used, then it is recommended that the water be heated up for a short time to temperatures of, for example, between about 50 and about 80 C. after the addition of the hydrazine but before it is used for treating the polyamides.
Since the hydrazine does not leave behind either solid materials such as possible salts in the case of hydrogen sulphite, or corrosive or saponifying materials such as sulphuric acid from the addition of sulphur dioxide, and finally, since it does not in any Way cause recognisable alteration of the polyamide, the process according to the invention also permits the production of polyamides of the highest quality.
The following example is given by way of illustration:
Example Chips of a polyamide which has been obtained in a known manner from caprolactam are placed in a container in which a stream of water heated to C. can be introduced from below. The container is provided with a heating device which heats the water to boiling point while it flows through the container. The water then runs away through an overflow. In order to reduce the content of monomeric and low molecular weight products in the polyamide to less than about 1 percent, a period of treatment of about 20 to 30 hours is necessary. If in this treatment of the polyamide, water is used without a special additive then the polyamide chips become yellow during the course of the treatment. This is especially true in the case of those chips lying in the proximity of the point of entry of the stream of water. If there are added 40 milligrams of hydrazine hydrate per litre of water before its admission to the heater, then the polyamide chips remain completely white. The polyamide treated according to the invention can be much more easily spun to a thread than a corresponding polyamide which has been treated with water without the addition of hydrazine. Furthermore, fibres made from a polyamide treated according to the invention have improved properties.
.I claim:
1. Process for the purification of chips of high molecular weight polyamides selected from the group consisting of poly-E-aminocaproic acid and mixed polyamides of E-aminocaproic acid with polyamide forming diamines and dicarboxylic acids, containing impurites selected from the group consisting of monomeric E-caprolactam and low molecular weight condensation products thereof, which comprises washing said chips with boiling aqueous solutions of hydrazine, the amount of hydrazine being from about 10-100 mg./l. solution.
2. A process according to claim 1 wherein the aqueous treatment solution contains 40 milligrams of hydrazine per litre.
3. A process according to claim 1 wherein the solution- References Cited in the file of this patent UNITED STATES PATENTS Mayner Jan. 17, 1956 Lynch Feb. 21, 1956
Claims (1)
1. PROCESS FOR THE PURIFICATION OF CHIPS OF HIGH MOLECULAR WEIGHT POLYAMIDES SELECTED FROM THE GROUP CONSISTING OF POLY-E-AMINOCAPROIC ACID AND MIXED POLYAMIDES OF E-AMINOCAPROIC ACID WITH POLYAMIDE FORMING DIAMINES AND DICARBOXYLIC ACIDS, CONTAINING IMPURITIES SELECTED FROM THE GROUP CONSISTING OF MONOMERIC E-CAPROLACTAM AND LOW MOLECULAR WEIGHT CONDENSATION PRODUCTS THEREOF, WHICH COMPRISES WASHING SAID CHIPS WITH BOILING AQUEOUS SOLUTIONS OF HYDRAZINE, THE AMOUNT OF HYDRAZINE BEING FROM ABOUT 10-100 MG./1. SOLUTION.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1188817X | 1957-03-20 | ||
| IT349075X | 1957-03-20 | ||
| IT2978439X | 1957-03-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2978439A true US2978439A (en) | 1961-04-04 |
Family
ID=30119217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US721108A Expired - Lifetime US2978439A (en) | 1957-03-20 | 1958-03-13 | Process for the purification of polyamides |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US2978439A (en) |
| FR (1) | FR1188817A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3149095A (en) * | 1960-08-24 | 1964-09-15 | Bemberg Spa | Process for the purification of polyamides |
| US3254059A (en) * | 1962-02-12 | 1966-05-31 | Monsanto Co | Treatment of chips of polycarbonamide containing organic derivative of hypophosphorous acid |
| US3373145A (en) * | 1965-04-29 | 1968-03-12 | Allied Chem | Washing of polymer particulates by regular periodic ebb and flow of aqueous solvent |
| US3374207A (en) * | 1964-11-12 | 1968-03-19 | Inventa Ag | Continuous process for the extraction of monomers and oligomers from highly polymerized caprolactam granules |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2731081A (en) * | 1953-04-13 | 1956-01-17 | Ind Rayon Corp | Method for the removal of monomers, etc. from molten polymers |
| US2735840A (en) * | 1956-02-21 | Vacuum pump |
-
1957
- 1957-12-19 FR FR1188817D patent/FR1188817A/en not_active Expired
-
1958
- 1958-03-13 US US721108A patent/US2978439A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2735840A (en) * | 1956-02-21 | Vacuum pump | ||
| US2731081A (en) * | 1953-04-13 | 1956-01-17 | Ind Rayon Corp | Method for the removal of monomers, etc. from molten polymers |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3149095A (en) * | 1960-08-24 | 1964-09-15 | Bemberg Spa | Process for the purification of polyamides |
| US3254059A (en) * | 1962-02-12 | 1966-05-31 | Monsanto Co | Treatment of chips of polycarbonamide containing organic derivative of hypophosphorous acid |
| US3374207A (en) * | 1964-11-12 | 1968-03-19 | Inventa Ag | Continuous process for the extraction of monomers and oligomers from highly polymerized caprolactam granules |
| US3373145A (en) * | 1965-04-29 | 1968-03-12 | Allied Chem | Washing of polymer particulates by regular periodic ebb and flow of aqueous solvent |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1188817A (en) | 1959-09-25 |
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