US3417049A - Stabilization of polyacrylonitrile - Google Patents
Stabilization of polyacrylonitrile Download PDFInfo
- Publication number
- US3417049A US3417049A US546207A US54620766A US3417049A US 3417049 A US3417049 A US 3417049A US 546207 A US546207 A US 546207A US 54620766 A US54620766 A US 54620766A US 3417049 A US3417049 A US 3417049A
- Authority
- US
- United States
- Prior art keywords
- polyacrylonitrile
- stabilising agent
- acid
- article
- fibre
- 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 22
- 230000006641 stabilisation Effects 0.000 title description 4
- 238000011105 stabilization Methods 0.000 title 1
- 239000003381 stabilizer Substances 0.000 description 19
- -1 N-substituted maleamic acid Chemical class 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GWGLGTKSTGSWGQ-UPHRSURJSA-N (z)-4-(carbamoylamino)-4-oxobut-2-enoic acid Chemical compound NC(=O)NC(=O)\C=C/C(O)=O GWGLGTKSTGSWGQ-UPHRSURJSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 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
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WHZLCOICKHIPRL-SREVYHEPSA-N (z)-4-anilino-4-oxobut-2-enoic acid Chemical group OC(=O)\C=C/C(=O)NC1=CC=CC=C1 WHZLCOICKHIPRL-SREVYHEPSA-N 0.000 description 1
- 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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 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
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
Definitions
- composition which comprises polyacrylonitrile and a stabilising agent which comprises maleamic acid or an N-substituted maleamic acid in which the N-substitutants are methyl, ethyl and phenyl groups or the amide group;
- the invention is concerned with the stabilisation of polyacrylonitrile :and particularly with stabilisation against discolouration on exposure to heat.
- polyacrylonitrile I mean both homopolymers of acrylonitrile and also copolymers containing at least 80 percent by weight of acrylonitrile units.
- Such copolymers may be the products of copolymerisation with acrylonitrile of such other monomers :as styrene, methyl acrylate, itaconic acid, methallyl sulphonic acid and its salts, vinyl acetate and vinyl pyridine.
- the invention is particularly applicable to copolymers containing 90 to 95 percent by weight of acrylonitrile units.
- Thermal discolouration of polyacrylonitrile has been known for some time.
- the discolouration is believed to be caused by conjugation of carbon-nitrogen double bonds derived from the cyanide groups.
- proposals for the prevention of this discolouration include, for example, the addition to polymer solutions of reducing agents, which may be organic or inorganic in nature. It has been found that some of the additives employed for the prevention of thermal discolouration interfere with other properties of the polyacrylonitrile, for example the dyeability may be impaired.
- the invention comprises a polyacrylonitrile article containing a stabilising agent which is maleamic acid or an N-substituted maleamic acid.
- a stabilising agent which is maleamic acid or an N-substituted maleamic acid.
- the N-substituents of N-substituted maleamic acids suitable as stabilising agents may be, for example, -CH -C H CO.NH CO.NHR', CO.NR'R -C H or C H R'.
- Examples of N-substituted maleamic acids which may be employed are Maleuric acid CI-I-CO.NHOONH2 CH-COOH.
- CH-COOH and Polyacrylonitrile articles to which the invention relates may take any of the usual forms.
- such an article may be a filament, a staple fibre, a thread, a fabric or a film.
- Such polyacrylonitrile articles may be used in conjunction with articles consisting of other material.
- a yarn or fabric may be a blend of polyacrylonitrile fibres with other fibres.
- the stabilising agent employed in the invention may be incorporated in the polyacrylonitrile article by known methods.
- the most common method of application is by addition of the stabilising agent to a spinning solution 3,417,049 Patented Dec. 17, 1968 of the polyacrylonitrile. This method may be employed Where suitable, but when the solvent is an inorganic salt solution, addition of the stabilising agent thereto can lead to contamination of the solvent if a recycling process is used.
- the stabilising agent should be applied to the polyacrylonitrile article after the article has been formed.
- one method of applying the stabilising agent consists in immersing the article in 'a solution of the agent followed by removal of excess liquor from the article and by drying. In suitable cases this process may be operated continuously. It is preferred that the impregnation of the polyacrylonitrile article with the solution of the stabilising agent should be performed before the article has been dried for the first time since its production.
- the amount of the stabilising agent which is incorporated in the polyacrylonitrile may vary according to such factors as the nature of the article, the degree of stabilisation required and the particular stabilising agent used. Normally, however, it is not necessary to employ more than 5 percent by weight of the compound on the article although more than this, up to 10 percent or higher, may be used. It is preferred to use a quantity of the order of 0.2 ml percent by weight.
- the stabilising agent in a neutralised or partially neutralised form.
- the polyacrylonitrile is dyeable with basic dyes.
- treatment with unneutralised stabilising agent considerably affects the dye uptake but that the effect may be mitigated by use of the agent in a solution which has been partially neutralised with sodium hydroxide, or other base.
- the invention includes polyacrylonitrile articles containing the salts of maleamic acid or N-substituted maleamic acids.
- Example 1 A 200 filament, 600 denier, bright polyacrylonitrile tow was passed continuously, before it had been dried after production, through a bath containing a 1 percent by weight aqueous solution of maleuric acid, which had been neutralised to pH 4.5 with sodium hydroxide. After im' mersion in the bath, the tow was padded to percent take-up and dried in an oven at 80 C.
- Example 5 which were stretched and dried and tested to measure their tability to thermal discolouration.
- the fibres were heated for one hour in an oven at 130 C. during which the fibre yellowness was found to rise from 0.075 to 0.297 compared with a final fibre yellowness of 0.35 for untreated fibre.
- N-substituted maleamic acid in which the N-substituent is selected from the group consisting Of CH3, 'C2H5, -CONH2, and C6H5;
- composition as claimed in claim 1 which contains from 0.1 to 5 percent by weight of the stabilising agent.
- composition as claimed in claim 1 which contains from 0.2 to 1 percent by weight of stabilising agent.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB18462/65A GB1138945A (en) | 1965-05-03 | 1965-05-03 | Improvements in and relating to the stabilisation of polyacrylonitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3417049A true US3417049A (en) | 1968-12-17 |
Family
ID=10112849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US546207A Expired - Lifetime US3417049A (en) | 1965-05-03 | 1966-04-29 | Stabilization of polyacrylonitrile |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3417049A (enrdf_load_stackoverflow) |
| BE (1) | BE680408A (enrdf_load_stackoverflow) |
| DE (1) | DE1669381A1 (enrdf_load_stackoverflow) |
| ES (1) | ES326259A1 (enrdf_load_stackoverflow) |
| GB (1) | GB1138945A (enrdf_load_stackoverflow) |
| NL (1) | NL6605901A (enrdf_load_stackoverflow) |
| SE (1) | SE314824B (enrdf_load_stackoverflow) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG96160A1 (en) * | 1995-06-26 | 2003-05-23 | Inst Textile Tech | Stabilizers for high nitrile multipolymers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2732363A (en) * | 1952-10-21 | 1956-01-24 | Polymerization of acrylonitrile in the | |
| US3210315A (en) * | 1963-02-11 | 1965-10-05 | Monsanto Co | Acrylic fibers made flame resistant with halogenated aliphatic acid esters |
| US3318983A (en) * | 1963-08-27 | 1967-05-09 | Monsanto Co | Recycling ammonium hydroxide-treated water in the production of polyacrylonitrile fibers |
-
1965
- 1965-05-03 GB GB18462/65A patent/GB1138945A/en not_active Expired
-
1966
- 1966-04-29 US US546207A patent/US3417049A/en not_active Expired - Lifetime
- 1966-05-02 NL NL6605901A patent/NL6605901A/xx unknown
- 1966-05-02 SE SE5962/66A patent/SE314824B/xx unknown
- 1966-05-03 ES ES0326259A patent/ES326259A1/es not_active Expired
- 1966-05-03 BE BE680408D patent/BE680408A/xx unknown
- 1966-05-03 DE DE19661669381 patent/DE1669381A1/de active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2732363A (en) * | 1952-10-21 | 1956-01-24 | Polymerization of acrylonitrile in the | |
| US3210315A (en) * | 1963-02-11 | 1965-10-05 | Monsanto Co | Acrylic fibers made flame resistant with halogenated aliphatic acid esters |
| US3318983A (en) * | 1963-08-27 | 1967-05-09 | Monsanto Co | Recycling ammonium hydroxide-treated water in the production of polyacrylonitrile fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1138945A (en) | 1969-01-01 |
| BE680408A (enrdf_load_stackoverflow) | 1966-10-17 |
| SE314824B (enrdf_load_stackoverflow) | 1969-09-15 |
| ES326259A1 (es) | 1967-07-01 |
| NL6605901A (enrdf_load_stackoverflow) | 1966-11-04 |
| DE1669381A1 (de) | 1971-08-05 |
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