US3300443A - Polyamides stabilized with manganous silicate and process for producing same - Google Patents
Polyamides stabilized with manganous silicate and process for producing same Download PDFInfo
- Publication number
- US3300443A US3300443A US287767A US28776763A US3300443A US 3300443 A US3300443 A US 3300443A US 287767 A US287767 A US 287767A US 28776763 A US28776763 A US 28776763A US 3300443 A US3300443 A US 3300443A
- Authority
- US
- United States
- Prior art keywords
- polymer
- light
- yarn
- manganous
- manganous silicate
- 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 12
- 229920002647 polyamide Polymers 0.000 title claims description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title description 27
- 238000000034 method Methods 0.000 title description 6
- 230000008569 process Effects 0.000 title description 5
- 239000002245 particle Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 21
- 239000011572 manganese Substances 0.000 description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- 150000002697 manganese compounds Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 210000002816 gill Anatomy 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- -1 manganese salts Chemical class 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
Definitions
- the sensitivity of the yarn in the presence of light increases with its content of titanium dioxide and when said content ranges between 0.4 and 3% by weight, the degradation is even rapid.
- manganese compounds are somewhat difiicult insofar as at the temperature at which the polymerization iscarried out and in the presence of water such compounds generally become brown thus colouring the polymer.
- the invention is characterized by the fact that the artificial or natural manganous silicate in Rately crushed and purified state, is incorporated either into the polyamides forming monomersor into the solutions of the monomers containing chain stabilizers, catalysts and opacifying agents, the polymerization being provided by usual methods.
- the manganous silicate may be incorporated at any operation stage, for instance, adding it to the monomer or the partly formed polymer before putting the autoclave under vacuum or to the polymer already formed as chips before their spinning.
- EXAMPLE I Into a 20 litre autoclave there are put 10 kg. of caprolactam containing 45 gr. of titanium dioxide of the anatase type, 500 gr. of water, 18 gr. of acetic acid and 10 gr. of natural manganous silicate finely crushed and purified the manganese content of which corresponds to 28% by weight.
- the autoclave is heated to 250 C. venting it from time to time to eliminate the steam. Under continuous stirring and at atmospheric pressure the autoclave is held at same temperature for further 14 hours, after which time it is put gradually under vacuum to ob tain a residual pressure of 260 mm. Hg within two hours time.
- the polymer formed is finally extruded by the pressure of an inert gas, cooled and cut into uniform chips.
- the polymer obtained is perfectly white and its visco6sity in sulfuric acid (concentration of 1%) is equalto 2. 5.
- the polymer After washing and drying, the polymer is spun on a head wit-h a melting grid providing single 15 denier yarns and 6 filament yarns of 30 deniers.
- the improved light fasteness of a yarn obtained from said polymer is readily apparent.
- the yarn made of a polymer obtained under the conditions described hereinabove, without the addition of manganous silicate shows, after 100 hours of exposure to light an average tenacity loss of 42% for the count 15/1 and 56% for the count 30/ 6.
- Example II The operation is the same as for Example I, however with the use of 200 gr. of titanium dioxide of the anatase type as opacifier (correspondintg to 2% by weight of the monomer).
- the polymer obtained is prefectly white and its relative viscosity in sulfuric acid is equal to 2.80.
- the average loss of tenacity of the yarns obtained with said polymer after 100 hours exposure in the Fade- Ometer under the conditions described in the Example I, is equal to 3.5% for the count 15/1 and to 5% for the count 40/10 as compared with an average loss of 41% for the count 15/1 and of 69% for the count 40/ observed in a yarn coming from a polymer obtained under similar conditions without any addition of manganous silicate.
- Example Ill The operation is the same as in Example I, but with the use of 1.8 gr. of natural crushed manganous silicate containing 28% by weight of Mn.
- the polymer obtained is perfectly white and its visocity in sulfuric acid is equal to 2.66.
- the average loss of tenacity of the yarns obtained from said polymer after 100 hours of exposure in the Fade-Ometer under the conditions described in Example I is equal to 6% for the count /1 and 9% for the count 30/6 as compared with the loss already disclosed in Example I for a yarn containing no manganous silicate.
- Example IV The operation is the same as in Example I but with the use of 13 gr. of finely crushed artificial mangaanous containing 28% by weight of Mn as stabilizer.
- the polymer obtained is perfectly white and its viscosity in sulfuric acid is 2.70.
- the average loss of tenacity of the yarns obtained from said polymer after 100 hours of exposure in the Fade-Ometer under the conditions described in Example I, is equal to 1% for the count 15/1 and to 2% for the count 30/6 as compared with the loss already disclosed in Example I for a yarn made without any addition of manganous silicate.
- Example V The operation is the same as in Example I, but with the use of 13 gr. of finely crushed artificial manganous silicate, the manganese content of which is equal to 22% by weight as a stabilizer to light degradation.
- Example VI Into a litre autoclave there are introduced 8 kg. of adipate of hexamethylenediammonium containing 0.32%
- the autoclave is heated to the temperature of 110 C.
- the pressure during 1 hour is gradually lowered to autmospheric pressure, while the mass under continuous stirring is heated to 275 C. and maintained during 2 hours at said temperature and pressure.
- Vacuum is then applied thus bringing gradually the autoclave to a pressure of a few mm. of mercury within 1 hour, and maintaining said reduced pressure during further half an hour. Finally, the pressure is restored with a dried inert gas and a polymer obtained is extruded. cooled and cut into uniform chips.
- the polymer obtained is perfectly white and is intrinsic viscosity in metacresol is 1.06.
- the average loss of tenacity of the yarn obtained from said polymer after hours of exposure to the Fade- Ometer under the conditions described in Example I is equal to 3% for the count 15/1 and to 5% for the count 30/6, as compared with an average loss of 32% for the count 15/1 and of 48% for the count 30/6 of a yarn made of a polymer obtained under the same conditions but without any incorporation of manganous silicate.
- Example VII The operation is the same as in Example I with the use however of a monomer constituted by 13 kg. of warnino-undecanoic acid containing 0.28% by weight of acetic acid, 58.5 gr. (0.45% by weight) of titanium dioxide of the anatase type, 4.250 kg. of distilled water and 12.5 gr. of finely crushed natural manganous silicate containing 0.28% by weight of manganese metal.
- the autoclave is heated to C. in about 2 hours showing then a pressure of 8 atmospheres.
- the temperature is raised still further to 225 C., while maintaining the pressure at its value of 8 atmospheres by venting the autoclave.
- the pressure is gradually lowered within 2 hours to atmospheric pressure while the temperature of the mass is raised to 260 C. Maintaining these conditions the mass is stirred for 4 hours.
- for half an hour into the autoclave there is fed a light stream of an inert gas, and, finally, the polymer obtained is extruded, cooled and cut into uniform chips.
- the polymer obtained is perfectly white and its viscosity in metacresol is equal to 1.02.
- the average loss of tenacity of the yarns obtained from said polymer after 100 hours of exposure in the Fade-Orneter under the conditions described in Example I, is equal to 2% for the count 15/1 and to 3% for the count 30/ 6, as against an average loss of 33% for the count 15/ 1 and of 42% for the count 30/6 measured on a yarn made from a polymer obtained under the same conditions but without any incorporation of manganous silicate.
- Example VIII The operation is the same as in Example 1, except for the fact that, instead of being introduced at the beginning of the polymerization, the manganous silicate is added to the polymer already partly formed immediately before the autoclave is vacuated.
- a light-stabilized, substantially color-free, substantially light-fast yarn comprising a fiber-forming polyamide and containing from .005 to .05 percent by weight of manganous silicate, calculated as metallic manganese,
- a process for producing a substantially color-free, light-stabilized polyamide yarn comprising the steps of evenly incorporating crushed particles of manganous silicate of a diameter less than ten microns into a polyamide, and of spinning filaments of said silicate-containing polyamide.
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)
- Polyamides (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1242862 | 1962-06-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3300443A true US3300443A (en) | 1967-01-24 |
Family
ID=11140028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US287767A Expired - Lifetime US3300443A (en) | 1962-06-20 | 1963-06-14 | Polyamides stabilized with manganous silicate and process for producing same |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3300443A (no) |
| BE (1) | BE633737A (no) |
| GB (1) | GB991087A (no) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858597A (en) * | 1995-09-04 | 1999-01-12 | Canon Kabushiki Kaisha | Toner for developing electrostatic image containing specified double oxide particles |
| US20070270531A1 (en) * | 2003-10-20 | 2007-11-22 | Bossennec Veronique | Composition Stabilized with Respect to Light and/or Heat |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2201741A (en) * | 1938-10-03 | 1940-05-21 | Du Pont | Polymeric materials |
| DE737943C (de) * | 1941-02-04 | 1943-08-05 | Ig Farbenindustrie Ag | Verfahren zur Verbesserung der Lichtechtheit fadenbildender synthetischer linearer Hochpolymeren |
| US2887462A (en) * | 1955-01-26 | 1959-05-19 | Du Pont | Polyester or polyamide-manganous salt composition and process of preparing same |
| US3009900A (en) * | 1958-10-01 | 1961-11-21 | Du Pont | Stabilizing polyamides |
| US3019210A (en) * | 1958-08-05 | 1962-01-30 | Polymer Corp | Polyamide oxidation inhibiting processes and resulting products |
| US3066034A (en) * | 1959-04-06 | 1962-11-27 | Midland Ross Corp | Identifiable polyamide fibers containing lead acetate |
| US3206430A (en) * | 1961-11-03 | 1965-09-14 | American Enka Corp | Stabilization of polyamides with manganous hypophosphite or acetate and cerous oxalate |
-
0
- BE BE633737D patent/BE633737A/xx unknown
-
1963
- 1963-06-12 GB GB23484/63A patent/GB991087A/en not_active Expired
- 1963-06-14 US US287767A patent/US3300443A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2201741A (en) * | 1938-10-03 | 1940-05-21 | Du Pont | Polymeric materials |
| DE737943C (de) * | 1941-02-04 | 1943-08-05 | Ig Farbenindustrie Ag | Verfahren zur Verbesserung der Lichtechtheit fadenbildender synthetischer linearer Hochpolymeren |
| US2887462A (en) * | 1955-01-26 | 1959-05-19 | Du Pont | Polyester or polyamide-manganous salt composition and process of preparing same |
| US3019210A (en) * | 1958-08-05 | 1962-01-30 | Polymer Corp | Polyamide oxidation inhibiting processes and resulting products |
| US3009900A (en) * | 1958-10-01 | 1961-11-21 | Du Pont | Stabilizing polyamides |
| US3066034A (en) * | 1959-04-06 | 1962-11-27 | Midland Ross Corp | Identifiable polyamide fibers containing lead acetate |
| US3206430A (en) * | 1961-11-03 | 1965-09-14 | American Enka Corp | Stabilization of polyamides with manganous hypophosphite or acetate and cerous oxalate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858597A (en) * | 1995-09-04 | 1999-01-12 | Canon Kabushiki Kaisha | Toner for developing electrostatic image containing specified double oxide particles |
| US20070270531A1 (en) * | 2003-10-20 | 2007-11-22 | Bossennec Veronique | Composition Stabilized with Respect to Light and/or Heat |
| KR100919153B1 (ko) * | 2003-10-20 | 2009-09-28 | 로디아닐 | 광- 및/또는 열-안정화 조성물 |
| US20100152324A1 (en) * | 2003-10-20 | 2010-06-17 | Rhodianyl | Composition stabilized with respect to light and/or heat |
Also Published As
| Publication number | Publication date |
|---|---|
| GB991087A (en) | 1965-05-05 |
| BE633737A (no) |
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