CN102030979A - Composite antioxidant for polyurethane - Google Patents
Composite antioxidant for polyurethane Download PDFInfo
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- CN102030979A CN102030979A CN 201010526439 CN201010526439A CN102030979A CN 102030979 A CN102030979 A CN 102030979A CN 201010526439 CN201010526439 CN 201010526439 CN 201010526439 A CN201010526439 A CN 201010526439A CN 102030979 A CN102030979 A CN 102030979A
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- antioxidant
- spandex
- composite antioxidant
- polyurethane
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Abstract
The invention discloses a composite antioxidant for spandex or thermal plastic polyurethane. Pentaerythritol tetrakis(4-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate is mixed with 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane according to a certain ratio, and the mixture is added into the spandex or thermal plastic polyurethane so as to improve the yellowing resistance and thermal stability. A weight ratio of the components in the composite antioxidant is 1-99:99-1, and the polyurethane accounts for 0.01 to 3.0 percent. The composite antioxidant can greatly improve the indoor yellowing resistance, NOX resistance and the thermal stability of the spandex or thermal plastic polyurethane.
Description
Technical field
The invention belongs to polymkeric substance organic oxidation-resistant agent, specifically a kind of thermoplastic polyurethane (TPU) and spandex of being used for is to promote TPU and spandex thermostability, anti-NO
XWith anti-indoor xanthochromic composite antioxidant.
Background technology
Urethane is a kind of long chain type synthetic polymer, the normally polymer of polyester or polyether polyol and vulcabond.Resistant polyurethane is hot, depend primarily on soft section (O-～-O-).From the isocyanic ester angle, the monomer of development high heat resistance does not almost have any possibility at present, even the isocyanic ester of existing production in enormous quantities, China does not all do entirely and carries out, and develop a new isocyanic ester difficulty and well imagine.Even the isocyanic ester thermotolerance improves, the thermotolerance of polyvalent alcohol still needs to improve.Therefore can only consider from polyvalent alcohol or amine, existing polyethers or polyester polyol, its thermotolerance is difficult to the raising of essence, and therefore, industrial normal interpolation antioxidant improves the thermotolerance of urethane.At present, though the commercial oxidation inhibitor that is used for urethane first characteristic such as fast light, heat-resisting, the anti-oxidant and anti-waste gas of tool so still exists its rerum natura instability to cause problems such as xanthochromia and mechanical properties variation.Many workers improve the problems referred to above with additive, antioxidant commonly used has 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-S-triazine-2,4,6 (1H, 2H, 3H)-triketone (antioxidant 3114), 2,6-two uncles base 4-butyl-methylphenol (BHT, antioxidant 264), four (4-hydroxyls-3,5-di-tert-butyl-phenyl propionic acid) tetramethylolmethane (antioxidant 1010), 3,5-di-t-butyl-hydroxyl-phenylpropionic acid octadecyl ester (antioxidant 1076), triethylene glycol ether-two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (antioxidant 245), triphenyl phosphite (TPP), tricresyl phosphite (nonyl phenyl ester) (TNP) etc.Document points out, 1,3, and 5-three (tertiary butyl-3 hydroxyl-2,6-dimethyl benzyl) isocyanic acid is effective antioxidant of urethane.Improve fast light and xanthochromia with benzotriazole and hindered phenol type antioxidant among the patent US3379675, US3386942, US3573251 and US4548975 more emphasize hindered phenol type antioxidant and organic phosphorous antioxidant and are used for improving the anti-xanthochromia effect of resistance to oxidation, especially the hindered phenol type antioxidant are combined with Polysaccharides among the patent US5028642 and improve the anti-xanthochromia of spandex.Though below, still have weak point separately with the hindered phenol type antioxidant or with oxidation inhibitor and other additive and with improving polyurethane heat resistant and antioxidant effect to a certain extent; For example urethane conventional oxidant when high temperature process can decompose or the Polysaccharides additive can dewater because of high-temperature part because of high-temperature part, thereby produces pin hole and the rerum natura of the back fiber that causes reeling off raw silk from cocoons presents phenomenons such as instability.And use separately single when forming the hindered phenol type antioxidant and can't satisfy the anti-xanthochromia effect of urethane.
Summary of the invention
A kind of composite antioxidant that is used for thermoplastic polyurethane (TPU) and spandex of providing at the deficiencies in the prior art is provided, and the use of this composite antioxidant can effectively promote the anti-indoor xanthochromia stability of thermoplastic polyurethane (TPU) and spandex, anti-NO
XAnd thermostability.
The object of the present invention is achieved like this:
A kind of composite antioxidant that is used for thermoplastic polyurethane (TPU) or spandex, this composite antioxidant is with four (4-hydroxyls-3,5-di-tert-butyl-phenyl propionic acid) tetramethylolmethane and 1,1,3-three (2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane mixes by a certain percentage, makes an addition in the urethane to promote the anti-xanthochromia and the heat-resistant stability of urethane.The weight ratio of this composite antioxidant component is: 1～99: 99～1; Its addition is: 0.01%～3.0% of thermoplastic polyurethane or spandex weight.
Described composite antioxidant is meant and all belongs to the hindered phenol type antioxidant.
Described composite antioxidant especially is suitable in heat build-up plasticity ammonia ester (TPU) or the spandex.
Use of the present invention can significantly improve thermoplastic polyurethane (TPU) or spandex resists indoor xanthochromia, anti-NO
XAnd heat-resistant stability.
Embodiment
Embodiment 1
1Kg plastic pellet (PU) and 2g antioxidant of the present invention or commercial antioxidant are mixed, with 80～100 ℃ of following dry 4hrs, fusion places the injection molding of screw rod machine to get the print of different ingredients, 185 ℃ of extrusion temperatures, 195 ℃ of injection temperatures, injection pressure 120kgf/cm
2
With the different ingredients print: following 7 days of 100 ℃ of sootiness 6 hours, baking oven, its Δ E value was surveyed in indoor placement in 60 days respectively.Shown in test result such as the table 1, table 2; No matter composite antioxidant of the present invention as shown in Table 1 is NO
X, the still anti-indoor xanthochromia effect of anti-oven ageing all obviously is better than not adding oxidation inhibitor or single antioxidant of forming commonly used on the market at present, improves the content of B component in the oxidation inhibitor of the present invention, its comprehensively anti-oxidant, anti-indoor xanthochromia, anti-NO
XPerformance can corresponding raising; As shown in Table 2, the consumption that suitably improves oxidation inhibitor of the present invention can improve anti-oxidant, the anti-indoor xanthochromia of thermoplastic polyurethane, anti-NO
XPerformance, consider cost factor, addition is 0.2% proper.
Embodiment 2
With 1mol ether type polyvalent alcohol (PTMEG; Molecular weight 2000 ± 100) mixes with 2mol vulcabond (MDI), under 80～90 ℃, be reacted into the polymkeric substance of terminal band isocyanic ester, be cooled to about 55 ℃ then, add N again, N-N,N-DIMETHYLACETAMIDE (DMAc) makes the solution that becomes to contain solid content 45%, and then adds second diamino and hexamethylene diamino as the chain extension agent, and with diethylamino as end-capping reagent, this moment, urethane resin content was about 36%, the about 2200 pool (poise of viscosity; 40 ℃).
This thick liquid is divided into several parts and add antioxidant of the present invention or commercial antioxidant respectively, coats again behind the mixed dissolution and make film forming on the flat glass, and in following 7 days of 100 ℃ of sootiness 6 hours, baking oven, its Δ E value was surveyed in indoor placement in 60 days respectively.Test result such as table 3 are shown in 4; No matter composite antioxidant of the present invention as shown in Table 3 is NO
X, the still anti-indoor xanthochromia effect of anti-oven ageing all obviously is better than not adding oxidation inhibitor or single component antioxidant commonly used on the market at present, improves the content of B component in the oxidation inhibitor of the present invention, its comprehensively anti-oxidant, anti-indoor xanthochromia, anti-NO
XPerformance can corresponding raising; As shown in Table 2, the consumption that suitably improves oxidation inhibitor of the present invention can improve anti-oxidant, the anti-indoor xanthochromia of spandex, anti-NO
XPerformance, consider cost factor, addition is 0.2% proper.。
Table 1: different additive is to thermoplastic polyurethane resin chromatic effects
Illustrate:
Contrast product: triethylene glycol ether-two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester
A: four (4-hydroxyl-3,5-di-tert-butyl-phenyl propionic acid) tetramethylolmethane
B: tetramethylolmethane and 1,1,3-three (2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane
Table 2: the additive addition is to thermoplastic polyurethane resin chromatic effects
Illustrate:
Contrast product: triethylene glycol ether-two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester
A: four (4-hydroxyl-3,5-di-tert-butyl-phenyl propionic acid) tetramethylolmethane
B: tetramethylolmethane and 1,1,3-three (2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane
Table 3: different additive is to the spandex chromatic effects
Illustrate:
Contrast product: triethylene glycol ether-two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester
A: four (4-hydroxyl-3,5-di-tert-butyl-phenyl propionic acid) tetramethylolmethane
B: tetramethylolmethane and 1,1,3-three (2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane
Table 4: the additive addition is to the spandex chromatic effects
Illustrate:
Contrast product: triethylene glycol ether-two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester
A: four (4-hydroxyl-3,5-di-tert-butyl-phenyl propionic acid) tetramethylolmethane
B: tetramethylolmethane and 1,1,3-three (2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane
Claims (2)
1. composite antioxidant that is used for spandex or thermoplastic polyurethane, it is characterized in that this composite antioxidant is with four (4-hydroxyls-3,5-di-tert-butyl-phenyl propionic acid) tetramethylolmethane and 1,1,3-three (2-methyl-4-hydroxyl-5-trimethylphenylmethane base) butane is by weight: 1～99: 99～1 mixed makes an addition in spandex or the thermoplastic polyurethane to promote its anti-indoor xanthochromia, anti-NO
XAnd heat-resistant stability, its addition is: 0.01%～3.0% of weight polyurethane.
2. composite antioxidant according to claim 1 is characterized in that described composite antioxidant is meant and all belongs to the hindered phenol type antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010526439 CN102030979A (en) | 2010-10-29 | 2010-10-29 | Composite antioxidant for polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010526439 CN102030979A (en) | 2010-10-29 | 2010-10-29 | Composite antioxidant for polyurethane |
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| Publication Number | Publication Date |
|---|---|
| CN102030979A true CN102030979A (en) | 2011-04-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010526439 Pending CN102030979A (en) | 2010-10-29 | 2010-10-29 | Composite antioxidant for polyurethane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828419A (en) * | 2012-09-19 | 2012-12-19 | 昆山市周市惠宏服装厂 | Production method of anti-creasing shirts |
| CN117382266A (en) * | 2023-09-13 | 2024-01-12 | 忠信（清远）光伏材料科技有限公司 | Sound insulation color ribbon PVB film for laminated glass and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003066718A1 (en) * | 2002-02-08 | 2003-08-14 | Solvay Polyolefins Europe - Belgium (S.A.) | Polyethylene-based composition |
| EP2133386A1 (en) * | 2007-04-05 | 2009-12-16 | Toray Industries, Inc. | Polylactic acid foam |
| CN101775204A (en) * | 2010-01-21 | 2010-07-14 | 迪比喜化学贸易(上海)有限公司 | Composite antioxidant for polyurethane fiber |
-
2010
- 2010-10-29 CN CN 201010526439 patent/CN102030979A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003066718A1 (en) * | 2002-02-08 | 2003-08-14 | Solvay Polyolefins Europe - Belgium (S.A.) | Polyethylene-based composition |
| EP2133386A1 (en) * | 2007-04-05 | 2009-12-16 | Toray Industries, Inc. | Polylactic acid foam |
| CN101775204A (en) * | 2010-01-21 | 2010-07-14 | 迪比喜化学贸易(上海)有限公司 | Composite antioxidant for polyurethane fiber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828419A (en) * | 2012-09-19 | 2012-12-19 | 昆山市周市惠宏服装厂 | Production method of anti-creasing shirts |
| CN117382266A (en) * | 2023-09-13 | 2024-01-12 | 忠信（清远）光伏材料科技有限公司 | Sound insulation color ribbon PVB film for laminated glass and preparation method and application thereof |
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Application publication date: 20110427 |