News Details
Antioxidant system
2018-1-11 11:20:46
Antioxidant system
To determine the antioxidant system, when the temperature, uv light intensity, humidity and other environmental conditions change, the stability of the system or anti aging performance changes, in general, the stability of the antioxidant system and decreased with the increase of environmental harshness.
Three antioxidant system, oven temperature of 140 ℃ and 150 ℃, environment temperature 10 ℃, the only change three antioxidant system of the thermal stability of days were significantly reduced. The antioxidant 3114 + DSTP system, the thermal stability of 150 ℃ days is 140 ℃ only a third of the thermal stability of days. When designing the antioxidant system of the formula, it is necessary to determine the variety and dosage of the antioxidant in the most severe environmental conditions.
Under the same environmental conditions, the thermal oxygen stability of different antioxidant systems is different. Under the condition of 125 ℃, 3114 + DSTP system to replace the 3114 to 1010, thermal stability, thermal stability of days cut by a third. So if without systemic experiment, do not have complete data, in hou resistance of plastic products and using the environment are relatively stable period, should not be arbitrarily change any of the antioxidants varieties, and should not reduce the cost and so on the reason and reduce the amount of adding antioxidants.
Formula Δ E value of 6, 7, 8, compare, and compared with blank formula Δ E, for variety, to join the same amount of antioxidant combination system, using different types or varieties of flame retardant, aging resistance of the system have very big difference. Formula 7 Δ E value more than twice the formula 6, flame retardant BPBPE can weaken the effect of antioxidant. Formula 8 Δ E value is about twice as many blank formula, flame retardant DBDPO completely not only suppresses the antioxidant effect, and accelerate the aging of the system.
Formula 4, 5, 6, compared with Δ E value of the formula 1, for flame retardant BTBPIE: (1) the antioxidant and light stabilizer system can obviously improve the aging resistance of flame retardant polystyrene; In the range of 1% to 15%, the addition of the flame retardant BTBPIE has not weakened the anti-oxygen agent in the system. (3) using the composite antioxidant formula 5 Δ E value is the optimal.
Titanium dioxide can be used as a plastic filling material, shielding ultraviolet light; It can also be used as a white coloring agent. Formula 9 in table 3 and the formula of 6 Δ E value comparison, reduce the amount of joining the titanium pigment, reduced to 3% from 0.5%, fairly light screening agent to reduce, the stability of the formula 9 effect is poor. Formula 1, 2, 3, compared with the blank Δ E value of the formula, different type and specification of titanium dioxide has a great influence on the corrosion resistance properties of the resin. Formula 3 used without surface treatment of A - 100 titanium pigment, its Δ E value is 13, higher than that of blank formula Δ E = 12, without surface treatment of titanium pigment, not only can't block uv light and catalytic degradation of resin has A role.
Triphenyl phosphite (antioxidant, stabilizer TPPi) production process
1. Phosphorus oxychloride as the direct method (also called thermal method) phenol with pyridine and anhydrous benzene as solvent, in no more than 10 ℃ temperature, slowly add oxygen phosphorus chloride, then under reflux temperature, the reaction of 3 ~ 4 h. After cooling to room temperature, the reactants are washed by water to recycle pyridine. After centrifugal dehydration, the reagents are dehydrated with dried sodium sulfate, which is filtered to remove sodium sulfate. The first atmospheric distillation recovery of benzene, vacuum distillation, collected 243 ~ 245 ℃ (1.47 kPa) fraction, by cooling, crystallization, crushing is the finished product.
2. After phenol melting, stirring under add phosphorus trichloride under 25 ℃, Triphenyl phosphite is generated; Then heat up to 70 ℃ ventilation with chlorine gas, generated two chlorinated triphenyl phosphate; Again at 50 ℃ water hydrolysis, triphenyl phosphate. The hydrolysate with 5% soda solution for neutralization, water washing, the evaporation and vacuum distillation, collected 243 ~ 245 ℃ (1.47 kPa) fractions, cooling, crystallization, crushing, packaging is the finished product.
Triphenyl phosphite (TPPi antioxidants, stabilizer) is mainly used in PVC, polyethylene, polypropylene, polystyrene, polyester, abs resin, epoxy resin, synthetic rubber antioxidant stabilizer, used in polyvinyl chloride (PVC) products as a chelating agent.
Kaolin is filled with plastic, which can have a certain degree of rotation and heat preservation. Table 4, according to data share, kaolin and light stabilizer kaolin strongly weaken the effect of light stabilizer, the main reason is that kaolinite exists in the transfer of heavy metal elements, can be dramatically accelerated aging of plastic materials.
The stabilization mechanism of HALS for polymer materials is as follows:
The secondary amines of the four methyl piperidine were oxidized by the hydrogen peroxides, such as hydrogen peroxide, which were produced by the light of the macromolecule material and the thermal oxygen, and changed to nitrogen oxide free radical NO? The oxidative reaction destroys some of the active substances that can cause the degradation process of macromolecule material, making it a relatively stable hydroxyl compound;
Oxygen free radical NO A destructive active group, such as R, that is produced by the capture of a polymer material. And RO? And ROO? Free radicals; It also makes it a relatively stable compound, e.g. R - R, R - O - R, R - OO - R, etc.
In this process, nitrogen oxide free radical NO? Regenerated, continued and other free radical reactions in the material, and so on and so on, greatly delayed the light and thermal oxygen aging of plastic materials. In addition, HALS also has the function of quenching singlet oxygen, which transforms it from excited state to ground state, and interferes with photooxidation reaction before photoaging chain.
Therefore, HALS has the ability to decompose hydrogen peroxide, quench excited oxygen, capture free radicals, recycle itself, and have four self-synergies. It is not only an efficient light stabilizer, but also an effective antioxidant.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
To determine the antioxidant system, when the temperature, uv light intensity, humidity and other environmental conditions change, the stability of the system or anti aging performance changes, in general, the stability of the antioxidant system and decreased with the increase of environmental harshness.
Three antioxidant system, oven temperature of 140 ℃ and 150 ℃, environment temperature 10 ℃, the only change three antioxidant system of the thermal stability of days were significantly reduced. The antioxidant 3114 + DSTP system, the thermal stability of 150 ℃ days is 140 ℃ only a third of the thermal stability of days. When designing the antioxidant system of the formula, it is necessary to determine the variety and dosage of the antioxidant in the most severe environmental conditions.
Under the same environmental conditions, the thermal oxygen stability of different antioxidant systems is different. Under the condition of 125 ℃, 3114 + DSTP system to replace the 3114 to 1010, thermal stability, thermal stability of days cut by a third. So if without systemic experiment, do not have complete data, in hou resistance of plastic products and using the environment are relatively stable period, should not be arbitrarily change any of the antioxidants varieties, and should not reduce the cost and so on the reason and reduce the amount of adding antioxidants.
Formula Δ E value of 6, 7, 8, compare, and compared with blank formula Δ E, for variety, to join the same amount of antioxidant combination system, using different types or varieties of flame retardant, aging resistance of the system have very big difference. Formula 7 Δ E value more than twice the formula 6, flame retardant BPBPE can weaken the effect of antioxidant. Formula 8 Δ E value is about twice as many blank formula, flame retardant DBDPO completely not only suppresses the antioxidant effect, and accelerate the aging of the system.
Formula 4, 5, 6, compared with Δ E value of the formula 1, for flame retardant BTBPIE: (1) the antioxidant and light stabilizer system can obviously improve the aging resistance of flame retardant polystyrene; In the range of 1% to 15%, the addition of the flame retardant BTBPIE has not weakened the anti-oxygen agent in the system. (3) using the composite antioxidant formula 5 Δ E value is the optimal.
Titanium dioxide can be used as a plastic filling material, shielding ultraviolet light; It can also be used as a white coloring agent. Formula 9 in table 3 and the formula of 6 Δ E value comparison, reduce the amount of joining the titanium pigment, reduced to 3% from 0.5%, fairly light screening agent to reduce, the stability of the formula 9 effect is poor. Formula 1, 2, 3, compared with the blank Δ E value of the formula, different type and specification of titanium dioxide has a great influence on the corrosion resistance properties of the resin. Formula 3 used without surface treatment of A - 100 titanium pigment, its Δ E value is 13, higher than that of blank formula Δ E = 12, without surface treatment of titanium pigment, not only can't block uv light and catalytic degradation of resin has A role.
Triphenyl phosphite (antioxidant, stabilizer TPPi) production process
1. Phosphorus oxychloride as the direct method (also called thermal method) phenol with pyridine and anhydrous benzene as solvent, in no more than 10 ℃ temperature, slowly add oxygen phosphorus chloride, then under reflux temperature, the reaction of 3 ~ 4 h. After cooling to room temperature, the reactants are washed by water to recycle pyridine. After centrifugal dehydration, the reagents are dehydrated with dried sodium sulfate, which is filtered to remove sodium sulfate. The first atmospheric distillation recovery of benzene, vacuum distillation, collected 243 ~ 245 ℃ (1.47 kPa) fraction, by cooling, crystallization, crushing is the finished product.
2. After phenol melting, stirring under add phosphorus trichloride under 25 ℃, Triphenyl phosphite is generated; Then heat up to 70 ℃ ventilation with chlorine gas, generated two chlorinated triphenyl phosphate; Again at 50 ℃ water hydrolysis, triphenyl phosphate. The hydrolysate with 5% soda solution for neutralization, water washing, the evaporation and vacuum distillation, collected 243 ~ 245 ℃ (1.47 kPa) fractions, cooling, crystallization, crushing, packaging is the finished product.
Triphenyl phosphite (TPPi antioxidants, stabilizer) is mainly used in PVC, polyethylene, polypropylene, polystyrene, polyester, abs resin, epoxy resin, synthetic rubber antioxidant stabilizer, used in polyvinyl chloride (PVC) products as a chelating agent.
Kaolin is filled with plastic, which can have a certain degree of rotation and heat preservation. Table 4, according to data share, kaolin and light stabilizer kaolin strongly weaken the effect of light stabilizer, the main reason is that kaolinite exists in the transfer of heavy metal elements, can be dramatically accelerated aging of plastic materials.
The stabilization mechanism of HALS for polymer materials is as follows:
The secondary amines of the four methyl piperidine were oxidized by the hydrogen peroxides, such as hydrogen peroxide, which were produced by the light of the macromolecule material and the thermal oxygen, and changed to nitrogen oxide free radical NO? The oxidative reaction destroys some of the active substances that can cause the degradation process of macromolecule material, making it a relatively stable hydroxyl compound;
Oxygen free radical NO A destructive active group, such as R, that is produced by the capture of a polymer material. And RO? And ROO? Free radicals; It also makes it a relatively stable compound, e.g. R - R, R - O - R, R - OO - R, etc.
In this process, nitrogen oxide free radical NO? Regenerated, continued and other free radical reactions in the material, and so on and so on, greatly delayed the light and thermal oxygen aging of plastic materials. In addition, HALS also has the function of quenching singlet oxygen, which transforms it from excited state to ground state, and interferes with photooxidation reaction before photoaging chain.
Therefore, HALS has the ability to decompose hydrogen peroxide, quench excited oxygen, capture free radicals, recycle itself, and have four self-synergies. It is not only an efficient light stabilizer, but also an effective antioxidant.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
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