Rubber anti-aging agent and preparation process thereof
By adding specific components to the rubber anti-aging agent and adopting high-temperature heating and distillation separation processes, the existing rubber anti-aging agent volatilizes and extracts in high temperature or vacuum environments are solved, which enhances the anti-ozone, anti-flexion and light stability of the anti-aging agent, significantly extends the service life of rubber products.
Patent Information
- Application Number
- CN202311365413.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-10-20
- Publication Date
- 2025-04-22
AI Technical Summary
The existing rubber anti-aging agents are prone to evaporation and extraction in high temperature or vacuum environments, resulting in a decrease in protective function and cannot effectively prevent static ozone cracks and flexural cracks. Their light stability and oxidation resistance are insufficient, resulting in a significant decrease in service life.
A rubber anti-aging agent formula, including p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, anti-flexural LAS p-styrene, free-based capture agent, hindered phenol, TMQ, 6PPD, 7PPD, 77PD and other components, is prepared by high-temperature heating and distillation separation processes to enhance the anti-ozone, anti-flexural and light stability of the anti-aging agent.
It effectively reduces the volatility and extraction of anti-aging agents, enhances the resistance to ozone cracks, anti-flexion cracks and light stability, and significantly extends the service life of rubber products.
Smart Images
Figure CN119859416A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of rubber antioxidants, in particular to a rubber antioxidant composition and a preparation process. Background Art
[0002] During long-term storage and use, rubber products will gradually become sticky, hard, brittle or cracked due to the effects of heat, oxygen, ozone, variable-valence metal ions, mechanical stress, light and high-energy rays. This phenomenon of physical and mechanical properties decreasing over time and elasticity decreasing is called aging. As the aging process proceeds and develops, the performance of rubber products will gradually decrease and completely lose their use value. For this reason, certain chemical substances need to be added to rubber products to improve their resistance to the above-mentioned various destructive effects, delay or inhibit the aging process, and thus extend the storage period and service life of rubber and its products. Such substances are called antioxidants. Existing rubber antioxidants will have their protective functions reduced due to rapid extraction under high temperature or vacuum environments, especially under long-term contact with liquid media; existing rubber antioxidants cannot effectively prevent static ozone cracking and flex cracking; existing rubber antioxidants have insufficient light stability and antioxidant properties, resulting in a significant reduction in their service life. Summary of the invention
[0003] The purpose of the present invention is to provide a rubber antioxidant and a preparation process to solve the problems raised in the above background technology.
[0004] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a rubber antioxidant formula comprises: p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, anti-flexing LAS p-styrene, free radical scavenger, hindered phenol, TMQ, 6PPD, 7PPD, 77PD, and the mass percentage content of each component is: 12-18% of p-aminodiphenylamine, 8-15% of allyl substituted phenol (TAP), 6-10% of microcrystalline wax, 5-12% of anti-flexing LAS p-styrene, 10-16% of free radical scavenger, 8-13% of hindered phenol, 3-5% of TMQ, 3-7% of 6PPD, 5-7% of 7PPD, and 15-21% of 77PD.
[0005] Preferably, the mass percentage contents of the components are: 17% p-aminodiphenylamine, 13% allyl substituted phenol (TAP), 6% microcrystalline wax, 8% anti-flexing LAS p-styrene, 12% free radical scavenger, 10% hindered phenol, 4% TMQ, 5% 6PPD, 6% 7PPD, and 19% 77PD.
[0006] Preferably, the free radical scavenger can be replaced by a phosphite-based hydroperoxide decomposer, and the microcrystalline wax can be replaced by paraffin.
[0007] Preferably, the free radical scavenger is one or more of 2,2,6,6-tetramethylpiperidinyl oxide (TEMPO), butylated hydroxytoluene (BHT), and 1,1-diphenylethylene, and the hindered phenol is 2,6-di-tert-butyl-4-methylphenol.
[0008] Preferably, the anti-flex LAS styrene can be replaced by tributyl urea (TBTU) and its derivatives or lactam derivatives.
[0009] The present invention also provides a preparation process of a rubber antioxidant, comprising step one, preparing raw materials; step two, mixing the raw materials; step three, high-temperature heating; step four, distillation separation; step five, washing and drying; Wherein, in the above step 1, the components are selected according to the mass percentage content: 12-18% of p-aminodiphenylamine, 8-15% of allyl substituted phenol (TAP), 6-10% of microcrystalline wax, 5-12% of anti-flexing LAS p-styrene, 10-16% of free radical scavenger, 8-13% of hindered phenol, 3-5% of TMQ, 3-7% of 6PPD, 5-7% of 7PPD, and 15-21% of 77PD, and the sum of the mass percentages is 1 for measurement; In the above step 2, p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, and anti-flexing LAS p-styrene are added to the free radical scavenger and hindered phenol in sequence under stirring, and finally TMQ, 6PPD, 7PPD, and 77PD are added and mixed evenly; In the above step 3, the objects mixed in step 2 are put into a reaction kettle, and the reaction kettle is heated; In the above step 4, the heated material is distilled and then phase separated; In the above step 5, the solid phase separated in step 4 is taken, first washed and then dried to obtain a rubber antioxidant.
[0010] Preferably, in step 1, the free radical scavenger can be replaced by a phosphite-based hydroperoxide decomposer, and the microcrystalline wax can be replaced by paraffin.
[0011] Preferably, in step 1, the free radical scavenger is one or more of 2,2,6,6-tetramethylpiperidinyl oxide (TEMPO), butylated hydroxytoluene (BHT), and 1,1-diphenylethylene, and the hindered phenol is 2,6-di-tert-butyl-4-methylphenol.
[0012] Preferably, in the step 1, the anti-flexing LAS styrene can be replaced by tributyl urea (TBTU) and its derivatives or lactam derivatives.
[0013] Preferably, in the step 2, the stirring speed of the free radical scavenger and hindered phenol is 120-180 r / min, and the stirring time is 5-10 min. The stirring speed of p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, and anti-flexion LAS styrene is 200-250 r / min, and the stirring time is 7-12 min. The stirring speed of TMQ, 6PPD, 7PPD, and 77PD is 160-260 r / min, and the stirring time is 20-30 min.
[0014] Preferably, in step 3, the heating temperature in the reactor is controlled to be 130-150° C., and the heating time is controlled to be 30-50 min.
[0015] Preferably, in step 4, the distillation equipment is selected from one of a scraped film distillation equipment, a centrifugal distillation equipment and a molecular distillation equipment.
[0016] Preferably, in step 5, the cleaning agent is pure water, the drying temperature in the drying oven is controlled to be 30-50° C., and the drying time is controlled to be 10-20 min.
[0017] Compared with the prior art, the present invention has the following beneficial effects: compared with the existing rubber antioxidant, the present invention adds p-aminodiphenylamine and allyl substituted phenol (TAP), which can reduce the volatilization and extraction of the antioxidant and avoid the decline of the protective function; by adding microcrystalline wax and anti-flex LAS styrene, the performance of the antioxidant against ozone cracking and flex cracking is improved; by adding free radical scavengers and hindered phenols, the light stability and antioxidant property of the antioxidant are enhanced, the dosage of the light stabilizer is reduced, and the service life of the rubber product after adding the antioxidant is greatly extended. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 The process flow chart of an embodiment of the present invention. Implementation
[0019] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0020] The preparation process in the following embodiment technical scheme is shown in the attached Figure 1 . Example 1
[0021] A rubber antioxidant comprises: p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, anti-flexing LAS p-styrene, free radical scavenger, hindered phenol, TMQ, 6PPD, 7PPD and 77PD, wherein the mass percentage of each component is: 17% of p-aminodiphenylamine, 13% of allyl substituted phenol (TAP), 6% of microcrystalline wax, 8% of anti-flexing LAS p-styrene, 12% of free radical scavenger, 10% of hindered phenol, 4% of TMQ, 5% of 6PPD, 6% of 7PPD and 19% of 77PD.
[0022] A preparation process of a rubber antioxidant, comprising the steps of: preparing raw materials; mixing the raw materials; heating at high temperature; separating by distillation; and washing and drying. Wherein, in the above step 1, the components are selected according to their mass percentage: 17% of p-aminodiphenylamine, 13% of allyl substituted phenol (TAP), 6% of microcrystalline wax, 8% of anti-flexing LAS p-styrene, 12% of free radical scavenger, 10% of hindered phenol, 4% of TMQ, 5% of 6PPD, 6% of 7PPD, and 19% of 77PD, and weighed according to the sum of the mass percentages being 1, wherein the free radical scavenger is 2,2,6,6-tetramethylpiperidinyl oxide (TEMPO), and the hindered phenol is 2,6-di-tert-butyl-4-methylphenol; In the above step 2, the radical scavenger and hindered phenol in step 1 are taken and put into a stirring tank for stirring, and then p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, and anti-flexing LAS styrene are added in sequence and stirred, and finally TMQ, 6PPD, 7PPD, and 77PD are put into a stirring tank and mixed evenly, wherein the stirring speed of the radical scavenger and hindered phenol is 160r / min, and the stirring time is 10min, the stirring speed of p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, and anti-flexing LAS styrene is 250r / min, and the stirring time is 11min, and the stirring speed of TMQ, 6PPD, 7PPD, and 77PD is 220r / min, and the stirring time is 25min; In the above step 3, the mixed objects in step 2 are put into a reactor, and high-temperature steam is introduced into the reactor to heat it. The heating temperature in the reactor is controlled to be 140° C. and the heating time is controlled to be 30 min. In the above step 4, the heated material is put into a distillation device, and phase separation is performed after distillation, and the distillation device is selected from one of a scraped film distillation device, a centrifugal distillation device and a molecular distillation device; In the above step 5, the solid phase separated in step 4 is taken, first washed with pure water, and then sent to a drying oven for drying to obtain a rubber antioxidant. The drying temperature in the drying oven is controlled at 40° C. and the drying time is controlled at 13 min. Example 2
[0023] A rubber antioxidant comprises: p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, anti-flexing LAS p-styrene, free radical scavenger, hindered phenol, TMQ, 6PPD, 7PPD and 77PD, wherein the mass percentage of each component is: 16% of p-aminodiphenylamine, 15% of allyl substituted phenol (TAP), 8% of microcrystalline wax, 9% of anti-flexing LAS p-styrene, 10% of free radical scavenger, 11% of hindered phenol, 3% of TMQ, 4% of 6PPD, 7% of 7PPD and 17% of 77PD.
[0024] A preparation process of a rubber antioxidant, comprising the steps of: preparing raw materials; mixing the raw materials; heating at high temperature; separating by distillation; and washing and drying. Wherein, in the above step 1, the components are selected according to the mass percentage content: 16% of p-aminodiphenylamine, 15% of allyl substituted phenol (TAP), 8% of microcrystalline wax, 9% of anti-flexing LAS p-styrene, 10% of free radical scavenger, 11% of hindered phenol, 3% of TMQ, 4% of 6PPD, 7% of 7PPD, and 17% of 77PD, and weighed according to the sum of the mass percentages being 1, wherein the anti-flexing LAS p-styrene is replaced by tributylthiourea, the free radical scavenger is butylated hydroxytoluene (BHT), and the hindered phenol is 2,6-di-tert-butyl-4-methylphenol; In the above step 2, the free radical scavenger and hindered phenol in step 1 are taken and put into a stirring tank for stirring, and then p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, and anti-flexing LAS styrene are added in sequence and stirred, and finally TMQ, 6PPD, 7PPD, and 77PD are put into a stirring tank and mixed evenly, wherein the stirring speed of the free radical scavenger and hindered phenol is 160r / min, and the stirring time is 10min, the stirring speed of p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, and tributylthiourea is 250r / min, and the stirring time is 11min, and the stirring speed of TMQ, 6PPD, 7PPD, and 77PD is 220r / min, and the stirring time is 25min; In the above step 3, the mixed objects in step 2 are put into a reactor, and high-temperature steam is introduced into the reactor to heat it. The heating temperature in the reactor is controlled to be 140° C. and the heating time is controlled to be 30 min. In the above step 4, the heated material is put into a distillation device, and phase separation is performed after distillation, and the distillation device is selected from one of a scraped film distillation device, a centrifugal distillation device and a molecular distillation device; In the above step 5, the solid phase separated in step 4 is taken, first washed with pure water, and then sent to a drying oven for drying to obtain a rubber antioxidant. The drying temperature in the drying oven is controlled at 40° C. and the drying time is controlled at 13 min. Example 3
[0025] A rubber antioxidant comprises: p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, anti-flexing LAS p-styrene, free radical scavenger, hindered phenol, TMQ, 6PPD, 7PPD and 77PD, wherein the mass percentage of each component is: 18% of p-aminodiphenylamine, 11% of allyl substituted phenol (TAP), 9% of microcrystalline wax, 11% of anti-flexing LAS p-styrene, 14% of free radical scavenger, 8% of hindered phenol, 3% of TMQ, 3% of 6PPD, 5% of 7PPD and 18% of 77PD.
[0026] A preparation process of a rubber antioxidant, comprising the steps of: preparing raw materials; mixing the raw materials; heating at high temperature; separating by distillation; and washing and drying. Wherein, in the above step 1, the components are selected according to the mass percentage content: 18% of p-aminodiphenylamine, 11% of allyl substituted phenol (TAP), 9% of microcrystalline wax, 11% of anti-flexing LAS p-styrene, 14% of free radical scavenger, 8% of hindered phenol, 3% of TMQ, 3% of 6PPD, 5% of 7PPD, and 18% of 77PD, and weighed according to the sum of the mass percentages being 1, wherein the anti-flexing LAS p-styrene is replaced by tributylthiourea (TBTU), the free radical scavenger is 1,1-diphenylethylene, and the hindered phenol is 2,6-di-tert-butyl-4-methylphenol; In the above step 2, the free radical scavenger and hindered phenol in step 1 are taken and put into a stirring tank for stirring, and then p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, and tributylthiourea (TBTU) are added in sequence and stirred, and finally TMQ, 6PPD, 7PPD, and 77PD are put into a stirring tank and mixed evenly, wherein the stirring speed of the free radical scavenger and hindered phenol is 160r / min, and the stirring time is 10min, the stirring speed of p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, and tributylthiourea (TBTU) is 250r / min, and the stirring time is 11min, and the stirring speed of TMQ, 6PPD, 7PPD, and 77PD is 220r / min, and the stirring time is 25min; In the above step 3, the mixed objects in step 2 are put into a reactor, and high-temperature steam is introduced into the reactor to heat it. The heating temperature in the reactor is controlled to be 140° C. and the heating time is controlled to be 30 min. In the above step 4, the heated material is put into a distillation device, and phase separation is performed after distillation, and the distillation device is selected from one of a scraped film distillation device, a centrifugal distillation device and a molecular distillation device; In the above step 5, the solid phase separated in step 4 is taken, first washed with pure water, and then sent to a drying oven for drying to obtain a rubber antioxidant. The drying temperature in the drying oven is controlled at 40° C. and the drying time is controlled at 13 min.
[0027] Table 1 Composition of each embodiment
[0028] Test method and operation steps for rubber anti-aging performance test using the prepared antioxidant: Main test formula: Rubber standard: German DIN industrial standard, EU rubber product environmental protection standard. (NR) is a low-polarity, unsaturated, and easily aged rubber. Anti-aging agent is one of the essential ingredients for NR rubber formula. There are many types of antioxidants. Considering the solubility, vulcanization characteristics, pollution, and heat resistance of antioxidants in NR, TMQ produced by Sinopec Nanjing Chemical Industry Co., Ltd. was selected for comparative experiments.
[0029] Test experiment recipe: Table 2 Main anti-aging test formula
[0030] Test steps: Table 3 Anti-aging test steps
[0031] Table 4 Main rheological properties test table
[0032] All data were subjected to 2 repeat experiments. Through 8 batches of testing, the protective performance was compared: tensile strength, elongation, tear strength, flex cracking and other anti-aging properties were significantly improved. Based on the above, the advantages of the present invention are that the volatilization of the antioxidant is reduced under high temperature and vacuum environment, and the extraction of the antioxidant in the rubber is reduced to prevent ozone cracking and flex cracking; the free radical scavenger and hindered phenol combination added in the present invention can provide a certain light stabilization effect, and can effectively decompose the hydroperoxide into inactive products such as alcohols and ketones, thereby inhibiting its automatic decomposition.
[0033] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.
Claims
1. A rubber antioxidant, characterized in that Its formula includes: p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, anti-flexing LAS p-styrene, free radical scavenger, hindered phenol, TMQ, 6PPD, 7PPD, and 77PD. The mass percentage content of each component is: 12-18% p-aminodiphenylamine, 8-15% allyl substituted phenol (TAP), 6-10% microcrystalline wax, 5-12% anti-flexing LAS p-styrene, 10-16% free radical scavenger, 8-13% hindered phenol, 3-5% TMQ, 3-7% 6PPD, 5-7% 7PPD, and 15-21% 77PD.
2. A rubber antioxidant according to claim 1, characterized in that: The mass percentage contents of the components are: 17% of p-aminodiphenylamine, 13% of allyl substituted phenol (TAP), 6% of microcrystalline wax, 8% of anti-flexing LAS p-styrene, 12% of free radical scavenger, 10% of hindered phenol, 4% of TMQ, 5% of 6PPD, 6% of 7PPD, and 19% of 77PD.
3. A rubber antioxidant according to claim 1 or 2, characterized in that: The free radical scavenger can be replaced by a phosphite-based hydroperoxide decomposer, and the microcrystalline wax can be replaced by paraffin.
4. A rubber antioxidant according to claim 1 or 2, characterized in that: The free radical scavenger is selected from 2,2,6,6- Tetramethylpiperidinyloxide The hindered phenol is one or more of TEMPO, butylated hydroxytoluene (BHT), 1,1-diphenylethylene, and 2,6-di-tert-butyl-4-methylphenol is selected.
5. A rubber antioxidant according to claim 1 or 2, characterized in that: The anti-flex LAS styrene can be replaced by tributylthiourea (TBTU) and its derivatives or lactam derivatives.
6. A process for preparing a rubber antioxidant, comprising step 1, preparing raw materials; step 2, mixing the raw materials; step 3, heating at high temperature; step 4, separating by distillation; step 5, washing and drying; characterized in that: Wherein, in the above step 1, the components are selected according to the mass percentage content: 12-18% of p-aminodiphenylamine, 8-15% of allyl substituted phenol (TAP), 6-10% of microcrystalline wax, 5-12% of anti-flexing LAS p-styrene, 10-16% of free radical scavenger, 8-13% of hindered phenol, 3-5% of TMQ, 3-7% of 6PPD, 5-7% of 7PPD, and 15-21% of 77PD, and the sum of the mass percentages is 1 for measurement; In the above step 2, p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, and anti-flexing LAS p-styrene are added to the free radical scavenger and hindered phenol in sequence under stirring, and finally TMQ, 6PPD, 7PPD, and 77PD are added and mixed evenly; In the above step 3, the objects mixed in step 2 are put into a reaction kettle, and the reaction kettle is heated; In the above step 4, the heated material is distilled and then phase separated; In the above step 5, the solid phase separated in step 4 is taken, first washed and then dried to obtain a rubber antioxidant.
7. The preparation process of a rubber antioxidant according to claim 6, characterized in that: In the step 1, the free radical scavenger can be replaced by a phosphite-based hydroperoxide decomposition agent, and the microcrystalline wax can be replaced by paraffin.
8. The preparation process of a rubber antioxidant according to claim 6, characterized in that: In the step 1, the free radical scavenger is 2,2,6,6- Tetramethylpiperidinyl oxide ( TEMPO), butylated hydroxytoluene (BHT), 1,1-diphenylethylene, and the hindered phenol is 2,6-di-tert-butyl-4-methylphenol.
9. The preparation process of a rubber antioxidant according to claim 6, characterized in that: In the step 1, the anti-flexing LAS styrene can be replaced by tributylthiourea (TBTU) and its derivatives or lactam derivatives.
10. The process for preparing a rubber antioxidant according to claim 6, characterized in that: In the step 2, the stirring speed of the free radical scavenger and hindered phenol is 120-180 r / min, and the stirring time is 5-10 min. The stirring speed of p-aminodiphenylamine, allyl substituted phenol (TAP), microcrystalline wax, and anti-flexion LAS styrene is 200-250 r / min, and the stirring time is 7-12 min. The stirring speed of TMQ, 6PPD, 7PPD, and 77PD is 160-260 r / min, and the stirring time is 20-30 min.
11. The process for preparing a rubber antioxidant according to claim 6, characterized in that: In the step 3, the heating temperature in the reaction kettle is controlled to be 130-150° C., and the heating time is controlled to be 30-50 min.
12. The process for preparing a rubber antioxidant according to claim 6, characterized in that: In the step 4, the distillation equipment is selected from one of a scraped film distillation equipment, a centrifugal distillation equipment and a molecular distillation equipment.
13. The preparation process of a rubber antioxidant according to claim 6, characterized in that: In the step 5, the cleaning agent is pure water, the drying temperature is controlled at 30-50° C., and the drying time is controlled at 10-20 min.