CN113603930A - Modified anti-aging agent and preparation method and application thereof - Google Patents
Modified anti-aging agent and preparation method and application thereof Download PDFInfo
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- CN113603930A CN113603930A CN202110996549.0A CN202110996549A CN113603930A CN 113603930 A CN113603930 A CN 113603930A CN 202110996549 A CN202110996549 A CN 202110996549A CN 113603930 A CN113603930 A CN 113603930A
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- aging agent
- phenylenediamine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a modified anti-aging agent, a preparation method of the modified anti-aging agent, a rubber composition containing the modified anti-aging agent and a tire sidewall prepared from the rubber composition, wherein the preparation method of the modified anti-aging agent comprises the following steps: (1) mixing unsaturated carboxylic acid and p-phenylenediamine anti-aging agent, and heating; (2) adding a catalyst, and carrying out heat preservation reaction for 3-5 hours to obtain the modified anti-aging agent. According to the invention, unsaturated carboxylic acid and p-phenylenediamine anti-aging agent are used as raw materials, and are modified under the action of a catalyst, so that the prepared modified anti-aging agent directly replaces the p-phenylenediamine anti-aging agent in the tire sidewall, the migration of the anti-aging agent is delayed, the appearance problems of color change, roughness and the like of rubber materials are obviously improved, and the durability is obviously improved while the physical property is not changed greatly.
Description
Technical Field
The invention belongs to the technical field of rubber anti-aging agents, and particularly relates to a modified anti-aging agent, a preparation method thereof and a rubber composition containing the modified anti-aging agent.
Background
It is known that a tire side wall is made of a rubber composition mainly comprising natural rubber and synthetic diene rubber, and olefin rubber is inferior in ozone resistance. When a tire sidewall made of such a rubber composition is subjected to tensile static stress and dynamic stress in addition to long-term sunlight exposure, ozone aging of the olefin-based rubber occurs in the tire sidewall energy and cracks are formed.
To reduce the effects of ozone, additives are often added, including, for example, p-phenylenediamine antioxidants such as N- (1,3 dimethylbutyl) -N' -phenyl-p-phenylenediamine (6PPD) and petroleum derived waxes. The combination of anti-aging agent and wax proved effective in minimizing cracking of the tire sidewall. In particular, waxes tend to migrate rapidly to the sidewall surface to form a protective film, providing static protection to the tire during transport and storage. The slower migration of the antioxidant provides dynamic protection during use of the tire mounted on the wheel, particularly fatigue due to the periodic alternation of compression and relaxation of the sidewall during normal use, and increased durability of the sidewall. But the anti-aging agent and the wax may migrate unevenly or excessively to the tire side surface during use of the tire, causing yellow-brown stain or color change, thereby causing deterioration in the appearance of the tire. Such deterioration in appearance affects the aesthetic appearance and use of the tire.
Some patents describe color changes that add special additives to the tire sidewall to improve appearance. For example, patent US6598632 describes elastomeric compositions for tyres comprising polymers of general formula R-O- (CnH2nO) x-H (for example PEG) useful for preventing the formation of surface stains caused by antiozonants. Patent US7365112 discloses a rubber composition comprising a natural and/or synthetic diene rubber, an amine antioxidant such as DMBPPD, a wax, and a polyoxyethylene type nonionic surfactant having a Hydrophilic Lipophilic Balance (HLB) of 2 to 19. Patent CN108884273 discloses salts of acids AC and amines AM for sidewalls, treads and anti-wear layers in tyre manufacture, improving the wear due to a combination of ozone degradation and mechanical stress. Although these methods can suppress the migration of antiozonants in a short period of time to improve the color change in appearance, the polymer is rapidly consumed in a dynamic use for a long period of time, and the color change improving effect is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a modified anti-aging agent, which takes unsaturated carboxylic acid and p-phenylenediamine anti-aging agent as raw materials, and is modified under the action of a catalyst, so that the prepared modified anti-aging agent directly replaces the p-phenylenediamine anti-aging agent in the tire side wall, the migration of the anti-aging agent is delayed, the appearance problems of color change, roughness and the like of rubber materials are obviously improved, and the durability is obviously improved while the physical property is not changed; another object of the present invention is to provide a rubber composition containing the modified antioxidant.
The invention is realized by the following technical scheme:
a modified antiager is prepared from unsaturated carboxylic acid and p-phenylenediamine antiager through reaction.
Further, the unsaturated carboxylic acid is a linear or branched unsaturated mono-or dicarboxylic acid.
Further, the unsaturated carboxylic acid is one or a mixture of more than two of acrylic acid, methacrylic acid, crotonic acid and 3-phenyl-2-acrylic acid.
Furthermore, the p-phenylenediamine anti-aging agent is one or a mixture of more than two of N- (1,3 dimethylbutyl) -N ' -phenyl-p-phenylenediamine, N-phenyl-N ' -isopropyl-p-phenylenediamine or N-cyclohexyl-N ' -phenyl-p-phenylenediamine.
The invention further improves the scheme as follows:
a preparation method of a modified anti-aging agent comprises the following steps:
(1) mixing unsaturated carboxylic acid and p-phenylenediamine anti-aging agent, and heating;
(2) adding a catalyst, and carrying out heat preservation reaction for 3-5 hours to obtain the modified anti-aging agent.
Further, in the step (1), the temperature is raised to 60-80 ℃ by mixing.
Further, the unsaturated carboxylic acid is a linear or branched unsaturated mono-or dicarboxylic acid.
Preferably, the unsaturated carboxylic acid is a linear unsaturated monocarboxylic or dicarboxylic acid.
Preferably, the unsaturated carboxylic acid is one or a mixture of more than two of acrylic acid, methacrylic acid, crotonic acid and 3-phenyl-2-acrylic acid.
Furthermore, the p-phenylenediamine anti-aging agent is one or a mixture of more than two of N- (1,3 dimethylbutyl) -N ' -phenyl-p-phenylenediamine, N-phenyl-N ' -isopropyl-p-phenylenediamine or N-cyclohexyl-N ' -phenyl-p-phenylenediamine.
Further, the catalyst is a lewis acid catalyst.
Preferably, the catalyst is one of aluminum trichloride, boron trifluoride, ferric bromide or sulfur trioxide.
Preferably, the catalyst is boron trifluoride.
Furthermore, the molar ratio of the unsaturated carboxylic acid to the p-phenylenediamine anti-aging agent to the catalyst is 1 (0.5-1.5) to 0.005-0.02.
The invention further improves the scheme as follows:
a rubber composition containing the modified antioxidant obtained by the above method.
The invention has the further improvement scheme that:
a tire sidewall is prepared from the rubber composition.
The invention has the beneficial effects that:
in the modification process, under the action of a catalyst, the-COOH of unsaturated carboxylic acid and the-NH-of secondary amino group in p-phenylenediamine anti-aging agent are subjected to selective reaction, the modified anti-aging agent contains unsaturated groups, and when the modified anti-aging agent is applied to a rubber composition, the unsaturated groups react with rubber molecular chains, so that the anti-aging agent and rubber molecules are stably combined, and the migration of the anti-aging agent is delayed, thereby playing a role in improving the change of appearance color;
the modified anti-aging agent prepared by the invention directly replaces p-phenylenediamine anti-aging agents in the tire side, and the anti-aging agent is delayed from emigrating while the processing, rheological and physical properties are not changed greatly, the appearance problems of color change, roughness and the like of rubber materials are obviously improved, and the durability is obviously improved.
Drawings
FIG. 1 is an infrared spectrum of sample 6PPD, age resister A obtained in example 1, and age resister B obtained in example 2;
FIG. 2 is a color change characterization chart of the vulcanizate of application examples 1-10;
as can be seen from FIG. 1, 1695cm-1The carbonyl peak of the unsaturated carboxylic acid is obviously changed, which shows that in the preparation process of the modified anti-aging agent, the-COOH of the unsaturated carboxylic acid and the secondary amino-NH-of 6PPD are selectively reacted, and when the modified 6PPD is applied to rubber, the unsaturated group of the unsaturated carboxylic acid and a rubber molecular chain are reacted and stably combined, so that the migration of the 6PPD is delayed, and the effect of improving the appearance color change is achieved.
Detailed Description
Example 1
Methacrylic acid (86g,1mol) and N- (1,3 dimethylbutyl) -N' -phenyl-p-phenylenediamine antioxidant (268g,1mol) are mixed in a reactor, the temperature is raised to 70 ℃, and the temperature is kept for 4 hours for reaction, so that the modified antioxidant is obtained.
Example 2
(1) Mixing methacrylic acid (86g,1mol) and N- (1,3 dimethylbutyl) -N' -phenyl-p-phenylenediamine anti-aging agent (268g,1mol) in a reactor, and heating to 70 ℃;
(2) adding boron trifluoride (1g,0.015mol) as a catalyst, and carrying out heat preservation reaction at 70 ℃ for 4h to obtain the modified anti-aging agent.
Example 3
(1) Mixing methacrylic acid (86g,1mol) and N- (1,3 dimethylbutyl) -N' -phenyl-p-phenylenediamine anti-aging agent (268g,1mol) in a reactor, and heating to 70 ℃;
(2) adding catalyst aluminum trichloride (1g,0.007mol), and carrying out heat preservation reaction at 70 ℃ for 4h to obtain the modified anti-aging agent.
Example 4
(1) Mixing butenoic acid (86g,1mol) and N- (1,3 dimethylbutyl) -N' -phenyl-p-phenylenediamine anti-aging agent (268g,1mol) in a reactor, and heating to 70 ℃;
(2) adding boron trifluoride (1g,0.015mol) as a catalyst, and carrying out heat preservation reaction at 70 ℃ for 4h to obtain the modified anti-aging agent.
Example 5
(1) Mixing methacrylic acid (86g,1mol) and N- (1,3 dimethylbutyl) -N' -phenyl-p-phenylenediamine anti-aging agent (268g,1mol) in a reactor, and heating to 60 ℃;
(2) adding boron trifluoride (1g,0.015mol) as a catalyst, and carrying out heat preservation reaction at 60 ℃ for 4 hours to obtain the modified anti-aging agent.
Example 6
(1) Mixing methacrylic acid (86g,1mol) and N- (1,3 dimethylbutyl) -N' -phenyl-p-phenylenediamine anti-aging agent (268g,1mol) in a reactor, and heating to 80 ℃;
(2) adding boron trifluoride (1g,0.015mol) as a catalyst, and carrying out heat preservation reaction at 80 ℃ for 4h to obtain the modified anti-aging agent.
Application examples 1 to 10: preparation of rubber composition
The formulations (mass ratios) of the rubber compositions in application examples 1 to 10 are shown in Table 1
TABLE 1 formulation of rubber composition
The rubber composition was compounded according to the following procedure:
first step, first-stage mixing: mixing natural rubber, butadiene rubber and carbon black in an internal mixer according to the mass ratio, cleaning when the rotating speed is 60rpm and the mixing temperature reaches 120 ℃, reducing the rotating speed to 50rpm and controlling the temperature to 145-150 ℃, discharging rubber, and discharging rubber by an open mill to obtain a section of master batch.
Second step, two-stage mixing: the rotation speed is 60rpm, the first-stage master batch, zinc oxide, stearic acid, an anti-aging agent RD, an anti-aging agent 4020 or the anti-aging agent prepared in the comparative example 1 or the anti-aging agent, protective wax and the like prepared in the example 1 are added into an internal mixer according to the mass ratio for mixing, when the mixing temperature reaches 120 ℃, cleaning is carried out, the temperature is controlled at 140 ℃ and 150 ℃ for rubber discharge, and the second-stage master batch is obtained by sheet discharging of an open mill.
Step three, final mixing: adding the two-stage masterbatch, insoluble sulfur, sulfur powder, an accelerator NS and the like into an internal mixer together according to the mass ratio, controlling the temperature at 95-100 ℃ for rubber discharge, then rolling for 5 times by an upper roll of an open mill, cutting rubber and producing pieces to obtain the rubber composition.
Test example
The rubber compositions obtained in application examples 1 to 10 were subjected to a performance test in accordance with the following methods:
the mechanical property test is carried out according to GB/T528-2009 determination of tensile stress strain property of vulcanized rubber or thermoplastic rubber, and the sample is prepared into a dumbbell shape with the tensile rate of 200 mm/min.
The vulcanization characteristics were determined according to GB/T16584-1996 "determination of vulcanization characteristics for rubber with a rotor-less vulcanizer".
Mooney scorch was measured according to GB T1233 + 2008 "measurement of initial vulcanization characteristics of unvulcanized rubber with disc shear viscometer
The hot air aging test is carried out according to GB/T3512-: 100 ℃ for 72h, 5 samples per specimen were used for the test, and the test results were taken as the median.
The compression Heat Generation test is carried out according to GB/T1687.3-2016, part 3 of determination of temperature rise and fatigue resistance of vulcanized rubber in a flexing test: measurement in the compression flexion test (constant strain type).
The flex-cracking test is according to GBT13934-2006 "determination of flex-cracking and crack growth in vulcanized or thermoplastic rubbers".
The infrared test is determined according to GBT21186-2007 Fourier transform infrared spectrometer.
The ozone cracking test is carried out according to GBT 13462-.
Vulcanized rubber appearance testing method: the sample is prepared into the vulcanization piece of equidimension, places and insolates 30 days under outdoor sunshine, observes vulcanized film appearance condition, describes vulcanization piece outward appearance with two kinds of situations, judges respectively according to the visual observation outward appearance: smooth, black, bright and rough
And (3) vulcanized rubber color change characterization: the vulcanized sheet was bound to white paper of the same size with a stapler, placed in a sealed bag, placed outdoors, and exposed to light on the side not coated with the white paper for 60 days, and the appearance was observed, and the observation result is shown in fig. 2, from which it is apparent that the antioxidant 4020 was easily precipitated, as shown in fig. 2.
The test results are shown in table 2.
TABLE 2 Properties of the rubber compositions
As can be seen from Table 2, the Mooney viscosities of all the formulations were not significantly different, and in comparison with application example 1, in application examples 2 to 10, since the antioxidants used had acidic groups and had adsorption effects on accelerators and the like, scorch times and T90 tended to increase, and the differences in physical properties were not significant.
After aging, compared with application example 1, in application examples 2 to 4, the aging retention rate is slightly improved along with the increase of the use amount of the modified anti-aging agent prepared in example 1; in application examples 5 to 7, the aging retention rate is obviously improved with the increase of the amount of the modified anti-aging agent (examples 2 to 5) prepared by the method of the present invention, and the durability of the tire can be improved when the modified anti-aging agent is applied to the tire. Compared with the application example 1, the ozone aging resistance and the flexing resistance of the application examples 2 to 4 are slightly improved; the ozone resistance and flex resistance improving effects of application examples 5 to 10 were good.
From the appearance characterization of the vulcanizate (fig. 2), it can be seen that the surface roughness of the vulcanized sheets of application examples 2-4 is improved after being placed outdoors for 30 days, compared with the surface roughness of application example 1; the surfaces of application examples 5-10 were smoother, darker and brighter than application example 1. The result of the vulcanized rubber color changing graph can be seen, and the white paper on the surface of the application example 1 has a reddish brown color changing phenomenon; the color change phenomenon of application examples 2-4 is slightly improved; the white paper on the surface of the application examples 5-10 has no reddish brown discoloration phenomenon, although the surfaces of the application examples 5-10 have wrinkles, the reddish brown discoloration phenomenon is obviously improved, and the samples of the application examples 5-10 can obviously improve the appearance of the vulcanized sheet and the discoloration phenomenon of the anti-aging agent.
Claims (12)
1. The modified anti-aging agent is characterized by being obtained by reacting unsaturated carboxylic acid with p-phenylenediamine anti-aging agent.
2. The modified antioxidant according to claim 1, wherein: the unsaturated carboxylic acid is a linear or branched unsaturated mono-or dicarboxylic acid.
3. The modified antioxidant according to claim 2, wherein: the unsaturated carboxylic acid is one or more of acrylic acid, methacrylic acid, crotonic acid and 3-phenyl-2-acrylic acid.
4. The modified antioxidant according to claim 1, wherein: the p-phenylenediamine anti-aging agent is one or a mixture of more than two of N- (1,3 dimethylbutyl) -N ' -phenyl-p-phenylenediamine, N-phenyl-N ' -isopropyl-p-phenylenediamine or N-cyclohexyl-N ' -phenyl-p-phenylenediamine.
5. A process for producing a modified antioxidant according to any one of claims 1 to 4, comprising the steps of:
(1) mixing unsaturated carboxylic acid and p-phenylenediamine anti-aging agent, and heating;
(2) adding a catalyst, and carrying out heat preservation reaction for 3-5 hours to obtain the modified anti-aging agent.
6. The method for preparing a modified antioxidant according to claim 5, wherein: and (2) mixing and heating to 60-80 ℃ in the step (1).
7. The method for preparing a modified antioxidant according to claim 5, wherein: the molar ratio of the unsaturated carboxylic acid to the p-phenylenediamine anti-aging agent to the catalyst is 1 (0.5-1.5) to 0.005-0.02.
8. The process for producing a modified antioxidant according to any one of claims 5 or 7, wherein: the catalyst is a lewis acid catalyst.
9. The method for preparing a modified antioxidant according to claim 8, wherein: the catalyst is one or a mixture of more than two of aluminum trichloride, boron trifluoride, ferric bromide or sulfur trioxide.
10. The process for producing a modified antioxidant according to any one of claims 5 or 7, wherein: the unsaturated carboxylic acid is one or a mixture of more than two of acrylic acid, methacrylic acid, crotonic acid or 3-phenyl-2-acrylic acid; the p-phenylenediamine anti-aging agent is one or a mixture of more than two of N- (1,3 dimethylbutyl) -N ' -phenyl-p-phenylenediamine, N-phenyl-N ' -isopropyl-p-phenylenediamine or N-cyclohexyl-N ' -phenyl-p-phenylenediamine.
11. A rubber composition comprising the modified antioxidant according to claim 1.
12. A tire sidewall prepared from the rubber composition of claim 10.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010031836A1 (en) * | 2000-03-17 | 2001-10-18 | Datta Rabindrah Nath | Rubber vulcanizates having improved ageing properties |
| CN101333304A (en) * | 2008-07-28 | 2008-12-31 | 常州市五洲化工有限公司 | Rubber antiager and method for preparing same |
| CN109400982A (en) * | 2018-11-22 | 2019-03-01 | 山东玲珑轮胎股份有限公司 | White tire sidewall base rubber with high white color retention performance |
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2021
- 2021-08-27 CN CN202110996549.0A patent/CN113603930A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010031836A1 (en) * | 2000-03-17 | 2001-10-18 | Datta Rabindrah Nath | Rubber vulcanizates having improved ageing properties |
| CN101333304A (en) * | 2008-07-28 | 2008-12-31 | 常州市五洲化工有限公司 | Rubber antiager and method for preparing same |
| CN109400982A (en) * | 2018-11-22 | 2019-03-01 | 山东玲珑轮胎股份有限公司 | White tire sidewall base rubber with high white color retention performance |
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