Ozone protection aid for dynamic rubber, process for its preparation, use and a rubber

Abstract

The application discloses an ozone protection aid for dynamic rubber, wherein a molecular main chain of the ozone protection aid is a saturated alkane structure, and a side group containing an aromatic amine group functional group is arranged on the molecular main chain. The application further discloses a preparation method and application of the ozone protection aid and a rubber. The ozone protection aid can form a protection film to isolate ozone in the air from contacting the rubber, and plays a physical protection role against ozone. On the other hand, the ozone protection aid can react with ozone, and plays a chemical protection role against ozone. The two roles work together to prevent the rubber molecular chain from being aged and cracked by ozone, and fully realize the anti-ozone effect. Meanwhile, the ozone protection aid can improve the adhesion between the protection film and the surface of the rubber product, the ozone protection film formed is not easy to be peeled or fallen off from the surface of the rubber product, and has a good anti-dynamic ozone effect.

Description

Technical Field

[0001] The present invention belongs to the field of rubber materials, and in particular relates to a rubber additive, a preparation method and application thereof, and a rubber. Background Art

[0002] During use, rubber products are exposed to ozone and mechanical stress, which can easily cause ozone cracking on the surface, seriously affecting the function and service life of rubber products.

[0003] The rubber industry often uses a combination of physical protective wax and chemical antiozonants to improve the dynamic ozone resistance of rubber products, especially those made with unsaturated carbon-carbon double bonds in their molecular chains. Protective wax, a saturated alkane, forms a protective film when it migrates to the surface of rubber products, isolating ozone from the air and preventing it from coming into contact with the rubber, thereby providing physical protection against ozone. However, the protective wax film has poor adhesion to the surface of rubber products and can easily peel or fall off under dynamic stress, causing ozone to attack the rubber surface and cause ozone cracking.

[0004] Therefore, it is of great significance to design and synthesize a rubber protective agent with good dynamic ozone resistance. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the above background technology and provide an ozone protection additive for dynamic rubber with good dynamic ozone resistance, a preparation method, an application thereof and a rubber.

[0006] In order to solve the above technical problems, the technical solution proposed by the present invention is:

[0007] An ozone protection auxiliary agent for dynamic rubber. The main molecular chain of the ozone protection auxiliary agent is a saturated alkane structure. There are side groups on the main molecular chain, and the side groups contain aromatic amine functional groups.

[0008] In the above ozone protection auxiliary agent, preferably, the aromatic amino functional group includes one or more of a dialkylphenylamine group, an alkylphenylamine group and a phenylamine group.

[0009] Among the above ozone protection aids, preferably, the molecular structure of the ozone protection aid is shown as follows:

[0010] ;

[0011] Wherein: the main chain of the molecule is a straight or branched alkane with 10-100 carbon atoms (preferably C18-C80);

[0012] , R 1 、R2 、R 3 、R 4 is hydrogen, or is the same or different linear or branched alkyl group having 1 to 8 carbon atoms.

[0013] In the present invention, there is no requirement for the distribution position of the side groups F, which has no effect on the results and is randomly distributed. The number of side groups F is controlled by the mass ratio of the first raw material to the alkane wax.

[0014] As a general technical concept, the present invention also provides a method for preparing the above-mentioned ozone protection auxiliary agent, comprising the following steps: reacting an alkane wax containing 10 to 100 carbon atoms with a first raw material under the action of an initiator to obtain the ozone protection auxiliary agent;

[0015] Wherein, the molecular structure formula of the first raw material is as follows:

[0016] .

[0017] In the above preparation method, preferably, the preparation method of the first raw material comprises the following steps: reacting a quaternary phosphine salt with a base to generate methylene triphenyl phosphine, and performing a Wittig reaction on the methylene triphenyl phosphine and the second raw material to obtain the first raw material;

[0018] Among them, the structural molecular formula of the second raw material is as follows:

[0019] .

[0020] When preparing the above-mentioned first raw material, preferably, a quaternary phosphine salt is reacted with a base to generate methylenetriphenylphosphine, comprising the following steps: under the protection of an inert gas, the quaternary phosphine salt and an organic solvent are configured into a mixed liquid, and an alkaline solution with a mass concentration of 2-50wt% (preferably 2-30wt%) is added under stirring at 0-20°C (preferably 0-10°C), and the stirring reaction is continued for 0.1-3h (preferably 0.3-2h) to obtain a methylenetriphenylphosphine mixed liquid; the quaternary phosphine salt includes one or more of methyltriphenylphosphine chloride, methyltriphenylphosphine bromide and methyltriphenylphosphine iodide; the organic solvent includes one or more of tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and diethyl ether; the base includes one or more of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, sodium hydroxide and sodium carbonate; and the molar ratio of the base to the quaternary phosphine salt is (1-2):1 (preferably (1-1.2):1).

[0021] When preparing the above-mentioned first raw material, preferably, methylenetriphenylphosphine and the second raw material are subjected to a Wittig reaction, comprising the following steps: under the protection of an inert gas, the second raw material is dissolved in an organic solvent, mixed with methylenetriphenylphosphine under stirring at 0-20°C (preferably 0-10°C), and the reaction is continued with stirring from room temperature to reflux temperature (preferably at reflux temperature) for 4-48 hours (preferably 5-12 hours). After the reaction is completed, the reaction mixture is poured into excess deionized water, and the organic layer is separated. The organic layer is washed with a saturated sodium bicarbonate aqueous solution until neutral, and then anhydrous magnesium sulfate is added and stirred to dry for a day and night, filtered, and the filtrate is rotary evaporated to obtain a crude product. The crude product is separated by column chromatography, rotary evaporated, and vacuum dried at 10-40°C (preferably 20-35°C) to constant weight to obtain the first raw material; the organic solvent comprises one or more of tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and diethyl ether; the molar ratio of the quaternary phosphine salt to the second raw material is (1-2):1 (preferably (1-1.6):1).

[0022] In the above preparation method, preferably, the alkane wax and the first raw material are first dissolved in an organic solvent, the initiator is added under stirring, the reaction is carried out at 60-150°C (preferably 65-135°C) for 1-10 hours (preferably 1-3 hours), isopropanol is added to terminate the reaction, and the ozone protection agent is obtained by vacuum drying at 10-40°C (preferably 20-35°C) to constant weight.

[0023] In the above preparation method, preferably, the mass ratio of the first raw material to the alkane wax is (0.2-2):1 (preferably (0.9-1.6):1); the mass ratio of the initiator to the alkane wax is (0.01-0.1):1 (preferably (0.01-0.05):1); the organic solvent includes one or more of n-hexane, cyclohexane, toluene and ethylbenzene; and the initiator includes one or more of 3,6,9-trimethyl-3,6,9-triethyl-1,4,7-triperoxane, benzoyl peroxide, 1,1-di(tert-butylperoxy)cyclohexane and 2,2-di(4,4-di-tert-butylperoxycyclohexyl)propane.

[0024] As a general technical concept, the present invention also provides an application of the above-mentioned rubber protective aid in ozone protection of dynamic rubber materials.

[0025] As a general technical concept, the present invention also provides a rubber comprising a rubber matrix and an additive, wherein the molecular chain of the rubber matrix contains carbon-carbon double bonds, and the additive comprises an ozone protection additive, which is the above-mentioned ozone protection additive.

[0026] The rubber matrix includes natural rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, nitrile rubber and mixed rubbers thereof in different proportions.

[0027] In the above rubber, preferably, the additive further comprises an antiozonant, and the molecular structure of the antiozonant is as follows:

[0028] ;

[0029] Among them, R 1 、R 2 、R 3 、R 4 is hydrogen, or is the same or different straight or branched chain alkyl group of 1 to 8 carbon atoms. More preferably, R 1 、R 2 、R 3 、R 4 The alkyl groups are straight or branched chain alkyl groups of 1 to 3 carbon atoms, which may be the same or different.

[0030] The antiozonant is a chemical ozone inhibitor for rubber, equivalent to the first raw material used in the preparation of ozone protection additives. It is used to achieve ozone protection through chemical methods. Specifically, the aromatic amine functional group in the antiozonant molecule readily reacts with the electron-withdrawing reagent ozone, consuming ozone while preventing it from attacking the unsaturated carbon-carbon double bonds in the rubber molecular chain. Furthermore, the reaction product forms a charred protective film on the surface of the product, preventing ozone from further penetrating the inner layer of the rubber and damaging the rubber molecular chain. The carbon-carbon double bonds in the antiozonant molecule can replace those in the rubber molecular chain, reacting with ozone, further enhancing the chemical antiozonation effect. The carbon-carbon double bond in the antiozonant molecule is connected to the two aromatic amine functional groups to form a conjugated structure. On the one hand, this structural form is conducive to the synergistic effect of the aromatic amine functional groups and the carbon-carbon double bond, which enhances the chemical anti-ozon effect through synergistic effect. On the other hand, the two aromatic amine functional groups contained in this structure can better react with the aldehyde and ketone groups generated by the rubber macromolecule after the chain break due to ozone aging, playing a similar "cross-linking" role, preventing further degradation of the rubber molecular chain and inhibiting the occurrence of ozone cracking. In addition, the antiozonant of the present invention has a moderate molecular weight and its molecular weight is reasonably controlled to ensure a suitable migration rate. If the antiozonant migrates from the interior of the rubber to the surface, the migration is too slow and it has no anti-ozon effect; if it migrates too quickly and is highly volatile, the anti-ozon effect is poor. The antiozonant with this structural form, by controlling the molecular weight of the terminal side chain, is conducive to ensuring a suitable molecular weight, has an appropriate migration rate and volatility, and can timely maintain a steady-state concentration on the surface of the rubber product. Therefore, the antiozonant has a better sustained anti-ozon effect.

[0031] The above-mentioned antiozonant mainly plays a chemical anti-ozone effect, and cooperates with the ozone protection auxiliary agent of the present invention which mainly plays a physical protection role, and has a better anti-ozone effect, and may be better suitable for dynamic use conditions. In addition, the chemical antiozonant and the material protection auxiliary agent have the same functional group and are more compatible.

[0032] The main molecular chain of the ozone protection agent of the present invention is a saturated alkane structure. When it migrates to the surface of the rubber product, it can form a protective film to isolate the ozone in the air from contacting the rubber on the surface of the product, thereby playing a role in physical protection against ozone. At the same time, the side chain of the ozone protection agent molecule contains aromatic amine functional groups, including dialkylphenylamine, alkylphenylamine and phenylamine, etc. On the one hand, it can react chemically with ozone to prevent ozone from continuing to penetrate into the inner layer of the rubber and destroy the rubber molecular chain, thereby further enhancing the anti-ozone effect. On the other hand, the polar aromatic amine groups contained in the side chain improve the adhesion of the formed ozone protection film to the surface of the rubber product, making it difficult to peel off or fall off from the surface of the rubber product, especially in the dynamic use conditions of the rubber product, and having a good anti-dynamic ozone effect. Moreover, the diamine functional groups in the side group can react with the aldehyde and ketone groups generated by the rubber macromolecules due to ozone aging and chain breakage, thereby playing a similar "cross-linking" role, thereby preventing the rubber molecular chain from further degradation and inhibiting the occurrence of ozone cracking.

[0033] Without both of these structural features (main chain + side chain), for example, without a saturated alkane main chain, a physical protective film cannot be formed on the surface of the rubber product, failing to provide physical ozone resistance. Without aromatic amine functional side chains, the ozone resistance is reduced, and adhesion to the product surface is poor, making it prone to peeling or falling off the rubber product surface during dynamic use, reducing dynamic ozone resistance. Containing both the main chain and side chains of the present invention can achieve excellent dynamic ozone resistance.

[0034] Compared with the prior art, the advantages of the present invention are:

[0035] 1. The molecular main chain of the ozone protection agent of the present invention is a saturated alkane structure, and the side group contains an aromatic amine functional group. It migrates to the surface of the rubber product and can form a protective film on the one hand to isolate the ozone in the air from contact with the rubber, thereby playing a role in physical protection against ozone; on the other hand, the aromatic amine functional group can react with ozone to play a role in chemical protection against ozone. The two work together to prevent the rubber molecular chain from being broken and cracked due to ozone aging, thereby fully achieving the anti-ozone effect.

[0036] 2. The molecular side groups of the ozone protection agent of the present invention contain aromatic amine polar groups, which can improve the adhesion between the protective film and the surface of the rubber product. The ozone protection film formed is not easy to peel off or fall off from the surface of the rubber product. It has good anti-dynamic ozone effect under the dynamic use conditions of the rubber product.

[0037] 3. The preparation method of the present invention has high universality, is simple and easy to operate, can share organic synthesis instruments and equipment, is easy to realize industrial production, and has good market application value in the rubber industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0039] Figure 1 This is the infrared spectrum of the ozone protection agent W1 in Example 1. DETAILED DESCRIPTION

[0040] To facilitate understanding of the present invention, the present invention will be described in more comprehensive and detailed form below in conjunction with the accompanying drawings and preferred embodiments. However, the protection scope of the present invention is not limited to the following specific embodiments.

[0041] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0042] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0043] Example 1:

[0044] An ozone protection auxiliary agent, the molecular structure is as follows:

[0045] .

[0046] Among them, the main chain has 60 carbons and there are 3 side groups. The side groups are randomly distributed and do not affect the effect.

[0047] The preparation method of the above-mentioned ozone protection auxiliary agent comprises the following steps:

[0048] 84 g of alkane wax with a carbon chain length of C60 and 79.8 g of 1,1-bis(4-dimethylaminophenyl)ethylene were weighed and dissolved in ethylbenzene. 0.84 g of initiator 3,6,9-trimethyl-3,6,9-triethyl-1,4,7-triperoxane was added with stirring. The mixture was reacted at 135°C for 2 h. Isopropanol was added to terminate the reaction. The mixture was rotary evaporated to obtain a crude product. The crude product was vacuum dried at 35°C to constant weight to obtain an ozone protection agent, which is abbreviated as W1.

[0049] Figure 1 This is the infrared spectrum of the ozone protection agent W1 provided in this embodiment. -1 The peak at 2957 cm is the characteristic peak of CH stretching vibration on the benzene ring.-1 The peak at 2919 cm is the characteristic peak of CH3 asymmetric stretching vibration. -1 and 2850cm -1 The characteristic peaks of CH2 asymmetric stretching vibration and symmetric stretching vibration are 1600 cm -1 and 1500cm -1 The peak at 1460 cm is the characteristic peak of C=C stretching vibration of benzene ring skeleton. -1 The characteristic peaks of CH3 asymmetric deformation vibration and CH2 in-plane deformation vibration are at 1378 cm -1 The peak at 1314 cm is the characteristic peak of CH3 symmetric deformation vibration. -1 and 1250cm -1 The characteristic peaks of CN and CC stretching vibrations are at 860 cm -1 The peak at 740 cm is the characteristic peak of CH deformation vibration on the benzene ring. -1 and 705cm -1 The peak at the bottom is the characteristic peak of CH2 horizontal rocking vibration. It can be seen that the ozone protection agent W1 was successfully prepared.

[0050] Example 2:

[0051] An ozone protection auxiliary agent, the molecular structure is as follows:

[0052] .

[0053] Among them, the main chain has 30 carbons and the side groups have 2. The side groups are randomly distributed and do not affect the effect.

[0054] The preparation method of the above-mentioned ozone protection auxiliary agent comprises the following steps:

[0055] 42 g of alkane wax with a carbon chain length of C30 and 64.4 g of 1,1-bis(4-diethylaminophenyl)ethylene were weighed and dissolved in toluene. 1.26 g of initiator benzoyl peroxide was added with stirring. The mixture was reacted at 90°C for 1.5 h. Isopropanol was added to terminate the reaction. The mixture was rotary evaporated to obtain a crude product. The crude product was vacuum dried at 23°C to constant weight to obtain an ozone protection agent, which is abbreviated as W2.

[0056] Application Example 1:

[0057] Rubber compounds were prepared according to the formulations shown in Table 1 below. Compounds 1#, 2#, and 3# were all mixed using conventional mixing techniques. Compound 1# did not contain an ozone protectant, while compound 2# contained a microcrystalline wax that did not contain aromatic amine functional groups. This was compared to compound 2#, which directly added the ozone protectant W1. Comparison of the properties of the compounds obtained from the three formulations demonstrates the ozone protection effect of the ozone protectant W1. Compounds without aromatic amine functional groups exhibit poor ozone protection.

[0058] Table 1: Basic formula of isoprene rubber composite materials (parts by mass)

[0059]

[0060] The rubber compound prepared according to the formulation shown in Table 1 was vulcanized at 150°C for 15 minutes. The properties of the resulting vulcanized rubber are shown in Table 2. Table 2 shows that ozone cracking occurs in the vulcanized rubber without the addition of an ozone protectant or with the addition of microcrystalline wax, whereas no ozone cracking occurs in the vulcanized rubber with the addition of ozone protectant W1. This demonstrates that ozone protectant W1 has a good ozone resistance effect on isoprene rubber composites and can effectively improve the dynamic ozone resistance of the vulcanized rubber.

[0061] Table 2: Properties of isoprene rubber vulcanizate

[0062]

[0063] Application Example 2:

[0064] The rubber compound was prepared according to the formula shown in Table 3 below. Both 4# and 5# were mixed according to the conventional mixing process.

[0065] Table 3: Basic formula of butadiene rubber composite materials (parts by mass)

[0066]

[0067] The rubber compound prepared according to the formulation shown in Table 3 was vulcanized at 150°C for 20 min. The properties of the resulting vulcanized rubber are shown in Table 4. As shown in Table 4, the ozone protection additive W2 has a good ozone resistance effect on the butadiene rubber composite material and can effectively improve the dynamic ozone resistance of the vulcanized rubber.

[0068] Table 4: Properties of butadiene rubber vulcanizate

[0069]

[0070] Application Example 3:

[0071] The rubber compound was prepared according to the formula shown in Table 5 below. Both 6# and 7# were mixed according to the conventional mixing process.

[0072] Table 5: Basic formula of chloroprene rubber composite materials (parts by mass)

[0073]

[0074] The rubber compound prepared according to the formula shown in Table 5 was vulcanized at 150°C for 30 min. The properties of the resulting vulcanized rubber are shown in Table 6. As shown in Table 6, the ozone protection additive W2 has a good ozone resistance effect on the chloroprene rubber composite material and can effectively improve the dynamic ozone resistance of the vulcanized rubber.

[0075] Table 6: Properties of chloroprene rubber vulcanizate

[0076]

[0077] Application Example 4:

[0078] The rubber compound was prepared according to the formula shown in Table 7 below. Both 8# and 9# were mixed according to the conventional mixing process.

[0079] Table 7: Basic formula of natural rubber composite materials (parts by mass)

[0080]

[0081] The rubber compound prepared according to the formulation shown in Table 7 was vulcanized at 150°C for 15 minutes. The properties of the resulting vulcanized rubber are shown in Table 8. As shown in Table 8, the ozone protection additive W1 has a good ozone resistance effect on natural rubber composites and can effectively improve the dynamic ozone resistance of the vulcanized rubber.

[0082] Table 8: Properties of natural rubber vulcanizates

[0083]

[0084] Application Example 5:

[0085] The rubber compound was prepared according to the formula shown in Table 9 below. 10# and 11# were mixed according to the conventional process.

[0086] Table 9: Basic formula of nitrile rubber composite materials (parts by mass)

[0087]

[0088] The rubber compound prepared according to the formulation shown in Table 9 was vulcanized at 150°C for 40 min. The properties of the resulting vulcanized rubber are shown in Table 10. As shown in Table 10, the ozone protection additive W1 has a good ozone resistance effect on the nitrile rubber composite material and can effectively improve the dynamic ozone resistance of the vulcanized rubber.

[0089] Table 10: Properties of Nitrile Rubber Vulcanizate

[0090]

[0091] Application Example 6:

[0092] The rubber compound was prepared according to the formula shown in Table 11. 12# and 13# were mixed according to the conventional process.

[0093] Table 11: Basic formula of styrene-butadiene rubber composite materials (parts by mass)

[0094]

[0095] The rubber compound prepared according to the formulation shown in Table 11 was vulcanized at 150°C for 15 min. The properties of the resulting vulcanized rubber are shown in Table 12. As shown in Table 12, the ozone protection additive W1 has a good ozone resistance effect on the styrene-butadiene rubber composite material and can effectively improve the dynamic ozone resistance of the vulcanized rubber.

[0096] Table 12: Properties of Styrene-Butadiene Rubber Vulcanizate

[0097]

[0098] Application Example 7:

[0099] The rubber compound was prepared according to the formula shown in Table 13 below. 14# and 15# were mixed according to the conventional process.

[0100] Table 13: Basic formula of rubber composite materials containing nitrile rubber and styrene butadiene rubber (parts by mass)

[0101]

[0102] The rubber compound prepared according to the formulation shown in Table 13 was vulcanized at 150°C for 30 min. The properties of the resulting vulcanized rubber are shown in Table 14. As shown in Table 14, the ozone protection additive W2 has a good ozone resistance effect on the rubber composite material of nitrile rubber and styrene butadiene rubber, and can effectively improve the dynamic ozone resistance of the vulcanized rubber.

[0103] Table 14: Properties of vulcanized rubber blended with nitrile rubber and styrene butadiene rubber

[0104]

[0105] Application Example 8:

[0106] The rubber compounds were prepared according to the formulation shown in Table 15 below. 16#, 17#, 18#, 19# and 20# were all prepared using conventional mixing processes.

[0107] Table 15: Basic formula of rubber composite materials containing natural rubber, butadiene rubber and chloroprene rubber (parts by mass)

[0108]

[0109] Among them, antiozonant 6PPD is a conventional chemical antiozonant containing an aromatic amine functional group. The molecular structure of antiozonant A1 is as follows:

[0110] .

[0111] The preparation method of antiozonant A1 comprises the following steps:

[0112] (1) Under nitrogen protection, weigh 19 g of potassium tert-butoxide and 140 g of tetrahydrofuran to prepare a potassium tert-butoxide solution. Weigh 58 g of methyltriphenylphosphine bromide and 90 g of tetrahydrofuran and add them to a three-necked round-bottom flask. Add the potassium tert-butoxide solution while stirring at 0°C and continue stirring for 2 h to obtain a methylenetriphenylphosphine mixed solution.

[0113] (2) Under nitrogen protection, 27 g of 4,4'-bis(dimethylamino)benzophenone and 100 g of tetrahydrofuran were weighed to prepare a solution, which was added to the above methylenetriphenylphosphine mixture at 0°C with stirring, and then the temperature was raised to reflux and the reaction was continued with stirring for 7 h. The reaction mixture was poured into excess deionized water, and the organic layer was separated. The organic layer was washed with saturated sodium bicarbonate aqueous solution until neutral, and then anhydrous magnesium sulfate was added and stirred to dry for a day and night. The filtrate was filtered and rotary evaporated to obtain a crude product. The crude product was separated by column chromatography, rotary evaporated, and vacuum dried at 35°C to constant weight to obtain antiozonant A1.

[0114] The rubber compound prepared according to the formulation shown in Table 15 was vulcanized at 150°C for 20 min. The properties of the resulting vulcanized rubber are shown in Table 16. As shown in Table 16, ozone protection agent W1 has a good ozone resistance effect on natural rubber, butadiene rubber, and chloroprene rubber composites, effectively improving the dynamic ozone resistance of the vulcanized rubber. The combined use of ozone protection agent W1 and antiozonant A1 produces even better results.

[0115] Table 16: Properties of natural rubber, butadiene rubber and chloroprene rubber vulcanizates

[0116]

[0117] As demonstrated in the aforementioned embodiments and application examples, the saturated alkane ozone shielding agent containing aromatic amine functional groups provided by the present invention exhibits excellent dynamic ozone resistance for rubber composites containing carbon-carbon double bonds in their molecular chains, significantly improving the dynamic ozone resistance of the vulcanized rubber. In particular, the combination of the ozone shielding agent of the present invention and antiozonant A1 exhibits even better dynamic ozone resistance.

Claims

1. An ozone protection agent for dynamic rubber, characterized in that: The molecular structure of the ozone protection auxiliary agent is shown below: ； Wherein: the main chain of the molecule is a straight or branched alkane with 18 to 80 carbon atoms; , R 1 、R 2 、R 3 、R 4 is hydrogen, or is the same or different linear or branched alkyl group having 1 to 8 carbon atoms.

2. A method for preparing the ozone protection auxiliary agent according to claim 1, characterized in that: The following steps are involved: Under the action of an initiator, an alkane wax containing 10 to 100 carbon atoms is reacted with the first raw material to obtain the ozone protection auxiliary agent; Wherein, the molecular structure formula of the first raw material is as follows: 。 3. The preparation method according to claim 2, characterized in that The preparation method of the first raw material comprises the following steps: reacting a quaternary phosphine salt with a base to generate methylene triphenyl phosphine, and performing a Wittig reaction on the methylene triphenyl phosphine and a second raw material to obtain the first raw material; Among them, the structural molecular formula of the second raw material is as follows: 。 4. The preparation method according to claim 2, characterized in that First, the alkane wax and the first raw material are dissolved in an organic solvent, an initiator is added under stirring, the reaction is carried out at 60-150° C. for 1-10 hours, isopropyl alcohol is added to terminate the reaction, and the ozone protection agent is obtained by vacuum drying at 10-40° C. to a constant weight.

5. The preparation method according to claim 4, characterized in that The mass ratio of the first raw material to the alkane wax is (0.2-2):1; the mass ratio of the initiator to the alkane wax is (0.01-0.1):1; the organic solvent is selected from one or more of n-hexane, cyclohexane, toluene and ethylbenzene; and the initiator is selected from one or more of 3,6,9-trimethyl-3,6,9-triethyl-1,4,7-triperoxane, benzoyl peroxide, 1,1-di(tert-butylperoxy)cyclohexane and 2,2-di(4,4-di-tert-butylperoxycyclohexyl)propane.

6. Use of the ozone protection auxiliary agent according to claim 1 or the ozone protection auxiliary agent prepared by the preparation method according to any one of claims 2 to 5 in ozone protection of dynamic rubber materials.

7. A rubber comprising a rubber matrix and an additive, characterized in that: The molecular chain of the rubber matrix contains carbon-carbon double bonds, and the additive comprises an ozone protection agent, which is the ozone protection agent according to claim 1 or the ozone protection agent prepared by the preparation method of any one of claims 2-5.

8. The rubber according to claim 7, characterized in that The additive further includes an antiozonant, and the molecular structure of the antiozonant is as follows: ； Among them, R 1 、R 2 、R 3 、R 4 is hydrogen, or is the same or different linear or branched alkyl group having 1 to 8 carbon atoms.

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