Novel multifunctional aromatic carbon resin as well as preparation method and application thereof

Abstract

The invention discloses novel multifunctional aromatic carbon resin and a preparation method and application thereof.The novel multifunctional aromatic carbon resin is prepared from one or more than two of petroleum resin, naphthalene solvent oil and heavy aromatics as raw materials, p-tolualdehyde or paraformaldehyde as a cross-linking agent and one of concentrated sulfuric acid and aluminum trichloride as a catalyst through a catalytic cross-linking thermal polymerization method. The novel multifunctional aromatic carbon resin is used as an additive in the rubber processing process to replace tackifying resin, aromatic hydrocarbon oil and part of carbon black, so that a rubber material is softened and plasticized, the processing performance of the rubber material is improved, meanwhile, the tensile strength, ductility and hardness of a rubber product are improved, the rubber product has an anti-ultraviolet function, the abrasion of the product is reduced, and the service life of the product is prolonged. And the compression set value is reduced.

Description

Technical Field

[0001] The present invention belongs to the field of rubber and plastic product additives, and particularly relates to a novel multifunctional aromatic carbon resin, a preparation method thereof, and an application thereof. Background Art

[0002] In the production process of tires and rubber products, various additives in the rubber compound are essential components. The main action mechanisms of rubber additives include the following aspects: (1) improving the viscosity and fluidity of rubber, thereby improving the processability and moldability of rubber; (2) enhancing the anti-aging, wear-resistant, and corrosion-resistant properties of rubber, thereby increasing the service life of products; (3) improving the toughness and hardness of rubber products, making them have higher tensile strength and pressure resistance. Currently, the types of additives used in rubber processing are limited and have single functions. For example, CN116323690A discloses a method for preparing a hydrogenated petroleum resin, which is a hydride of C9 petroleum resin and has a single performance as a rubber additive. The preparation method of a high softening point hydrogenated petroleum resin disclosed in CN110078847B only solves the problem of increasing the softening point of resin products. In addition, the "method for preparing resin carbon materials from tar coupling components" disclosed in CN118419904A refers to a binder used in the preparation of carbon materials, which has low activity and can only play a role in bonding and curing by high-temperature thermal conversion reactions during the preparation of carbon materials and cannot be used as an additive for rubber products. Therefore, to meet the growing needs of rubber products, it is very necessary to research and develop novel multifunctional rubber product additives that simultaneously have plasticizing functions, anti-aging functions, wear-resistant functions, and can improve the toughness and hardness of products. Summary of the Invention

[0003] To solve the above problems, the present invention provides a novel multifunctional aromatic carbon resin, a preparation method thereof, and an application thereof. Specifically, the aromatic carbon resin provided by the present invention includes the following formula components in parts by mass: 1-8 parts of petroleum resin, 1-9 parts of naphthalene solvent oil, and / or 1-3 parts of heavy aromatic hydrocarbons.

[0004] The preferred aromatic carbon resin includes the following formula components in parts by mass: 3-6 parts of petroleum resin, 3-7 parts of naphthalene solvent oil, and / or 2-3 parts of heavy aromatic hydrocarbons.

[0005] The further preferred aromatic carbon resin includes the following formula components in parts by mass: 6 parts of petroleum resin, 4 parts of naphthalene solvent oil, and 2 parts of heavy aromatic hydrocarbons.

[0006] The further preferred aromatic carbon resin includes the following formula components in parts by mass: 7 parts of petroleum resin and 3 parts of heavy aromatic hydrocarbons.

[0007] The present invention also relates to a preparation method of the novel multifunctional aromatic carbon resin, which includes the following steps:

[0008] Step 1: Weigh petroleum resin, naphthalene solvent oil and / or heavy aromatic hydrocarbons according to the formula.

[0009] Step 2: Add a crosslinking agent and a catalyst. The crosslinking agent is p-methylbenzaldehyde or paraformaldehyde, and the catalyst is concentrated sulfuric acid or aluminum trichloride.

[0010] Step 3: Add petroleum resin, naphthalene solvent oil and / or heavy aromatic hydrocarbons, crosslinking agent, and catalyst into a reaction kettle for catalytic crosslinking thermal polymerization reaction. The reaction temperature is 250°C - 450°C, and the reaction time is 3 hours - 5 hours to obtain a multifunctional aromatic carbon resin.

[0011] In Step 2, the mass fraction of the crosslinking agent is 1 - 6 parts, and the mass fraction of the catalyst is 0.01 - 0.06 parts. In Step 3, the reaction temperature is 375°C, and the reaction time is 3.5 hours.

[0012] The present invention also relates to the application of the novel multifunctional aromatic carbon resin in replacing tackifying resins in rubber product formulations.

[0013] The present invention also relates to the application of the novel multifunctional aromatic carbon resin in replacing aromatic oils in rubber product formulations.

[0014] The present invention also relates to the application of the novel multifunctional aromatic carbon resin in replacing general resin plasticizers in rubber product formulations.

[0015] Advantages of the present invention:

[0016] 1. The specific functions of the novel multifunctional aromatic carbon resin of the present invention during the processing of rubber products are as follows: It softens and plasticizes the rubber compound, improves the processing performance of the rubber compound, and at the same time increases the tensile strength, ductility, and hardness of the rubber product. It has an anti-ultraviolet function, reduces the wear of the product, and reduces the compression set value. The results of the comparative test show that adding an appropriate amount of the aromatic carbon resin of the present invention during rubber processing can completely replace tackifying resins, aromatic oils, and part of carbon black, and the performance indicators of the obtained rubber compound are significantly improved.

[0017] 2. After adding the novel multifunctional aromatic carbon resin of the present invention to the rubber formulation, it can act as an aromatic oil and a general resin, obtaining a rubber compound with good softening and plasticizing properties. The rubber compound has good plastic processing performance, and at the same time can improve the mechanical property indicators of the rubber compound, and the Mooney viscosity index remains unchanged. Specific Embodiments

[0018] In order to make the objectives, technical solutions, and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

[0019] Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the technical field. For the test methods without specific experimental conditions indicated in the following examples, they are generally carried out according to conventional experimental conditions or the experimental conditions recommended by the manufacturer. Unless otherwise specified, the reagents and raw materials used in the present invention can be obtained commercially. For example, petroleum resin, naphthalene solvent oil, and / or heavy aromatics are from PetroChina Fushun Petrochemical Company.

[0020] Example 1

[0021] Weigh 6 portions of petroleum resin, 4 portions of naphthalene solvent oil, 2 portions of heavy aromatics, 1.5 portions of p-tolualdehyde, and 0.02 portion of concentrated sulfuric acid, with each portion corresponding to 20 grams. Add them to a reaction kettle, with a reaction temperature of 375 °C and a reaction time of 3.5 hours. A new type of multifunctional aromatic carbon resin is obtained, having a softening point of 90 °C, a coking value of 37%, quinoline insoluble matter of 0.2%, toluene insoluble matter of 2.1%, ash content of 0.09%, and sulfur content of 0.13%.

[0022] Example 2

[0023] Weigh 7 portions of petroleum resin, 3 portions of heavy aromatics, 2 portions of p-tolualdehyde, and 0.06 portion of aluminum trichloride, with each portion corresponding to 20 grams. Add them to a reaction kettle, with a reaction temperature of 350 °C and a reaction time of 5.5 hours. A new type of multifunctional aromatic carbon resin is obtained, having a softening point of 85 °C, a coking value of 35%, quinoline insoluble matter of 0.2%, toluene insoluble matter of 2.0%, ash content of 0.10%, and sulfur content less than 0.14%.

[0024] Example 3

[0025] Weigh 8 portions of petroleum resin, 2 portions of naphthalene solvent oil, 2 portions of heavy aromatics, 3 portions of p-tolualdehyde, and 0.02 portion of concentrated sulfuric acid, with each portion corresponding to 20 grams. Add them to a reaction kettle, with a reaction temperature of 375 °C and a reaction time of 3.5 hours. A new type of multifunctional aromatic carbon resin is obtained, having a softening point of 92 °C, a coking value of 40%, quinoline insoluble matter of 0.2%, toluene insoluble matter of 2.1%, ash content of 0.09%, and sulfur content of 0.13%.

[0026] Example 4

[0027] Weigh 7 portions of petroleum resin, 5 portions of naphthalene solvent oil, 2 portions of methylbenzaldehyde, and 0.02 portion of concentrated sulfuric acid, with each portion corresponding to 20 grams. Add them to a reaction kettle, with a reaction temperature of 370 °C and a reaction time of 3.7 hours. A new type of multifunctional aromatic carbon resin is obtained, having a softening point of 87 °C, a coking value of 38%, quinoline insoluble matter of 0.2%, toluene insoluble matter of 2.1%, ash content of 0.09%, and sulfur content of 0.13%.

[0028] Application Example

[0029] The novel multifunctional aromatic carbon resin prepared in the examples was added to different rubber compounds to replace the existing components, and the performance of the rubber compounds was tested.

[0030] 1. The novel multifunctional aromatic carbon resin obtained in Example 1 was added to the rubber compound with a medium rubber content. After replacing 1.3% of the tackifying resin with 1.3% of the aromatic carbon resin, the strength, elongation rate and other indicators of the rubber compound with the aromatic carbon resin were significantly higher than those of the rubber compound with the tackifying resin. Among them, the strength increased by 0.6 MPa, the elongation increased by 11.5%, the hardness increased by 2 degrees, the 300% modulus increased by 0.11 MPa, and the abrasion decreased by 0.176 cm3 / 1.61 Km.

[0031] The specific formula of the rubber compound with a medium rubber content is as follows:

[0032]

[0033] Performance comparison of the rubber compound with a medium rubber content:

[0034] Tensile strength / MPa Elongation at break / % Hardness 300% modulus / MPa <![CDATA[Wear per cm 3 / 1.61 Km]]> Original formulation 14.29 524 67 7.27 0.656 After replacement 14.89 535.5 69 7.38 0.48

[0035] 2. The novel multifunctional aromatic carbon resin obtained in Example 2 was added to the rubber compound formula with a high rubber content (47.44%). Using 1.5% of the aromatic carbon resin to replace 1.5% of the tackifying resin, with the formula and process conditions unchanged, the physical and mechanical properties of the rubber compound with the added aromatic carbon resin were significantly improved. The specific data are shown in Table 1. Among them, the strength of the sample increased by 1.52 MPa, the elongation rate increased by 41.5%, the hardness increased by 1 degree, the 300% modulus increased by 0.1 MPa, the wear resistance was improved, and the abrasion decreased by 0.01 cm 3 / 1.61 Km, and the permanent deformation remained the same.

[0036] The specific formula of the rubber compound with a high rubber content is as follows:

[0037]

[0038] Performance comparison of the rubber compound with a high rubber content:

[0039] Tensile strength / MPa Elongation at break / % Hardness 300% modulus / MPa <![CDATA[Wear / cm 3 / 1.61Km]]> Original formulation 13.8 412 64 10.23 0.8 After replacement 15.32 453.5 65 10.33 0.79

[0040] 3. The novel multifunctional aromatic carbon resin obtained in Example 1 was added to the SBR synthetic rubber compound system. Using 1.7% of the aromatic carbon resin to replace 1.7% of the tackifying resin, the strength of the rubber compound increased by 2.09 MPa, the elongation rate increased by 7.5%, the hardness increased by 2 degrees, the 300% modulus increased by 1.63 MPa, the wear resistance was improved, and the abrasion decreased by 0.05 cm 3 / 1.61 Km.

[0041] The specific formula of the SBR synthetic rubber compound is as follows:

[0042]

[0043]

[0044] Comparison of compound properties:

[0045] Tensile strength / MPa Elongation at break / % Hardness 300% modulus / MPa <![CDATA[Wear / cm 3 / 1.61Km]]> Original formulation 11.85 369 76 10.47 0.74 After replacement 13.94 376.5 78 12.1 0.69

[0046] 4. Add the novel multifunctional aromatic carbon resin obtained in Example 2 to the BR synthetic rubber compound system, use 1.7% of the aromatic carbon resin to replace 1.7% of the tackifying resin. The strength of the compound increases by 1.26 MPa, the elongation at break increases by 45%, the hardness remains the same, the 300% modulus increases by 1.15 MPa, the wear resistance improves, and the abrasion loss decreases by 0.21 cm 3 / 1.61 Km, and the permanent set decreases by 1.6%.

[0047] The specific compound formula is as follows:

[0048]

[0049] Comparison of compound properties:

[0050]

[0051] Referring to Application Examples 1-4, replacing the tackifying resin in the compound formula with the aromatic carbon resins prepared in Examples 3 and 4 also achieved substantially the same effect.

[0052] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A novel multifunctional aromatic carbon resin, characterized in that, The aryl carbon resin comprises the following formula components in parts by mass: 1-8 parts of petroleum resin, 1-9 parts of naphthalene solvent oil and / or 1-3 parts of heavy aromatic hydrocarbon.

2. The novel multifunctional aromatic carbon resin according to claim 1, characterized in that, The aryl carbon resin comprises the following formula components in parts by mass: 3-6 parts of petroleum resin, 3-7 parts of naphthalene solvent oil and / or 2-3 parts of heavy aromatic hydrocarbon.

3. The novel multifunctional aromatic carbon resin according to claim 1, characterized in that, The aryl carbon resin comprises the following formula components in parts by mass: 6 parts of petroleum resin, 4 parts of naphthalene solvent oil, 2 parts of heavy aromatic hydrocarbon.

4. The novel multifunctional aromatic carbon resin according to claim 1, wherein The aryl carbon resin comprises the following formula components in parts by mass: 7 parts of petroleum resin, 3 parts of heavy aromatic hydrocarbon.

5. The preparation method of the novel multifunctional aromatic carbon resin according to any one of claims 1 to 4, characterized in that, It includes the following steps: Step 1: Weigh petroleum resin, naphthalene solvent oil and / or heavy aromatic hydrocarbon according to the formula. Step 2: Add a crosslinking agent and a catalyst. The crosslinking agent is p-methylbenzaldehyde or paraformaldehyde, and the catalyst is concentrated sulfuric acid or aluminum trichloride. Step 3: Add the petroleum resin, naphthalene solvent oil and / or heavy aromatic hydrocarbon, crosslinking agent, and catalyst into a reaction kettle for catalytic crosslinking thermal polymerization reaction. The reaction temperature is 250°C - 450°C, and the reaction time is 3 hours - 6 hours to obtain a multifunctional aryl carbon resin.

6. The preparation method of the novel multifunctional aryl carbon resin according to claim 5, wherein In step 2, the mass fraction of the crosslinking agent is 1-6 parts, and the mass fraction of the catalyst is 0.01-0.06 parts. In step 3, the reaction temperature is 375°C, and the reaction time is 3.5 hours.

7. Application of the novel multifunctional aryl carbon resin according to any one of claims 1 to 4 in replacing the tackifying resin in the rubber product formula.

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