Hydroxymethylated alkylphenol formaldehyde resin addition asphalt and preparation method thereof, and rubber composition

Abstract

The embodiment of the present application provides a hydroxymethylated alkylphenol formaldehyde resin addition asphalt and a preparation method thereof, and a rubber composition, which belongs to the technical field of rubber materials. The preparation method comprises: in the presence of an alkaline catalyst, a hydroxymethylation reaction is carried out on alkylphenol and formaldehyde to generate hydroxymethylated alkylphenol; a heating treatment is performed to dehydrate the hydroxymethylated alkylphenol and then react with asphalt to obtain alkylphenol addition asphalt; in the presence of an alkaline catalyst, a secondary hydroxymethylation reaction is carried out on the alkylphenol addition asphalt and formaldehyde to obtain hydroxymethylated alkylphenol formaldehyde resin addition asphalt. In the prepared hydroxymethylated alkylphenol formaldehyde resin addition asphalt, the hydroxymethylated alkylphenol formaldehyde resin matrix can play a role of cross-linking, and the asphalt end introduced by addition can improve the processing performance, mechanical properties and airtightness of the rubber compound.

Description

Technical Field

[0001] The present application relates to the technical field of rubber materials, and in particular to a hydroxymethylated alkylphenol formaldehyde resin addition asphalt and a preparation method thereof, as well as a rubber composition. Background Art

[0002] In the rubber field, hydroxymethylated alkylphenol-formaldehyde resin is used as a vulcanizing agent, also called vulcanized resin, such as SL7025 of Huaqi Chemical. A lot of work has been done on the modification of hydroxymethylated alkylphenol-formaldehyde resin in the prior art. For example, C9 petroleum resin is added to the preparation method of some modified vulcanized resins, so that the prepared modified vulcanized resin has a higher molecular weight, and after being applied to chloroprene adhesives, it is beneficial to improve heat resistance and bonding strength.

[0003] However, in general, vulcanized resin is a vulcanizing agent for rubbers such as butyl rubber and natural rubber, which plays a role in vulcanization and cross-linking. It has no obvious effect on the combination of filler and rubber. In addition, it has no obvious benefit on the air tightness of vulcanized bladders or airtight layer rubber materials mainly based on butyl rubber. Summary of the invention

[0004] The purpose of the present application is to provide a hydroxymethylated alkylphenol formaldehyde resin addition asphalt and a preparation method thereof, as well as a rubber composition. The hydroxymethylated alkylphenol formaldehyde resin addition asphalt can play a cross-linking role and can improve the processing performance, mechanical properties and airtightness of the rubber.

[0005] The embodiment of the present application is implemented as follows:

[0006] In a first aspect, the present application provides a method for preparing a hydroxymethylated alkylphenol formaldehyde resin addition asphalt, comprising:

[0007] In the presence of an alkali catalyst, alkylphenol and formaldehyde undergo a hydroxymethylation reaction to generate hydroxymethyl alkylphenol;

[0008] Heat treatment to dehydrate hydroxymethyl alkylphenol and then react with asphalt to obtain alkylphenol addition asphalt;

[0009] In the presence of an alkali catalyst, the alkylphenol addition asphalt is subjected to a secondary hydroxymethylation reaction with formaldehyde to obtain hydroxymethylated alkylphenol formaldehyde resin addition asphalt.

[0010] In some possible embodiments, the alkylphenol is p-alkylphenol, wherein the carbon number of the alkyl group is C1 to C20.

[0011] In some possible embodiments, the alkylphenol includes at least one of p-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, and p-methylphenol.

[0012] In some possible embodiments, in the first hydroxymethylation step and / or the second hydroxymethylation step, the molar ratio of the alkylphenol structure to the formaldehyde is 1:1 to 1:1.7, and optionally 1:1 to 1:1.5.

[0013] In some possible embodiments, in the step of the primary hydroxymethylation reaction and / or the step of the secondary hydroxymethylation reaction, the reaction temperature is 10°C to 100°C, optionally 30°C to 90°C.

[0014] In some possible embodiments, in the first hydroxymethylation step and / or the second hydroxymethylation step, the molar ratio of the base catalyst to the alkylphenol structure is 0.01 to 0.5:1, and optionally 0.01 to 0.3:1.

[0015] In some possible embodiments, in the step of addition reaction, the reaction temperature is 150°C to 250°C, optionally 160°C to 220°C.

[0016] In a second aspect, an embodiment of the present application provides a hydroxymethylated alkylphenol formaldehyde resin addition asphalt, which is prepared by the preparation method provided in the above embodiment.

[0017] In a third aspect, an embodiment of the present application provides a rubber composition, comprising rubber, a filler, and a hydroxymethylated alkylphenol formaldehyde resin addition asphalt prepared by the preparation method provided in the above embodiment.

[0018] In some possible embodiments, based on 100 parts by weight of the rubber, the weight of the filler is 1 to 150 parts by weight, and the weight of the hydroxymethylated alkylphenol formaldehyde resin addition asphalt is 1 to 30 parts by weight; alternatively, based on 100 parts by weight of the rubber, the weight of the filler is 1 to 100 parts by weight, and the weight of the hydroxymethylated alkylphenol formaldehyde resin addition asphalt is 1 to 15 parts by weight.

[0019] The hydroxymethylated alkylphenol formaldehyde resin addition asphalt and its preparation method, as well as the rubber composition provided in the embodiments of the present application have the following beneficial effects:

[0020] In the hydroxymethylated alkylphenol formaldehyde resin addition asphalt prepared by the preparation method provided in the embodiment of the present application, the hydroxymethylated alkylphenol formaldehyde resin matrix can play a cross-linking role; the asphalt end is connected in the form of addition asphalt, and the asphalt end can better combine with the filler, which can reduce the Mooney viscosity of the rubber, making the mixing of the rubber easier and requiring less energy consumption, thereby improving the processing performance of the rubber. At the same time, the asphalt end can also improve the interaction between rubber and filler, thereby improving the mechanical properties and airtightness of the rubber. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0022] It should be noted that “and / or” in this application, such as “Feature 1 and / or Feature 2”, refers to the three situations of “Feature 1” alone, “Feature 2” alone, or “Feature 1” plus “Feature 2”.

[0023] In addition, in the description of the present application, unless otherwise specified, the meaning of "multiple" in "one or more" refers to more than two types; the meanings of "above" and "below" include the number itself; the range of "value a ~ value b" includes the two end values ​​"a" and "b", and the "unit" in "value a ~ value b + unit of measurement" represents the "unit of measurement" of both "value a" and "value b".

[0024] The hydroxymethylated alkylphenol formaldehyde resin addition asphalt and its preparation method, as well as the rubber composition according to the embodiments of the present application are described in detail below.

[0025] In a first aspect, the present application provides a method for preparing a hydroxymethylated alkylphenol formaldehyde resin addition asphalt, comprising:

[0026] In the presence of an alkali catalyst, alkylphenol and formaldehyde undergo a hydroxymethylation reaction to generate hydroxymethyl alkylphenol;

[0027] Heat treatment to dehydrate hydroxymethyl alkylphenol and then react with asphalt to obtain alkylphenol addition asphalt;

[0028] In the presence of an alkali catalyst, the alkylphenol addition asphalt is subjected to a secondary hydroxymethylation reaction with formaldehyde to obtain hydroxymethylated alkylphenol formaldehyde resin addition asphalt.

[0029] In the preparation method provided in the embodiment of the present application, the primary hydroxymethylation reaction refers to the hydroxymethylation reaction carried out for the first time in the above process steps; the heating treatment causes the hydroxymethyl alkylphenol molecule to be dehydrated to generate a quinone methyl intermediate product, and the quinone methyl intermediate product reacts with the unsaturated bonds of asphalt to obtain alkylphenol addition asphalt; the secondary hydroxymethylation reaction refers to the hydroxymethylation reaction carried out for the second time in the above process steps, and during the reaction, the remaining reactive sites in the alkylphenol react with formaldehyde under alkali catalysis to undergo a hydroxymethylation reaction.

[0030] In the hydroxymethylated alkylphenol formaldehyde resin addition asphalt prepared by the preparation method provided in the embodiment of the present application, the hydroxymethylated alkylphenol formaldehyde resin matrix can play a cross-linking role; the asphalt end is connected in the form of addition asphalt, and the asphalt end can better combine with the filler, which can reduce the Mooney viscosity of the rubber, making the mixing of the rubber easier and requiring less energy consumption, thereby improving the processing performance of the rubber. At the same time, the asphalt end can also improve the interaction between rubber and filler, thereby improving the mechanical properties and airtightness of the rubber.

[0031] In the present application, p-alkylphenol is preferably used. P-alkylphenol is a common industrial product and is easily available in large quantities. Moreover, p-alkylphenol products have been widely used in the rubber additive industry. In addition, the hydroxymethylated alkylphenol generated by the hydroxymethylation reaction of p-alkylphenol and formaldehyde is conducive to the subsequent addition reaction with asphalt.

[0032] Optionally, in the alkylphenol, the number of carbon atoms in the alkyl group is C1 to C20 (C1 means 1 carbon atom, C20 means 20 carbon atoms), for example but not limited to any one of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19 and C20 or a range between any two of them. It is understood that the number of carbon atoms in the alkyl group is a positive integer, and when the value is a range, the actual value is a positive integer corresponding to the range.

[0033] As an example, the alkylphenol includes at least one of p-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol and p-methylphenol, for example, one thereof.

[0034] It should be noted that, in the two hydroxymethylation reactions, reasonable control of the usage ratio of the raw materials and / or reasonable control of the usage ratio of the raw materials and the base catalyst is conducive to a more controllable and thorough hydroxymethylation reaction.

[0035] In some possible embodiments, in the step of a hydroxymethylation reaction, the molar ratio of the alkylphenol structure to the formaldehyde is 1:1 to 1:1.7, and optionally 1:1-1:1.5.

[0036] In some possible embodiments, in the step of secondary hydroxymethylation, the molar ratio of the alkylphenol structure to formaldehyde is 1:1 to 1:1.7, and optionally 1:1-1:1.5.

[0037] In the above embodiment, in the step of the first methylolation reaction, the alkylphenol structure is the alkylphenol fed in; in the step of the second methylolation reaction, the alkylphenol structure is the alkylphenol corresponding to the alkylphenol addition asphalt.

[0038] As an example, in the two hydroxymethylation steps, the molar ratio of the alkylphenol structure to the formaldehyde is, for example but not limited to, any one of 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6 and 1:1.7 or a range between any two of them.

[0039] In some possible embodiments, in the step of the primary hydroxymethylation reaction, the molar ratio of the base catalyst to the alkylphenol structure is 0.01 to 0.5:1, and optionally 0.01 to 0.3:1.

[0040] In some possible embodiments, in the step of the secondary hydroxymethylation reaction, the molar ratio of the base catalyst to the alkylphenol structure is 0.01 to 0.5:1, and optionally 0.01 to 0.3:1.

[0041] In the above embodiment, similarly, in the step of the first methylolation reaction, the alkylphenol structure is the alkylphenol fed in; in the step of the second methylolation reaction, the alkylphenol structure is the alkylphenol corresponding to the alkylphenol addition asphalt.

[0042] As an example, in the two hydroxymethylation steps, the molar ratio of the base catalyst to the alkylphenol structure is, for example but not limited to, any one of 0.01:1, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1 and 0.5:1, or a range between any two of them.

[0043] It should be noted that, in the two hydroxymethylation reactions, reasonable control of the reaction temperature is conducive to a more controllable and thorough hydroxymethylation reaction. Similarly, in the addition reaction step, reasonable control of the reaction temperature is conducive to a more controllable and effective addition reaction.

[0044] In some possible embodiments, in the step of the primary hydroxymethylation reaction, the reaction temperature is 10°C to 100°C, optionally 30°C to 90°C.

[0045] In some possible embodiments, in the step of secondary hydroxymethylation, the reaction temperature is 10°C to 100°C, optionally 30°C to 90°C.

[0046] As an example, in the two hydroxymethylation reaction steps, the reaction temperature is, for example but not limited to, any one of 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C and 90°C, or a range between any two of them.

[0047] In some possible embodiments, in the step of addition reaction, the reaction temperature is 150°C to 250°C, optionally 160°C to 220°C.

[0048] As an example, in the addition reaction step, the reaction temperature is, for example but not limited to, any one of 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C and 250°C, or a range between any two of them.

[0049] In a second aspect, an embodiment of the present application provides a hydroxymethylated alkylphenol formaldehyde resin addition asphalt, which is prepared by the preparation method provided in the above embodiment.

[0050] It can be understood that the hydroxymethylated alkylphenol formaldehyde resin addition asphalt provided in the embodiments of the present application is prepared by adding asphalt to the hydroxymethylated alkylphenol formaldehyde resin through the preparation method provided in the above embodiments, that is, the hydroxymethylated alkylphenol formaldehyde resin addition asphalt includes a hydroxymethylated alkylphenol formaldehyde resin matrix and asphalt added to the matrix.

[0051] In a third aspect, an embodiment of the present application provides a rubber composition, comprising rubber, a filler, and a hydroxymethylated alkylphenol formaldehyde resin addition asphalt prepared by the preparation method provided in the above embodiment.

[0052] In the present application, the types of rubber and filler are not limited and can be selected according to conventional types or needs.

[0053] As for the rubber, as an example, the rubber includes at least one of various rubbers such as various natural rubbers, isoprene rubbers, various polybutadiene rubbers, various polystyrene-butadiene copolymer rubbers, various butyl rubbers, various EPDM rubbers, various nitrile rubbers, and the like.

[0054] As for the filler, as an example, the filler includes carbon black, such as carbon black.

[0055] In some possible embodiments, based on 100 parts by weight of the rubber, the weight of the filler is 1 to 150 parts by weight, and the weight of the hydroxymethylated alkylphenol formaldehyde resin addition asphalt is 1 to 30 parts by weight; alternatively, based on 100 parts by weight of the rubber, the weight of the filler is 1 to 100 parts by weight, and the weight of the hydroxymethylated alkylphenol formaldehyde resin addition asphalt is 1 to 15 parts by weight.

[0056] As an example, based on the weight of the rubber as 100 parts by weight, the weight of the filler may be, for example but not limited to, 1 part by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, or 150 parts by weight, or any range between two of them.

[0057] As an example, based on 100 parts by weight of rubber, the weight of the hydroxymethylated alkylphenol formaldehyde resin addition asphalt is, for example but not limited to, any one of 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight and 30 parts by weight, or a range between any two of them.

[0058] It should be noted that, in addition to the above basic components, the rubber composition provided in the embodiments of the present application may also contain a variety of commonly used additives, such as vulcanizers, zinc oxide, stearic acid, antioxidants, processing aids, operating oils, etc.

[0059] In the present application, the rubber composition can be prepared by mixing the components in a conventional manner.

[0060] The hydroxymethylated alkylphenol formaldehyde resin addition asphalt and its preparation method, as well as the rubber composition provided in the present application will be exemplarily described below in conjunction with specific experiments.

[0061] 1. Preparation of Hydroxymethylated Alkylphenol Formaldehyde Resin Addition Asphalt

[0062] Example 1

[0063] Add 150 grams of p-tert-butylphenol and 24 grams of 10% sodium hydroxide aqueous solution to a four-necked flask, heat up and melt and stir, then add 85.1 grams of 37% formaldehyde aqueous solution drop by drop at 65°C, and then react at a constant temperature for 3 hours. Add 15 grams of 20% sulfuric acid aqueous solution to neutralize, let stand for stratification, and separate the water layer. Then add dropwise to 1050 grams of 180°C stirred asphalt, then continue stirring and reacting for 2 hours, and gradually heat up to 195°C within these 2 hours. Then, reduce the material temperature to 70°C, add 30 grams of 10% sodium hydroxide aqueous solution, add 89.1 grams of 37% formaldehyde dropwise, and then react for 3 hours. Add 19 grams of 20% sulfuric acid aqueous solution to neutralize, wash with water, and remove salt. Vacuum distillation removes water to obtain the product hydroxymethylated p-tert-butylphenol formaldehyde resin addition asphalt.

[0064] Example 2

[0065] Add 206 grams of p-tert-octylphenol and 30.9 grams of 20% potassium hydroxide aqueous solution to a four-necked flask, heat to melt, stir, and drop 66 grams of 50% formaldehyde aqueous solution at 80°C for 3 hours. Then add 42 grams of 10% hydrochloric acid aqueous solution to neutralize, let stand for stratification, separate the water layer, and then vacuum distill at 80°C to remove residual moisture. Then drop it into 1000 grams of 190°C, stirred asphalt, and react for 2 hours. Then lower the temperature to 85°C, add 26.9 grams of 25% potassium hydroxide aqueous solution, drop 69 grams of 50% formaldehyde aqueous solution, and react for 3.5 hours. Add 44 grams of 10% hydrochloric acid aqueous solution to neutralize, wash with water to remove salt. Vacuum distill to remove moisture to obtain the product hydroxymethylated p-tert-octylphenol formaldehyde resin addition asphalt.

[0066] Example 3

[0067] Add 262.5 grams of p-dodecylphenol and 17.3 grams of 30% sodium hydroxide aqueous solution to a four-necked flask, stir, add 72 grams of 50% formaldehyde aqueous solution at 90°C, and then react for 4 hours. Add 8.3 grams of oxalic acid dihydrate to neutralize, stir for 20 minutes, let stand for stratification, separate the water layer, and then remove residual moisture by vacuum distillation at 90°C. Then, gradually add dropwise to 950 grams of asphalt stirred at 200°C, then stir and react for 3 hours and heat to 205°C. Then, lower the temperature to 90°C, add 28 grams of 20% sodium hydroxide aqueous solution, add 80 grams of 50% formaldehyde aqueous solution under stirring, and then continue to react for 4 hours. Add 8.9 grams of oxalic acid dihydrate, stir for 30 minutes, and then wash with water to remove salt. Vacuum distillation removes moisture to obtain the product hydroxymethylated p-dodecylphenol formaldehyde resin addition asphalt.

[0068] Example 4

[0069] Add 108 grams of p-methylphenol and 21 grams of 10% sodium hydroxide aqueous solution to a four-necked flask, stir, and drop 83.5 grams of 37% formaldehyde aqueous solution at 50°C, and react for 2 hours. Add 27 grams of 10% sulfuric acid aqueous solution to neutralize, let stand for stratification, and separate the water layer. Then add dropwise to 1100 grams of 175°C stirred asphalt, continue to react for 2 hours after the addition is complete, and gradually heat up to 190°C within these 2 hours. Then, cool to 50°C, add 22 grams of 10% sodium hydroxide aqueous solution, dropwise add 85.1 grams of 37% formaldehyde aqueous solution, and react for 2 hours. Add 27 grams of 10% sulfuric acid aqueous solution and stir for 30 minutes. Wash with water to remove salt. Vacuum distillation to remove moisture. The product hydroxymethylated p-methylphenol formaldehyde resin addition asphalt is obtained.

[0070] 2. Preparation of Rubber Composition

[0071] The raw materials of the rubber composition were prepared according to the recipe in Table 1, and the rubber, carbon black, sulfur and other components except the vulcanization accelerator were mixed for 6 minutes using a 1.6-liter Bambury internal mixer to obtain a masterbatch, and then the vulcanization accelerator and sulfur were mixed in the masterbatch using an open rubber mixer to obtain a rubber composition, and each of the obtained rubber compositions was vulcanized at a temperature of 175° C. for 60 minutes to obtain a vulcanized rubber.

[0072] Table 1

[0073]

[0074]

[0075] Note: In each embodiment and comparative example, the dosage unit of each component is part by weight. The sources of raw materials in each embodiment and comparative example are as follows:

[0076] 4-tert-Butylphenol, Sinopharm Group

[0077] 4-tert-Octylphenol, Sinopharm Group

[0078] 4-Dodecylphenol, Sinopharm Group

[0079] p-Cresol, Sinopharm Group

[0080] Sodium hydroxide, Sinopharm Group

[0081] Potassium hydroxide, Sinopharm Group

[0082] Formaldehyde, Sinopharm Group

[0083] Sulfuric acid, Sinopharm Group

[0084] Hydrochloric acid, Sinopharm Group

[0085] Oxalic acid, Sinopharm Group

[0086] Asphalt, Luoyang Petrochemical

[0087] Butyl rubber, JSR Group

[0088] Carbon black, Evonik

[0089] Zinc Oxide, Dalian Zinc Oxide Factory

[0090] Vulcanized resin, Huaqi (China) Chemical Co., Ltd.

[0091] The equipment information in each embodiment and comparative example is as follows:

[0092] 1.6L BR1600 internal mixer, manufactured by Farrel, USA

[0093] BH-KL-6 type mixing mill, product of Baihong Machinery (Shanghai) Co., Ltd.

[0094] RPA2000, ALPHA, USA

[0095] XLB-D 600×600 flat plate vulcanizing press, product of Zhejiang Huzhou Hongqiao Machinery Factory

[0096] 3. Testing the properties of rubber compositions

[0097] The Mooney viscosity (reaction processing performance), mechanical properties and air tightness properties of the vulcanized rubber provided in each embodiment and comparative example were tested.

[0098] The testing equipment information is as follows:

[0099] MV2000 Mooney Viscometer, ALPHA, USA

[0100] Model 3365 electronic tensile testing machine, INSTRON, USA

[0101] VAC-V1 differential pressure gas permeameter, Jinan Languang Electromechanical Technology Co., Ltd.

[0102] The test results are shown in Table 2.

[0103] Table 2

[0104]

[0105] According to Table 1 and Table 2, we can know that:

[0106] The rubber provided in the embodiment of the present application uses asphalt added to the vulcanized resin. Compared with the comparative example 1 without the addition of asphalt, the Mooney viscosity of the rubber is reduced, and the processing performance of the rubber is improved; at the same time, the mechanical properties of the rubber are improved to a certain extent, and the airtightness performance is significantly improved.

[0107] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents the selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

Claims

1. A method for preparing a hydroxymethylated alkylphenol formaldehyde resin addition asphalt, characterized in that: include: In the presence of an alkaline catalyst, an alkylphenol and formaldehyde are subjected to a hydroxymethylation reaction to generate hydroxymethyl alkylphenol, wherein the alkylphenol is p-alkylphenol, wherein the number of carbon atoms of the alkyl group is C1 to C20; Heating the hydroxymethyl alkylphenol to dehydrate the hydroxymethyl alkylphenol and then react with asphalt to obtain alkylphenol addition asphalt; In the presence of an alkali catalyst, the alkylphenol addition asphalt is subjected to a secondary hydroxymethylation reaction with formaldehyde to obtain a hydroxymethylated alkylphenol formaldehyde resin addition asphalt; In the step of the primary hydroxymethylation reaction and / or the step of the secondary hydroxymethylation reaction, the molar ratio of the alkylphenol structure to the formaldehyde is 1:1 to 1:1.7, and the molar ratio of the base catalyst to the alkylphenol structure is 0.01 to 0.5:

1.

2. The preparation method according to claim 1, characterized in that: The alkylphenol includes at least one of p-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol and p-methylphenol.

3. The preparation method according to claim 1, characterized in that: In the step of the primary hydroxymethylation reaction and / or in the step of the secondary hydroxymethylation reaction, The molar ratio of the alkylphenol structure to the formaldehyde is 1:1-1:1.

5.

4. The preparation method according to claim 1, characterized in that: In the step of the primary hydroxymethylation reaction and / or the step of the secondary hydroxymethylation reaction, the reaction temperature is 10°C to 100°C.

5. The preparation method according to claim 4, characterized in that: In the step of the primary hydroxymethylation reaction and / or the step of the secondary hydroxymethylation reaction, the reaction temperature is 30°C to 90°C.

6. The preparation method according to claim 1, 4 or 5, characterized in that: In the step of the primary hydroxymethylation reaction and / or in the step of the secondary hydroxymethylation reaction, The molar ratio of the base catalyst to the alkylphenol structure is 0.01 to 0.3:

1.

7. The preparation method according to claim 1, characterized in that: In the step of the addition reaction, the reaction temperature is 150°C to 250°C.

8. The preparation method according to claim 7, characterized in that: In the step of the addition reaction, the reaction temperature is 160°C to 220°C.

9. A hydroxymethylated alkylphenol formaldehyde resin addition asphalt, characterized in that: The method is prepared according to any one of claims 1 to 8.

10. A rubber composition, characterized in that: The invention comprises rubber, filler and the hydroxymethylated alkylphenol formaldehyde resin addition asphalt prepared by the preparation method according to any one of claims 1 to 8.

11. The rubber composition according to claim 10, characterized in that Based on 100 parts by weight of the rubber, the weight of the filler is 1 to 150 parts by weight, and the weight of the hydroxymethylated alkylphenol formaldehyde resin addition asphalt is 1 to 30 parts by weight.

12. The rubber composition according to claim 11, characterized in that Based on 100 parts by weight of the rubber, the weight of the filler is 1 to 100 parts by weight, and the weight of the hydroxymethylated alkylphenol formaldehyde resin addition asphalt is 1 to 15 parts by weight.

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