An inorganic filler block copolymer modifier for rubber, its preparation method, modified inorganic filler, and its application.

Abstract

This invention provides a block copolymer modifier for rubber, its preparation method, the modified inorganic filler, and its application. The modified liquid rubber is prepared by esterification of a hydroxyl-containing liquid rubber and a RAFT reagent with carboxyl groups. The modified liquid rubber then initiates the polymerization of vinyl functional monomers to obtain the block copolymer modifier. The block copolymer modifier is dissolved in a solvent, and the solution is sprayed onto the surface of the inorganic filler. After drying, the modified inorganic filler is obtained and used for reinforcing rubber materials. Compared with existing technologies, this invention utilizes the co-vulcanization of the liquid rubber and the rubber matrix, and the bonding effect of the vinyl functional monomers. Chemical bonds are formed at the interface of the modified inorganic filler, connecting it to the matrix material, effectively improving the dispersion performance and interfacial compatibility of the inorganic filler. The modified inorganic filler shows significant advantages in enhancing the tensile strength, tear strength, elongation at break, or stress at a given elongation of rubber materials.

Description

Technical Field

[0001] This invention belongs to the field of rubber fillers, and particularly relates to an inorganic filler block copolymer modifier for rubber, its preparation method, modified inorganic filler and its application. Background Technology

[0002] In recent years, it has been discovered that incorporating inorganic fillers into rubber and plastic materials can significantly improve their tensile and wear resistance. Inorganic fillers include materials such as silica, calcium carbonate, kaolin, and talc. Furthermore, the smaller the particle size and the more uniform the dispersion of the inorganic filler, the better its performance enhancement effect. However, smaller particle sizes often result in higher surface energy, which can lead to filler agglomeration, uneven dispersion, and a weakened reinforcing effect. Therefore, developing inorganic fillers that possess both good mechanical reinforcing properties and good dispersibility has become a key research focus.

[0003] There are many methods for chemically modifying inorganic fillers. Some inorganic fillers possess hydroxyl groups on their surface, which can be directly used for grafting. More often, reactions are designed based on hydroxyl groups to introduce various functional groups before grafting. There are three main methods for grafting polymers onto the surface of inorganic particles;

[0004] 1) Introduce double bonds on the particle surface, followed by copolymerization with monomers;

[0005] 2) Utilize the reaction between functional groups on the particle surface and polymer end groups to attach the polymer to the particle surface;

[0006] 3) Introduce active sites on the particle surface that can initiate polymerization, so that monomers grow into polymers on the particle surface.

[0007] Prucker (Macromolecules, 1998, 3(31):592-601) modified silica using traditional free radical polymerization. His method involved grafting nitrogen-containing free radical initiators onto the silica surface, followed by free radical polymerization initiated by these modified silica particles, resulting in polymer grafting onto the silica surface. Huck summarized methods for grafting polymer molecular brushes onto SiO2 spheres, including atom transfer radical polymerization (ATRP), oxynitrite-stabilized free radical polymerization, reversible addition-fragmentation chain transfer polymerization (RAFT), and active anionic surface-initiated polymerization (LASIP) (Chemical Society Reviews, 2004, 33, 14-22). These methods primarily involve modifying the silica surface to initiate monomer polymerization. While these modified fillers can improve polymer performance to some extent, they are difficult to prepare in large quantities, limiting their large-scale production and hindering product industrialization.

[0008] A patent published on January 15, 2019, with publication number CN 109206567A, provides a method for preparing inorganic nanoparticles with surface-grafted vinyl polymers. The method involves dispersing inorganic nanoparticles in a solvent, then reacting them with an anhydride containing double bonds to prepare inorganic nanoparticles that can copolymerize with vinyl monomers. These nanoparticles are then mixed with vinyl monomers and an initiator, and reacted to obtain inorganic nanoparticles with surface-grafted vinyl polymers. However, its method does not provide ideal results in improving blending. Summary of the Invention

[0009] The present invention aims to provide an inorganic filler block copolymer modifier for rubber and its preparation method. The modified liquid rubber is prepared by esterification of hydroxyl-containing liquid rubber and a carboxyl-containing RAFT reagent; the modified liquid rubber then initiates a polymerization reaction of vinyl functional monomers to obtain the block copolymer modifier. The preparation process involves few steps, is simple to operate, and uses mild reaction conditions, facilitating large-scale production.

[0010] Another objective of this invention is to provide a modified inorganic filler and its application. The modified inorganic filler is obtained by spraying the block copolymer modifier for rubber filler prepared above onto the surface of the inorganic filler, which can be used in rubber materials.

[0011] The specific technical solution of this invention is as follows:

[0012] A method for preparing an inorganic filler block copolymer modifier for rubber includes the following steps:

[0013] 1) Disperse hydroxyl-containing liquid rubber in a solvent, add RAFT reagent with carboxyl groups, esterification catalyst and dehydrating agent, react to obtain modified liquid rubber;

[0014] 2) Add the modified liquid rubber to the solvent, add vinyl functional monomers and free radical initiators, and heat the mixture under an inert atmosphere to obtain an inorganic filler block copolymer modifier for rubber.

[0015] The molar ratio of the hydroxyl-containing liquid rubber, the carboxyl-containing RAFT reagent, the esterification catalyst, and the dehydrating agent in step 1) is 1:1 to 10:0.005 to 0.1:0.1 to 4.

[0016] The mass ratio of the hydroxyl-containing liquid rubber to the solvent in step 1) is 1:1-10.

[0017] The reaction conditions described in step 1) refer to reacting at room temperature for 24-72 hours.

[0018] Step 1) The hydroxyl-containing liquid rubber is selected from hydroxyl-terminated liquid nitrile rubber, hydroxyl-terminated liquid styrene-butadiene rubber, hydroxyl-terminated polybutadiene, and hydroxyl-terminated polyisoprene.

[0019] The solvent in step 1) is selected from any one of dichloromethane, toluene, 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide;

[0020] Step 1) The RAFT reagent with a carboxyl group is selected from: 2-(dodecylthiothiocarbonylthio)-2-methylpropionic acid, 4-cyano-4-(dodecylthioalkylthiocarbonyl)thioalkylpentanoic acid, 4-cyano-4-(phenylthiocarboxylthio)pentanoic acid or ethyl xanthic acid;

[0021] The esterification catalyst in step 1) is selected from 4-dimethylaminopyridine;

[0022] The dehydrating agent in step 1) is selected from 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and dicyclohexylcarbodiimide;

[0023] In step 1), after the reaction is complete, precipitate with a precipitating agent, then dry, and repeat 3-5 times;

[0024] In step 1), the product is precipitated with a precipitant, dried to constant weight, and then precipitated again with a precipitant. This process is repeated three times to completely remove the RAFT reagent.

[0025] In step 1), the precipitant is selected from methanol, ethanol, petroleum ether or n-hexane.

[0026] The drying operation described in step 1) refers to drying in a vacuum oven at 40-70℃ for 12-36 hours.

[0027] In step 2), the molar ratio of the modified liquid rubber, free radical initiator, and vinyl functional monomer is 1:0.1-0.3:1-200.

[0028] In step 2), the mass ratio of the vinyl functional monomer to the solvent is 1:5-50.

[0029] The vinyl functional monomer mentioned in step 2) is selected from methacrylic anhydride, glycidyl methacrylate, 3-(methacryloyloxy)propyltrimethoxysilane or vinyltrimethoxysilane;

[0030] The free radical initiator mentioned in step 2) is selected from azobisisobutyronitrile, benzoyl peroxide, tert-butyl peroxide, and dimethyl azobisisobutyrate.

[0031] The solvent mentioned in step 2) is selected from toluene, 1,4-dioxane, or tetrahydrofuran.

[0032] The heating reaction in step 2) specifically involves a polymerization temperature of 50-130℃ and a reaction time of 1-10 hours.

[0033] Step 2) The inert atmosphere refers to a nitrogen atmosphere or an argon atmosphere.

[0034] After the heating reaction in step 2) is completed, the product is precipitated, washed, and dried; the drying refers to drying in a vacuum oven at 20-60℃ for 12-36 hours.

[0035] The present invention provides an inorganic filler block copolymer modifier for rubber, which is prepared by the above preparation method. The inorganic filler block copolymer modifier for rubber has a molecular weight of 500-100000 g / mol and contains 10-70 wt% vinyl functional monomers.

[0036] This invention utilizes the co-vulcanization of liquid rubber and the rubber matrix, along with the bonding effect of vinyl functional monomers, to form chemical bonds at the interface of the modified inorganic filler that connect with the matrix material. This effectively improves the dispersion performance and interfacial compatibility of the inorganic filler. The modified inorganic filler exhibits significant advantages in enhancing the tensile strength, tear strength, elongation at break, and stress at a given elongation of rubber materials.

[0037] The modified inorganic filler provided by the present invention is obtained by modification with the above-mentioned block copolymer modifier for inorganic fillers used in rubber.

[0038] The specific modification method is as follows: dissolve the inorganic filler block copolymer modifier for rubber in a solvent, then spray the resulting modified solution onto the inorganic filler and dry it.

[0039] In the method for modifying rubber with an inorganic filler block copolymer modifier, the spraying is carried out by aerosol spraying; the solvent is selected from 1,4-dioxane, tetrahydrofuran, toluene, or dichloromethane; the concentration of the modification solution is 0.5-10 wt%; the inorganic filler is selected from talc, silica, kaolin, calcium carbonate, and / or montmorillonite. The mass ratio of the modification solution to the inorganic filler is controlled at 3:1-1:3; the drying is carried out first at atmospheric pressure and then under vacuum; the atmospheric pressure drying conditions are: reaction at 50-130℃ for 12-48 hours; the vacuum drying refers to drying in a vacuum oven at 40-80℃ for 12-36 hours.

[0040] This invention utilizes the co-vulcanization of liquid rubber and the rubber matrix, along with the bonding effect of vinyl functional monomers, to form chemical bonds at the interface of the modified inorganic filler that connect with the matrix material. This effectively improves the dispersion performance and interfacial compatibility of the inorganic filler. The modified inorganic filler exhibits significant advantages in enhancing the tensile strength, tear strength, elongation at break, and stress at a given elongation of rubber materials.

[0041] The modified inorganic filler provided by this invention is used in rubber materials, mainly for enhancing the performance of rubber materials.

[0042] The rubber material includes one or more blends of natural rubber, styrene-butadiene rubber, cis-butadiene rubber, isoprene rubber, nitrile rubber, ethylene propylene diene monomer (EPDM) rubber, or SBS.

[0043] The modified inorganic filler is used in rubber materials at a rate of 2-80 wt% of the rubber compound.

[0044] Existing technologies utilize inorganic fillers, whose small particle size effectively improves the tensile and abrasion resistance of materials. However, inorganic fillers have high surface energy, are prone to agglomeration, and have poor compatibility with rubber materials, resulting in poor dispersion within the matrix and causing stress concentration, which reduces the mechanical properties of rubber materials. The high-performance modified inorganic filler prepared in this invention utilizes the compatibility between grafted liquid rubber and the matrix material, as well as the interaction between vinyl functional monomers and fillers, to effectively improve the performance of inorganic filler-reinforced rubber materials, providing a better foundation for more effectively leveraging the synergistic properties of different components. For example, the PGMA-PB-PGMA block copolymer synthesized in Example 1 was used to modify talc. The modified talc reinforced nitrile rubber. Performance-modified talc can increase the tensile strength of nitrile rubber by 30.2%; tear strength by 15.6%; elongation at break by 11.4%; Shore hardness to 85; and permanent compression set by up to 37.6%, with the maximum deformation remaining at around 10%. The preparation method of the modified inorganic filler provided by this invention is simple and can be widely applied industrially. The interfacial compatibility between the inorganic filler and the rubber material modified by spray drying is significantly improved. The mechanical properties of the rubber material, including tensile strength, stress at a given elongation, elongation at break and tear strength, are all improved, and the compression set is significantly reduced. Attached Figure Description

[0045] Figure 1 The 1H NMR spectrum of the PGMA-PB-PGMA block copolymer modifier in Example 1;

[0046] Figure 2 The GPC curve of the PGMA-PB-PGMA block copolymer modifier in Example 1 is shown below.

[0047] Figure 3 The 1H NMR spectrum of the PTPM-PB-PTPM block copolymer modifier in Example 2;

[0048] Figure 4 The GPC curve for the PTPM-PB-PTPM block copolymer modifier in Example 2 is shown. Detailed Implementation

[0049] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be effectively described below. The descriptions below are only some embodiments of this invention.

[0050] Example 1

[0051] A method for preparing an inorganic filler block copolymer modifier for rubber includes the following steps:

[0052] 1) Hydroxyl-terminated polybutadiene (10.2000 g, 3.4 mmol) was dispersed in dichloromethane (20 mL), and then 2-(dodecylthiothiocarbonylthio)-2-methylpropionic acid (12.4100 g, 34 mmol), 4-dimethylaminopyridine (0.0415 g, 0.34 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (2.6070 g, 13.6 mmol) were added. The reaction was carried out at room temperature for 24 hours. After the reaction was completed, the product was precipitated with methanol to obtain a yellow viscous liquid. The product was dried in a vacuum drying oven at 40 °C for 24 hours. The precipitation and drying were repeated 3 times to obtain polybutadiene esterified with RAFT reagent (CTA-PB-CTA).

[0053] 2) The RAFT-esterified polybutadiene (1.5000 g, 0.4 mmol) was dissolved in 1,4-dioxane (10 mL), and glycidyl methacrylate (2.0000 g, 14.1 mmol) and azobisisobutyronitrile (0.0114 g, 0.07 mmol) were added. The mixture was heated at 60 °C for 6 hours under an argon atmosphere. After the reaction was completed, the mixture was precipitated, washed, and then dried in an oven at 25 °C for 12 hours to obtain the block copolymer poly(methacrylic acid glycidyl ether)-polybutadiene-poly(methacrylic acid glycidyl ether) modifier (PGMA-PB-PGMA). The 1H NMR spectrum was analyzed as follows: Figure 1 The measured copolymer molar ratio of polybutadiene and polyglycidyl methacrylate was approximately 4:3, as determined by GPC. Figure 2 The molecular weight and molecular weight distribution were tested. Mn = 10000 Da, and the molecular weight distribution Mw / Mn = 2.13.

[0054] The above-prepared inorganic filler block copolymer modifier (PGMA-PB-PGMA) for rubber is used for the modification of inorganic fillers for rubber. The specific modification operation is as follows:

[0055] The prepared inorganic filler block copolymer modifier for rubber (2.5000g) was dissolved in dichloromethane (125.0000g). The modified solution was then sprayed evenly onto inorganic filler talc powder (5000 mesh, 125.0000g). The product was dried at 65°C under normal pressure for 24 hours, and then placed in a vacuum drying oven and dried at 50°C for 24 hours to obtain modified talc powder.

[0056] The modified talc powder prepared above is used to reinforce nitrile rubber materials. The following formulation is used to reinforce nitrile rubber, according to the following weight parts: 100 parts of nitrile rubber (NBR), 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of accelerator (thiazole vulcanization accelerator DM), 2 parts of sulfur, and 10 parts, 20 parts, 30 parts, and 40 parts of modified talc powder respectively; or pure talc powder (unmodified) can be replaced with modified inorganic filler, with the same amounts of 10 parts, 20 parts, 30 parts, and 40 parts respectively.

[0057] The preparation method is as follows:

[0058] 1) Place the specified amount of nitrile rubber, modified talc or pure talc into an oven and set the oven temperature to 55℃;

[0059] 2) Set the front roll temperature of the two-roll mill to 45℃ and the rear roll temperature to 40℃. When the temperature of the mill reaches the preset temperature, add the nitrile rubber plasticizer treated in step 1).

[0060] 3) Add the various compounding agents in the specified amounts evenly along the roller axis. After each addition, wait until the material is fully absorbed, then cut the rollers twice with a 20-second interval between each cut, using the left and right 3 / 4 cuts respectively. The order of addition is: stearic acid, sulfur, zinc oxide, modified talc or talc powder, and accelerator. Cut and remove the rubber compound, adjust the roller gap, and then pass the rubber compound through a thin tube, making a triangular loop. Pass the thin tube five times to obtain the compound.

[0061] 4) After the rubber compound has been left to stand for 24 hours, it is vulcanized on a flat vulcanizing machine at a vulcanization temperature of 170℃, according to t 90 Time-cured vulcanization; and preparation of a permanent compression set type A standard sample, height: 12.5 mm, diameter: 29 mm;

[0062] Step 4) Perform tensile property testing: According to GB / T 528-2009 standard, the test dimensions of the dumbbell-shaped specimen are 2×4×20mm. 3 The test speed was 500 mm / min.

[0063] Step 4) Perform Shore C hardness test: The test is performed using a Shore hardness tester in accordance with the national standard GB / T531.1-2008, and the test temperature is room temperature.

[0064] Step 4) Perform permanent compression set test: Test the compression set according to ASTM-D395 standard. The specimen is a type A specimen with a compression ratio of 25%. The test conditions are 100℃ for 22 hours. After 22 hours, remove the specimen and open the clamps. After cooling for 0.5 hours, measure the thickness and calculate the permanent compression set.

[0065] The performance test data of Example 1 are shown in Table 1 below, which shows the performance improvement of nitrile rubber material by modified talc.

[0066] Table 1 Mechanical properties of nitrile rubber material in Example 1

[0067]

[0068]

[0069] Table 1 shows that high-performance modified talc can increase the tensile strength of nitrile rubber materials by 30.2%, tear strength by 15.6%, elongation at break by 11.4%, Shore hardness to 85, and permanent compression set by up to 37.6%, with the maximum deformation remaining at around 10%.

[0070] Example 2

[0071] A method for preparing an inorganic filler block copolymer modifier for rubber includes the following steps:

[0072] 1) The preparation method of polybutadiene esterified with RAFT reagent is the same as that in Example 1;

[0073] 2) The RAFT-esterified liquid rubber (1.5000 g, 0.4 mmol) was dissolved in tetrahydrofuran (6 mL), and 3-(methacryloyloxy)propyltrimethoxysilane (3.0000 g, 12.1 mmol) and azobisisobutyronitrile (0.0114 g, 0.07 mmol) were added. The mixture was heated at 60 °C for 4 hours under an argon atmosphere. After the reaction was completed, the mixture was precipitated, washed, and then dried in an oven at 25 °C for 12 hours to obtain the block copolymer poly(methacryloyloxy)propyltrimethoxysilane-polybutadiene-poly(3-(methacryloyloxy)propyltrimethoxysilane) modifier (PTPM-PB-PTPM). The 1H NMR spectrum was analyzed as follows: Figure 3 The measured molar ratio of polybutadiene and poly3-(methacryloyloxy)propyltrimethoxysilane was approximately 2:1, as determined by GPC. Figure 4 The molecular weight and molecular weight distribution were tested. Mn = 13500 Da, and the molecular weight distribution Mw / Mn = 3.01.

[0074] The block copolymer modifier (PTPM-PB-PTPM) prepared above is used for the modification of inorganic fillers for rubber. The specific modification operation is as follows:

[0075] The prepared inorganic filler macromolecular modifier for rubber (2.5000g) was dissolved in dichloromethane (125.0000g). The modified solution was then sprayed evenly onto talc powder (5000 mesh, 125.0000g). The product was dried at 65°C under normal pressure for 24 hours, and then placed in a vacuum drying oven and dried at 50°C for 24 hours to obtain modified talc powder.

[0076] A modified talc powder for rubber is used to reinforce EPDM rubber materials. The following formulation is used to reinforce EPDM rubber: By weight: 100 parts EPDM rubber (NBR), 5 parts zinc oxide, 2 parts stearic acid, 0.5 parts vulcanization accelerator MBT, 1.5 parts TMTD, 1.5 parts sulfur, and 10 parts, 20 parts, 30 parts, and 40 parts pure talc powder respectively; or the pure talc powder can be replaced with modified inorganic fillers, with the same amounts of 10 parts, 20 parts, 30 parts, and 40 parts respectively.

[0077] The preparation method is as follows:

[0078] 1) Place the specified amounts of EPDM rubber, modified talc powder, and pure talc powder into an oven and set the oven temperature to 55℃.

[0079] 2) Set the front roll temperature of the two-roll mill to 55℃ and the rear roll temperature to 50℃. When the temperature of the mill reaches the preset temperature, add the EPDM rubber treated in step 1) for plasticizing.

[0080] 3) Add the various compounding agents in the specified amounts evenly along the roller axis. After each addition, wait until the material is fully absorbed, then cut the material twice with the left and right 3 / 4 cuts, with a 30-second interval between the two cuts. The order of addition is: vulcanization accelerator, stearic acid, zinc oxide, modified talc or pure talc, and sulfur. Cut and remove the rubber compound, adjust the roller gap, add the rubber compound through a thin pass, and make a triangular loop. Repeat this thin pass 10 times to obtain the compound.

[0081] 4) After the rubber compound has been left to stand for 24 hours, it is vulcanized on a flat vulcanizing machine at a vulcanization temperature of 170℃, according to t 90 Time-cured vulcanization; and preparation of a permanent compression set type A standard sample, height: 12.5 mm, diameter: 29 mm;

[0082] Step 4) Perform tensile property testing: According to GB / T 528-2009 standard, the test dimensions of the dumbbell-shaped specimen are 2×4×20mm. 3 The test speed was 500 mm / min.

[0083] Step 4) Perform permanent compression set test: Test the compression set according to ASTM-D395 standard. The specimen is a type A specimen with a compression rate of 25%. The test conditions are 100℃ × 22h. After 22h, the specimen is removed and the clamp is opened. After cooling the specimen for 0.5h, the thickness is measured and the permanent compression set is calculated.

[0084] The performance test data of Example 2 are shown in Table 2 below. From this, we can intuitively observe the performance improvement of EPDM rubber material by modified talc.

[0085] Table 2 Mechanical properties of EPDM rubber material in Example 2

[0086]

[0087] The data in Table 2 show that in Example 2, the tensile strength, 300% elongation stress, and tear strength of the modified talc-filled EPDM rubber were improved, while the compression set was significantly reduced.

[0088] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A method for preparing an inorganic filler block copolymer modifier for rubber, characterized in that, The preparation method includes the following steps: 1) Disperse hydroxyl-containing liquid rubber in a solvent, add RAFT reagent with carboxyl groups, esterification catalyst and dehydrating agent, react to obtain modified liquid rubber; 2) Add the modified liquid rubber to the solvent, add vinyl functional monomers and free radical initiators, and heat the reaction under an inert atmosphere to obtain an inorganic filler block copolymer modifier for rubber. The vinyl functional monomer mentioned in step 2) is selected from methacrylic anhydride, glycidyl methacrylate, 3-(methacryloyloxy)propyltrimethoxysilane or vinyltrimethoxysilane.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the hydroxyl-containing liquid rubber, the carboxyl-containing RAFT reagent, the esterification reaction catalyst and the dehydrating agent in step 1) is 1:1~10:0.005~0.1:0.1~4.

3. The preparation method according to claim 1 or 2, characterized in that, Step 1) The hydroxyl-containing liquid rubber is selected from hydroxyl-terminated liquid nitrile rubber, hydroxyl-terminated liquid styrene-butadiene rubber, hydroxyl-terminated polybutadiene, and hydroxyl-terminated polyisoprene.

4. The preparation method according to claim 1 or 2, characterized in that, Step 1) The RAFT reagent with a carboxyl group is selected from: 2-(dodecylthiothiocarbonylthio)-2-methylpropionic acid, 4-cyano-4-(dodecylthioalkylthiocarbonyl)thioalkylpentanoic acid or 4-cyano-4-(phenylthiocarboxylthio)pentanoic acid.

5. The preparation method according to claim 1, characterized in that, Step 2) The molar ratio of the modified liquid rubber, free radical initiator, and vinyl functional monomer is 1:0.1~0.3:1~200.

6. The preparation method according to claim 1 or 5, characterized in that, Step 2) The heating reaction specifically involves a polymerization temperature of 50-130℃ and a reaction time of 1-10 hours.

7. An inorganic filler block copolymer modifier for rubber prepared by the preparation method according to any one of claims 1-6.

8. A modified inorganic filler, characterized in that, The modified inorganic filler is obtained by modifying the rubber inorganic filler block copolymer modifier prepared by the preparation method according to any one of claims 2-6.

9. An application of the modified inorganic filler according to claim 8, characterized in that, Used in rubber materials.

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