Modified spherical particle-based rubber composite material and preparation method thereof
By adding modified spherical pellets to the rubber material and performing modification treatment, the problem of insufficient mechanical properties of the rubber material under high-strength loads and complex environmental conditions is solved, and the effect of significantly improving mechanical properties and anti-aging properties is achieved.
Patent Information
- Application Number
- CN202411986944.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-04-11
AI Technical Summary
The existing rubber materials lack mechanical properties under high-strength loads and complex environmental conditions, especially the problems of insufficient strength, poor wear resistance and insufficient impact resistance, limit their application potential in the high-end manufacturing field.
Using modified spherical particle-based rubber composite materials, by adding spherical pelletized materials containing steel materials to the rubber matrix and performing modification treatment, the phosphate ester or polycarboxylic acid group in the modifier undergoes chelation with the metal oxide on the surface of the steel spherical pelletized materials to enhance the interface bond between the spherical pelletized materials and the rubber matrix.
The mechanical properties and anti-aging properties of rubber materials are significantly improved, and the bond between particles and rubber matrix is stronger. Plasticizers and processing aids improve fluidity, and antioxidants improve aging resistance.
Abstract
Description
Technical Field
[0001] The invention relates to the field of rubber preparation, and in particular to a modified spherical particle-based rubber composite material and a preparation method thereof. Background Art
[0002] Rubber materials, as an indispensable basic material in modern industrial production and daily life, have a very wide range of applications, from automobile manufacturing, electronic equipment to daily necessities, almost everywhere. However, despite their many advantages such as low cost and easy processing, these materials often expose significant problems of insufficient mechanical properties under high-intensity loads and complex environmental conditions due to the inherent limitations of their molecular structure. Specifically, these materials may exhibit defects such as insufficient strength, poor wear resistance, and insufficient impact resistance, which greatly limit their application potential in the field of high-end manufacturing.
[0003] In view of the shortcomings of mechanical properties of rubber materials, although traditional modification methods have been tried and improved to a certain extent, the results are not ideal. For example, by introducing inorganic fillers such as carbon black and silica, although the hardness of the material can be enhanced to a certain extent, the addition of too many inorganic fillers will not only significantly reduce the ductility of the material, making the material more prone to brittle fracture when subjected to external forces, but also, even when the hardness is improved, the improvement of wear resistance by these inorganic fillers is often limited. More importantly, the interface bonding between inorganic reinforcing materials and rubber or plastics is generally poor. This poor interface bonding will not only greatly reduce the reinforcement effect, but may even cause the overall mechanical properties of the material to decline due to stress concentration at the interface.
[0004] In addition, the introduction of some traditional fillers will also bring about the problem of excessive material density. In today's era of pursuing lightweight, energy conservation and emission reduction, excessively high material density is undoubtedly not in line with market demand. Especially in fields such as automobiles and aerospace that require strict weight control, the increase in material density will directly lead to an increase in energy consumption and a decrease in performance, which is undoubtedly a huge negative impact on the market competitiveness of products.
[0005] Therefore, developing a new type of rubber material that can effectively enhance the mechanical properties of rubber materials not only has important theoretical significance, but also has broad practical application value. Summary of the invention
[0006] In view of the above-mentioned existing technical problems, the present invention provides a modified spherical particle-based rubber composite material and a preparation method thereof. The modified spherical particle-based rubber composite material prepared by this method has good mechanical properties and anti-aging properties, and the bonding between the particles and the rubber matrix is more firm.
[0007] The present invention discloses a modified spherical particle-based rubber composite material, comprising the following components in parts by weight:
[0008] 70-90 parts of rubber; 15-30 parts of spherical particles; 5-8 parts of modifier; 2-3 parts of antioxidant; 0.6-1.1 parts of plasticizer; 3-5 parts of vulcanizer; 0.5-1 part of vulcanization accelerator.
[0009] Preferably, the spherical granules are spherical granules containing a rigid material; the diameter of the spherical granules is 10 μm-30 μm.
[0010] Preferably, the structural formula of the modifier is R1-(PO4) x –(CH2) n –R2.
[0011] Preferably, the R1 group is a phosphate or a carboxyl group; the R2 group is a thiol group or an unsaturated double bond; n=2-10; and x=0-2.
[0012] Preferably, the antioxidant is 2,6-di-tert-butyl-p-cresol; the plasticizer is epoxidized soybean oil; the vulcanizer is dicumyl peroxide; and the vulcanization accelerator is dibenzothiazole disulfide.
[0013] The present invention also discloses a method for preparing a modified spherical particle-based rubber composite material, comprising the following steps:
[0014] S1 Preparation of modified spherical particles: Add polyether polyol to a reactor, then add ethanol, stir evenly, then add phosphate compound or carboxyl compound, then add thiol compound or unsaturated double bond compound to obtain a mixture, heat the reactor to heat the mixture to perform condensation reaction, and obtain a reaction liquid after the reaction is completed, then extract the reaction liquid, collect the organic phase, and concentrate it under reduced pressure to obtain a modifier; dissolve the modifier in ethanol to obtain a modifier solution, dry the spherical particles, add them to the modifier solution, perform ultrasonic treatment, filter and collect the filter cake after the ultrasonic treatment is completed, and dry the collected filter cake to obtain a modified spherical particle;
[0015] Preparation of S2 modified spherical particle-based rubber composite material: add rubber to an open mill, set the temperature of the open mill and start pre-plasticizing the rubber, slowly add the modified spherical particles to the open mill after the pre-plasticizing is completed, keep stirring during the addition, and after the modified spherical particles and rubber are evenly mixed, add plasticizer, antioxidant, vulcanizer and vulcanization accelerator in sequence, and then mix to obtain a mixed material; place the mixed material in a tablet press for pressing, set the temperature and pressure of the tablet press, and obtain a preformed sheet after the pressing is completed, place the preformed sheet into a vulcanization mold for vulcanization, and cool after the vulcanization is completed to obtain a modified spherical particle-based rubber composite material.
[0016] Preferably, in the S1 modified spherical granular material preparation step, the reactor is heated to 60-120° C. for condensation reaction, and the condensation reaction time is 2-4 hours.
[0017] Preferably, in the step of preparing the S1 modified spherical granules, the ultrasonic frequency of the ultrasonic treatment is 500 to 1000 Hz; and the time of the ultrasonic treatment is 20 to 40 min.
[0018] Preferably, in the preparation step of the S2 modified spherical particle-based rubber composite material, the pre-plasticizing temperature of the open mill is set to 70-80°C, and the pre-plasticizing time is 30-40 min; the mixing time is 25-50 min; the temperature of the tablet press is set to 60-80°C, and the pressure of the tablet press is set to 5-10 MPa.
[0019] Preferably, in the step of preparing the S1 mixed solution, the reaction temperature of the reactor is 60-70° C.; and the reaction pressure of the reactor is 2-3 MPa.
[0020] Preferably, in the step of preparing the S2 modified spherical particle-based rubber composite material, the vulcanization temperature is set to 150-170° C., the vulcanization pressure is set to 15-30 MPa, and the vulcanization time is set to 10-30 min.
[0021] Compared with the prior art, the present invention has the following beneficial effects:
[0022] Compared with the existing rubber materials on the market, the present invention provides a modified spherical particle-based rubber composite material with significantly improved mechanical properties. The bond between the particles and the rubber matrix is more firm, the fluidity is improved by plasticizers and processing aids, and the aging resistance is improved by antioxidants.
[0023] The modified spherical particle-based rubber composite material provided by the present invention has excellent mechanical properties because spherical particles containing rigid materials are added on the basis of rubber as a matrix. However, due to the special material properties of the spherical particles, it is difficult to perfectly combine them with the rubber matrix using a general coupling agent. Therefore, the present invention performs a modification treatment on the spherical particles. The modifier used for the modification treatment contains a phosphate ester or a polycarboxylic acid group, which can chelate with the metal oxide on the surface of the rigid spherical particles to generate a stable metal-organic coordination structure, thereby realizing the activation of the steel slag surface; the thiol group or unsaturated double bond at the other end of the modifier is combined with the rubber matrix, so that the interface between the rigid spherical particles and the rubber matrix is more compact, and the filler is evenly dispersed in the rubber matrix. A short-chain aliphatic group is introduced between the modified end of the rigid spherical particles and the rubber binding end of the modifier to further improve the flexibility and reaction uniformity of the modifier.
[0024] The present invention also provides a method for preparing a modified spherical particle-based rubber composite material. In the preparation step of the S2 modified spherical particle-based rubber composite material: the temperature during pre-plasticization is controlled to avoid premature vulcanization of the rubber, ensure uniform dispersion of each component during the mixing process, and avoid particle agglomeration; the vulcanization temperature, pressure and time are accurately controlled to ensure the optimal cross-linking density and prevent insufficient vulcanization or excessive vulcanization. DETAILED DESCRIPTION
[0025] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.
[0026] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.
[0027] Example 1: A modified spherical particle-based rubber composite material, comprising the following components in parts by weight:
[0028] 70 parts of rubber; 15 parts of steel spherical particles; 5 parts of modifier; 2 parts of antioxidant; 0.6 parts of plasticizer; 3 parts of vulcanizer; 0.5 parts of vulcanization accelerator.
[0029] The antioxidant is 2,6-di-tert-butyl-p-cresol; the plasticizer is epoxidized soybean oil; the vulcanizer is diisopropylbenzene peroxide; the vulcanization accelerator is dibenzothiazole disulfide; and the diameter of the rigid spherical particles is 10 μm.
[0030] A method for preparing a modified spherical particle-based rubber composite material comprises the following preparation steps:
[0031] Preparation of S1 modified spherical particles: Add polyether polyol to the reactor, then add ethanol and stir evenly, then add phosphate compound and thiol compound in turn to obtain a mixture, heat the reactor to 80℃ and heat the mixture for condensation reaction, the condensation reaction time is 3h, after the reaction is completed, obtain the reaction liquid, then extract the reaction liquid with ethyl acetate 3 to 5 times, and combine and collect the organic phase to obtain the modifier after vacuum concentration; the structural formula of the modifier is PO4-(CH2)5-SH. Dissolve the modifier in ethanol to obtain the modifier solution, dry the spherical particles and add them to the modifier solution, perform ultrasonic treatment, the ultrasonic frequency during the ultrasonic treatment is 800Hz, the ultrasonic treatment time is 30min, after the ultrasonic treatment is completed, filter and collect the filter cake, dry the collected filter cake to obtain the modified spherical particles.
[0032] Preparation of S2 modified spherical particle-based rubber composite material: add rubber to an open mill, set the temperature of the open mill to 75°C and start pre-plasticizing the rubber. After pre-plasticizing for 35 minutes, slowly add the modified spherical particles to the open mill, keep stirring during the addition, and after the modified spherical particles and rubber are evenly mixed, add plasticizer, antioxidant, vulcanizer and vulcanization accelerator in sequence, and then mix them. After mixing for 40 minutes, a mixed material is obtained; the mixed material is placed in a tablet press for pressing, and the temperature of the tablet press is set to 70°C and the pressure of the tablet press is set to 8MPa. After the pressing is completed, a preformed sheet is obtained, and the preformed sheet is placed in a vulcanization mold, and the vulcanization temperature is controlled to 160°C and the vulcanization pressure is 26MPa for vulcanization. The vulcanization time is 20min, and after the vulcanization is completed, it is cooled to room temperature to obtain a modified spherical particle-based rubber composite material.
[0033] Example 2: A modified spherical particle-based rubber composite material, comprising the following components in parts by weight:
[0034] 75 parts of rubber; 18 parts of steel spherical particles; 6 parts of modifier; 2.2 parts of antioxidant; 0.7 parts of plasticizer; 3.5 parts of vulcanizer; 0.6 parts of vulcanization accelerator.
[0035] The antioxidant is 2,6-di-tert-butyl-p-cresol; the plasticizer is epoxidized soybean oil; the vulcanizer is diisopropylbenzene peroxide; the vulcanization accelerator is dibenzothiazole disulfide; and the diameter of the rigid spherical particles is 25 μm.
[0036] The preparation method of a modified spherical particle-based rubber composite material is the same as that in Example 1.
[0037] Example 3: A modified spherical particle-based rubber composite material, comprising the following components in parts by weight:
[0038] 80 parts of rubber; 20 parts of steel spherical particles; 7 parts of modifier; 2.5 parts of antioxidant; 0.8 parts of plasticizer; 4 parts of vulcanizer; 0.7 parts of vulcanization accelerator.
[0039] The antioxidant is 2,6-di-tert-butyl-p-cresol; the plasticizer is epoxidized soybean oil; the vulcanizer is diisopropylbenzene peroxide; the vulcanization accelerator is dibenzothiazole disulfide; and the diameter of the rigid spherical particles is 20 μm.
[0040] The preparation method of a modified spherical particle-based rubber composite material is the same as that in Example 1.
[0041] Example 4: A modified spherical particle-based rubber composite material, comprising the following components in parts by weight:
[0042] 85 parts of rubber; 25 parts of steel spherical particles; 7.5 parts of modifier; 2.7 parts of antioxidant; 1.0 part of plasticizer; 4.5 parts of vulcanizer; 0.8 parts of vulcanization accelerator; the diameter of the steel spherical particles is 15μm.
[0043] The antioxidant is 2,6-di-tert-butyl-p-cresol; the plasticizer is epoxidized soybean oil; the vulcanizer is diisopropylbenzene peroxide; and the vulcanization accelerator is dibenzothiazole disulfide.
[0044] The preparation method of a modified spherical particle-based rubber composite material is the same as that in Example 1.
[0045] Example 5: A modified spherical particle-based rubber composite material, comprising the following components in parts by weight:
[0046] 90 parts of rubber; 30 parts of steel spherical particles; 8 parts of modifier; 3 parts of antioxidant; 1.1 parts of plasticizer; 5 parts of vulcanizer; 1 part of vulcanization accelerator.
[0047] The antioxidant is 2,6-di-tert-butyl-p-cresol; the plasticizer is epoxidized soybean oil; the vulcanizer is diisopropylbenzene peroxide; the vulcanization accelerator is dibenzothiazole disulfide; and the diameter of the rigid spherical particles is 30 μm.
[0048] The preparation method of a modified spherical particle-based rubber composite material is the same as that in Example 1.
[0049] Example 6: The weight proportions of the components of a modified spherical particle-based rubber composite material are the same as those of Example 4.
[0050] A method for preparing a modified spherical particle-based rubber composite material comprises the following preparation steps:
[0051] Preparation of S1 modified spherical particles: add polyether polyol to the reactor, then add ethanol and stir evenly, then add phosphate compound and thiol compound in sequence to obtain a mixture, heat the reactor to 60°C and heat the mixture for condensation reaction, the condensation reaction time is 2h, after the reaction is completed, obtain a reaction solution, then extract the reaction solution with ethyl acetate for 3 to 5 times, and combine and collect the organic phases and concentrate under reduced pressure to obtain a modifier; the structural formula of the modifier is PO4-PO4-(CH2)7-SH, dissolve the modifier in ethanol to obtain a modifier solution, dry the spherical particles and add them to the modifier solution for ultrasonic treatment, the ultrasonic frequency during the ultrasonic treatment is 500Hz, the ultrasonic treatment time is 20min, after the ultrasonic treatment is completed, filter and collect the filter cake, dry the collected filter cake to obtain modified spherical particles.
[0052] Preparation of S2 modified spherical particle-based rubber composite material: add the rubber to an open mill, set the temperature of the open mill to 70°C and start pre-plasticizing the rubber. After pre-plasticizing for 30 minutes, slowly add the modified spherical particles to the open mill, keep stirring during the addition, and after the modified spherical particles and rubber are evenly mixed, add plasticizer, antioxidant, vulcanizer and vulcanization accelerator in sequence, and then mix them. After mixing for 25 minutes, a mixed material is obtained; the mixed material is placed in a tablet press for pressing, and the temperature of the tablet press is set to 60°C and the pressure of the tablet press is set to 5MPa. After the pressing is completed, a preformed sheet is obtained, and the preformed sheet is placed in a vulcanization mold, and the vulcanization temperature is controlled to 150°C and the vulcanization pressure is 15MPa for vulcanization. The vulcanization time is 10 minutes. After the vulcanization is completed, it is cooled to room temperature to obtain a modified spherical particle-based rubber composite material.
[0053] Example 7: The weight proportions of the components of a modified spherical particle-based rubber composite material are the same as those of Example 4.
[0054] A method for preparing a modified spherical particle-based rubber composite material comprises the following preparation steps:
[0055] Preparation of S1 modified spherical particles: add polyether polyol to the reactor, then add ethanol and stir evenly, then add phosphate compound and unsaturated double bond compound in sequence to obtain a mixture, heat the reactor to 100°C and heat the mixture for condensation reaction, the condensation reaction time is 2.5h, after the reaction is completed, obtain a reaction solution, then extract the reaction solution with ethyl acetate for 3 to 5 times, and combine and collect the organic phases and concentrate under reduced pressure to obtain a modifier; the structural formula of the modifier is PO4-(PO4)2-(CH2)2-CH=CH2, dissolve the modifier in ethanol to obtain a modifier solution, dry the spherical particles and add them to the modifier solution for ultrasonic treatment, the ultrasonic frequency during the ultrasonic treatment is 650Hz, the ultrasonic treatment time is 25min, after the ultrasonic treatment is completed, filter and collect the filter cake, dry the collected filter cake to obtain modified spherical particles.
[0056] Preparation of S2 modified spherical particle-based rubber composite material: Add the rubber to an open mill, set the temperature of the open mill to 72°C and start pre-plasticizing the rubber. After pre-plasticizing for 33 minutes, slowly add the modified spherical particles to the open mill, keep stirring during the addition, and after the modified spherical particles and rubber are evenly mixed, add plasticizer, antioxidant, vulcanizer and vulcanization accelerator in sequence, and then mix them. After mixing for 30 minutes, a mixed material is obtained; the mixed material is placed in a tablet press for pressing, and the temperature of the tablet press is set to 65°C and the pressure of the tablet press is set to 6MPa. After the pressing is completed, a preformed sheet is obtained, and the preformed sheet is placed in a vulcanization mold, and the vulcanization temperature is controlled to 150°C and the vulcanization pressure is 18MPa for vulcanization. The vulcanization time is 15 minutes. After the vulcanization is completed, it is cooled to room temperature to obtain a modified spherical particle-based rubber composite material.
[0057] Example 8: The weight proportions of the components of a modified spherical particle-based rubber composite material are the same as those of Example 4.
[0058] A method for preparing a modified spherical particle-based rubber composite material comprises the following preparation steps:
[0059] Preparation of S1 modified spherical particles: add polyether polyol to the reactor, then add ethanol and stir evenly, then add carboxyl compounds and unsaturated double bond compounds in sequence to obtain a mixture, heat the reactor to 110°C and heat the mixture to perform a condensation reaction. The condensation reaction time is 3.5 hours. After the reaction is completed, a reaction solution is obtained, and then the reaction solution is extracted with ethyl acetate for 3 to 5 times, and the organic phases are combined and collected and concentrated under reduced pressure to obtain a modifier; the structural formula of the modifier is HOOC–(PO4)2–(CH2) 10 –CH=CH2, dissolve the modifier in ethanol to obtain a modifier solution, dry the spherical particles and add them to the modifier solution for ultrasonic treatment. The ultrasonic frequency during the ultrasonic treatment is 900 Hz and the ultrasonic treatment time is 35 min. After the ultrasonic treatment is completed, filter and collect the filter cake, dry the collected filter cake to obtain modified spherical particles.
[0060] Preparation of S2 modified spherical particle-based rubber composite material: add the rubber to an open mill, set the temperature of the open mill to 77°C and start pre-plasticizing the rubber. After pre-plasticizing for 37 minutes, slowly add the modified spherical particles to the open mill, keep stirring during the addition, and after the modified spherical particles and rubber are evenly mixed, add plasticizer, antioxidant, vulcanizer and vulcanization accelerator in sequence, and then mix them. After mixing for 40 minutes, a mixed material is obtained; the mixed material is placed in a tablet press for pressing, and the temperature of the tablet press is set to 75°C and the pressure of the tablet press is set to 9MPa. After the pressing is completed, a preformed sheet is obtained, and the preformed sheet is placed in a vulcanization mold, and the vulcanization temperature is controlled to 150°C and the vulcanization pressure is 23MPa for vulcanization. The vulcanization time is 20 minutes. After the vulcanization is completed, it is cooled to room temperature to obtain a modified spherical particle-based rubber composite material.
[0061] Example 9: The weight proportions of the components of a modified spherical particle-based rubber composite material are the same as those of Example 4.
[0062] A method for preparing a modified spherical particle-based rubber composite material comprises the following preparation steps:
[0063] Preparation of S1 modified spherical particles: add polyether polyol to the reactor, then add ethanol and stir evenly, then add carboxyl compounds and thiol compounds in sequence to obtain a mixture, heat the reactor to 120°C and heat the mixture to perform a condensation reaction, the condensation reaction time is 4 hours, after the reaction is completed, a reaction solution is obtained, and then the reaction solution is extracted with ethyl acetate for 3 to 5 times, and the organic phases are combined and collected and concentrated under reduced pressure to obtain a modifier; the structural formula of the modifier is HOOC–(PO4)2–(CH2) 10 –SH, dissolve the modifier in ethanol to obtain a modifier solution, dry the spherical particles and add them to the modifier solution for ultrasonic treatment. The ultrasonic frequency during the ultrasonic treatment is 1000 Hz and the ultrasonic treatment time is 40 min. After the ultrasonic treatment is completed, filter and collect the filter cake, dry the collected filter cake to obtain modified spherical particles.
[0064] Preparation of S2 modified spherical particle-based rubber composite material: add rubber to an open mill, set the temperature of the open mill to 80°C and start pre-plasticizing the rubber. After pre-plasticizing for 40 minutes, slowly add the modified spherical particles to the open mill, keep stirring during the addition, and after the modified spherical particles and rubber are evenly mixed, add plasticizer, antioxidant, vulcanizer and vulcanization accelerator in sequence, and then mix them. After mixing for 50 minutes, a mixed material is obtained; the mixed material is placed in a tablet press for pressing, and the temperature of the tablet press is set to 80°C and the pressure of the tablet press is set to 10MPa. After the pressing is completed, a preformed sheet is obtained, and the preformed sheet is placed in a vulcanization mold, and the vulcanization temperature is controlled to 150°C and the vulcanization pressure is 30MPa for vulcanization. The vulcanization time is 30min, and after the vulcanization is completed, it is cooled to room temperature to obtain a modified spherical particle-based rubber composite material.
[0065] Example 10: A modified spherical particle-based rubber composite material, comprising the following components in parts by weight:
[0066] 85 parts of rubber; 25 parts of spherical silica particles; 7.5 parts of modifier; 2.7 parts of antioxidant; 1.0 parts of plasticizer; 4.5 parts of vulcanizer; and 0.8 parts of vulcanization accelerator.
[0067] The antioxidant is 2,6-di-tert-butyl-p-cresol; the plasticizer is epoxidized soybean oil; the vulcanizer is diisopropylbenzene peroxide; the vulcanization accelerator is dibenzothiazole disulfide; and the diameter of the silica spherical particles is 15 μm.
[0068] The preparation method of a modified spherical particle-based rubber composite material is the same as that in Example 1.
[0069] The modified spherical particle-based rubber composite materials prepared in Examples 1 to 10 were subjected to performance testing. The anti-aging performance testing method is to test the mechanical properties of the rubber composite materials prepared in Examples 1 to 10 after thermal oxidation aging for 72 hours, and then calculate the mechanical retention rate to obtain the strength of the anti-aging performance. The wear index in the table refers to the ratio of the volume loss of the standard rubber to the test rubber measured under the same specified conditions. The higher the wear resistance index, the better the wear resistance of the rubber composite material. The test results are shown in the following table:
[0070] Example Tensile strength(MPa) Hardness(HA) Wear index (%) Mechanical properties retention rate (%) 1 25 80 280 85 2 26 82 301 88 3 28 85 320 92 4 32 88 338 95 5 32 88 337 93 6 20 72 250 73 7 23 75 264 76 8 29 79 279 82 9 27 77 273 80 10 15 55 150 50
[0071] As can be seen from the above table, the tensile strength of the modified spherical particle-based rubber composite material prepared in Examples 1 to 9 is not less than 23MPa, the hardness is not less than 72HA, the wear index is not less than 250%, and the mechanical property retention rate is not less than 73%; therefore, it can be seen that the composite material prepared by combining the rigid spherical particle material with the rubber base material has excellent mechanical properties and anti-aging properties. Example 10 is a rubber composite material prepared by replacing the rigid spherical particle material in the raw material with a silica spherical particle material. The mechanical properties and anti-aging properties of this composite material are far lower than those of the modified spherical particle-based rubber composite material prepared in Examples 1 to 9.
[0072] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the scope of protection of the invention.
Claims
1. A modified spherical particle-based rubber composite material, characterized in that: It is composed of the following ingredients in parts by weight: 70-90 parts of rubber; 15-30 parts of spherical particles; 5-8 parts of modifier; 2-3 parts of antioxidant; 0.6-1.1 parts of plasticizer; 3-5 parts of vulcanizer; 0.5-1 part of vulcanization accelerator.
2. A modified spherical particle-based rubber composite material according to claim 1, characterized in that: The spherical granules are spherical granules containing rigid materials; the diameter of the spherical granules is 10 μm to 30 μm.
3. A modified spherical particle-based rubber composite material according to claim 1, characterized in that: The structural formula of the modifier is R1-(PO4) x -(CH2) n -R2.
4. A modified spherical particle-based rubber composite material according to claim 3, characterized in that: The R1 group is a phosphate or a polycarboxyl group; the R2 group is a thiol group or an unsaturated double bond; n=2-10; and x=0-2.
5. The modified spherical particle-based rubber composite material according to claim 1, characterized in that: The antioxidant is 2,6-di-tert-butyl-p-cresol; the plasticizer is epoxidized soybean oil; the vulcanizer is diisopropylbenzene peroxide; and the vulcanization accelerator is dibenzothiazole disulfide.
6. A method for preparing a modified spherical particle-based rubber composite material, characterized in that: The method comprises the following preparation steps: Preparation of S1 modified spherical particles: add polyether polyol to a reactor, then add ethanol and stir evenly, then add a phosphate compound or a carboxyl compound, and then add a thiol compound or an unsaturated double bond compound to obtain a mixture, heat the reactor to heat the mixture to perform a condensation reaction, and after the reaction is completed, obtain a reaction liquid, then extract the reaction liquid, collect the organic phase, and concentrate it under reduced pressure to obtain a modifier; The modifier is dissolved in ethanol to obtain a modifier solution, the spherical particles are dried and added to the modifier solution, and ultrasonic treatment is performed. After the ultrasonic treatment is completed, the filter cake is filtered and collected, and the collected filter cake is dried to obtain a modified spherical particle material; Preparation of S2 modified spherical particle-based rubber composite material: add rubber to an open mill, set the temperature of the open mill and start pre-plasticizing the rubber, slowly add the modified spherical particles to the open mill after the pre-plasticizing is completed, keep stirring during the addition, and after the modified spherical particles and rubber are evenly mixed, add plasticizer, antioxidant, vulcanizer and vulcanization accelerator in sequence, and then mix to obtain a mixed material; place the mixed material in a tablet press for pressing, set the temperature and pressure of the tablet press, and obtain a preformed sheet after the pressing is completed, place the preformed sheet into a vulcanization mold for vulcanization, and cool after the vulcanization is completed to obtain a modified spherical particle-based rubber composite material.
7. The method for preparing a modified spherical particle-based rubber composite material according to claim 6, characterized in that: In the S1 modified spherical granular material preparation step, the reactor is heated to 60-120° C. for condensation reaction, and the condensation reaction time is 2-4 hours.
8. The method for preparing a modified spherical particle-based rubber composite material according to claim 6, characterized in that: In the step of preparing the S1 modified spherical particles, the ultrasonic frequency of the ultrasonic treatment is 500 to 1000 Hz; and the time of the ultrasonic treatment is 20 to 40 minutes.
9. The method for preparing a modified spherical particle-based rubber composite material according to claim 6, characterized in that: In the preparation step of the S2 modified spherical particle-based rubber composite material, the pre-plasticizing temperature of the open mill is set to 70-80°C, and the pre-plasticizing time is 30-40 minutes; the mixing time is 25-50 minutes; the temperature of the tablet press is set to 60-80°C, and the pressure of the tablet press is set to 5-10MPa.
10. The method for preparing a modified spherical particle-based rubber composite material according to claim 6, characterized in that: In the step of preparing the S2 modified spherical particle-based rubber composite material, the vulcanization temperature is set to 150-170° C., the vulcanization pressure is set to 15-30 MPa, and the vulcanization time is set to 10-30 min.