Toughened vulcanized rubber based on C-H activation strategy and preparation method and application thereof
The vulcanized rubber is modified through the C-H bond activation strategy, and the use of diazo compounds as crosslinking agents and modifiers solves the problem that traditional vulcanization processes cannot improve rubber performance, and achieves a significant improvement in rubber strength and breaking energy.
Patent Information
- Application Number
- CN202510340277.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-21
- Publication Date
- 2025-05-23
AI Technical Summary
Traditional vulcanization processes cannot meet the needs of modern automobiles and aviation industries to improve the performance of rubber materials, and the existing technology is difficult to effectively improve the strength and breaking energy of the vulcanization network.
The vulcanized mesh chain is modified by the C-H bond activation strategy, and the vulcanized by specific diazon compounds as crosslinking agents and modifiers are used to form a tough vulcanized rubber.
It significantly improves the tensile strength and breaking energy of rubber, expands the application range of rubber, and has good application prospects.
Smart Images
Figure BDA0005322964540000031
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of polymer synthesis, and in particular to a toughened vulcanized rubber based on a CH activation strategy, and a preparation method and application thereof. Background Art
[0002] As an important type of engineering material, rubber is widely used in military and civilian fields such as aerospace, electronics, medical care, weapons and equipment due to its unique properties. So far, vulcanization is a necessary process in the rubber industry, and only rubber materials that have been vulcanized have usability. However, with the rapid development of industries such as automobiles and aviation, the performance requirements of rubber materials are increasing, and the traditional vulcanization process can no longer meet the performance requirements. Although people are currently designing new network structures in the rubber matrix to effectively improve the various properties of rubber, the vulcanization network still occupies a dominant position in the rubber industry, and it is difficult to replace the traditional vulcanization network with a new cross-linked network. Therefore, further improving the performance of the vulcanization network is an urgent problem to be solved in the rubber industry. Summary of the invention
[0003] In view of this, the present application provides a toughened vulcanized rubber based on a CH activation strategy and a preparation method and application thereof. The present application utilizes the CH bond activation technology to modify the vulcanized network chain to achieve toughening of the vulcanized network, which can effectively overcome the defects of the above-mentioned prior art.
[0004] In a first aspect, the present application provides a toughened vulcanized rubber based on a CH activation strategy, wherein the toughened vulcanized rubber based on a CH bond is prepared from raw materials in the following weight ratio:
[0005] 100 parts of rubber, 0.1-10 parts of CH bond activator, 1-5 parts of zinc oxide, 1-5 parts of stearic acid, 1-6 parts of accelerator, and 0.3-6 parts of sulfur.
[0006] Specifically, the CH bond-based toughened vulcanized rubber is prepared from the following raw materials in the following weight ratio:
[0007] 100 parts of rubber, 0.5-4 parts of CH bond activator, 1-5 parts of zinc oxide, 1-2 parts of stearic acid, 1-1.5 parts of accelerator, and 1-1.5 parts of sulfur.
[0008] Preferably, the CH bond-toughened vulcanized rubber is prepared from raw materials in the following weight ratio:
[0009] 100 parts of rubber, 3 parts of CH bond activator, 5 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of accelerator, and 1.5 parts of sulfur.
[0010] Preferably, the CH bond activator is a diazo compound.
[0011] Preferably, the diazo compound is a diazo compound obtained by a diazo transfer reaction.
[0012] Preferably, the preparation process of the diazo compound is:
[0013] 2-Hydroxyethyl disulfide, pyridine and phenylacetyl chloride are mixed and reacted at room temperature for 12 hours to obtain a primary product; the primary product, p-toluenesulfonyl azide and 1,8-dichloroheterobicyclo[5.4.0]undec-7-ene are then mixed and reacted at room temperature for 12 hours to obtain a diazo compound.
[0014] Preferably, the rubber is natural rubber or synthetic rubber; and / or
[0015] The accelerator is accelerator CZ.
[0016] Preferably, the synthetic rubber is styrene-butadiene rubber.
[0017] The second aspect of the present application also provides a method for preparing the above-mentioned toughened vulcanized rubber based on the CH activation strategy, comprising the following steps:
[0018] The raw rubber, CH bond activator, zinc oxide, stearic acid, accelerator and sulfur are weighed according to the weight ratio; the raw materials are mixed evenly and then vulcanized to obtain the CH bond-strengthened vulcanized rubber.
[0019] Preferably, the vulcanization temperature is 150-160° C., the vulcanization time is 15-30 minutes, and the vulcanization pressure is 10-15 MPa.
[0020] The third aspect of the present application also provides the use of the above-mentioned toughened vulcanized rubber based on the CH activation strategy in the preparation of preparations or equipment for tires, seals, and shock absorbers.
[0021] Compared with the prior art, this application has the following beneficial effects:
[0022] The CH activation strategy based toughening of vulcanized rubber in the present application uses a specific diazo compound as a crosslinker and modifier. Under a specific accelerator, the vulcanization network can be toughened and the rubber strength and fracture energy can be significantly improved, further expanding the application range of rubber, and has good application prospects. DETAILED DESCRIPTION
[0023] In order to make the purpose, technical solution and advantages of this application clearer, the technical solution in this application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.
[0024] Unless otherwise specified, the experimental methods used in the examples of this application are all conventional methods.
[0025] In the following examples and comparative examples, unless otherwise specified, all raw materials can be obtained by commercial purchase or conventional methods.
[0026] Example 1 Preparation of Diazo Compound Strengthened Vulcanized Rubber
[0027] On an open mixing mill, 1 g of a diazo compound, 5 g of zinc oxide, 2 g of stearic acid, 1.5 g of accelerator CZ and 1.5 g of sulfur were added to 100 g of styrene-butadiene rubber, mixed evenly and then vulcanized at a vulcanization temperature of 155°C, a vulcanization time of 25 minutes and a vulcanization pressure of 15 MPa to finally obtain a diazo compound toughened vulcanized rubber (sheet).
[0028] Preparation method of diazo compound: 7.7g 2-hydroxyethyl disulfide and 8.7g pyridine are charged into a flat-bottomed flask, mixed evenly at room temperature with a magnetic stirrer at a speed of 400rpm, then 17.0g phenylacetyl chloride is slowly added, and the mixture is reacted at room temperature for 12 hours. The above product is then rotary evaporated and washed and charged into a flat-bottomed flask with 59.2g p-toluenesulfonyl azide, mixed evenly at room temperature with a magnetic stirrer at a speed of 400rpm, then 38.1g 1,8-dichloroheterobicyclo[5.4.0]undec-7-ene is slowly added, and the mixture is reacted at room temperature for 12 hours to obtain a diazo compound.
[0029] According to GB / T 528-2009, the prepared sheet was cut into I-type dumbbell specimens, and the stress-strain curve was obtained using the high-speed rail AI-3000 electronic tensile testing machine, and the tensile strength of the sheet was 2.51MPa. A 1mm long incision was pre-cut in the sheet with a length of 75mm and a width of 5mm, and the fracture energy of the specimen was tested, and the fracture energy of the specimen was 1.30kJ / m 2 .
[0030] The tensile strength is the stress when the sample breaks; the fracture energy is the energy absorbed per unit area of the sample during the fracture process.
[0031]
[0032] (λ c is the elongation at break, with a minimum value of 1, the length of the sample after deformation divided by the initial length. c is the crack length, and W is the strain energy density calculated by integrating the stress and engineering strain of the unnotched sample until ε (ε = λ c -1)) Obtain fracture energy.
[0033] Comparative Example 1
[0034] On an open mill, 1.5 g of sulfur, 5 g of zinc oxide, 2 g of stearic acid and 1.5 g of accelerator CZ were added to 100 g of styrene-butadiene rubber, mixed evenly and then vulcanized at a vulcanization temperature of 155°C, a vulcanization time of 30 minutes and a vulcanization pressure of 15 MPa to finally obtain a vulcanized rubber (sheet).
[0035] The tensile strength and fracture energy of the sheet were tested according to the method described in Example 1, and the tensile strength of the sheet was 2.09 MPa and the fracture energy was 0.73 kJ / m 2 The test results show that the tensile strength and breaking energy of the diazo compound toughened vulcanized rubber prepared in Example 1 of the present application are increased to a certain extent compared with the traditional vulcanized rubber.
[0036] Example 2 Preparation of Diazo Compound Strengthened Vulcanized Rubber
[0037] On an open mixing mill, 2g of diazo compound, 5g of zinc oxide, 2g of stearic acid, 1.5g of accelerator CZ and 1.5g of sulfur were added to 100g of styrene-butadiene rubber, mixed evenly and then vulcanized at a vulcanization temperature of 155°C, a vulcanization time of 23 minutes and a vulcanization pressure of 15MPa to finally obtain diazo compound toughened vulcanized rubber (sheet).
[0038] Preparation method of diazo compound: 7.7g 2-hydroxyethyl disulfide and 8.7g pyridine are charged into a flat-bottomed flask, mixed evenly at room temperature with a magnetic stirrer at a speed of 400rpm, then 17.0g phenylacetyl chloride is slowly added, and the mixture is reacted at room temperature for 12 hours. The above product is then rotary evaporated and washed and charged into a flat-bottomed flask with 59.2g p-toluenesulfonyl azide, mixed evenly at room temperature with a magnetic stirrer at a speed of 400rpm, then 38.1g 1,8-dichloroheterobicyclo[5.4.0]undec-7-ene is slowly added, and the mixture is reacted at room temperature for 12 hours to obtain a diazo compound.
[0039] The tensile strength and fracture energy of the sheet were tested according to the method described in Example 1, and the tensile strength of the sheet was 2.49 MPa and the fracture energy was 1.11 kJ / m 2 .
[0040] Comparative Example 2
[0041] On an open mill, 1.5 g of sulfur, 5 g of zinc oxide, 2 g of stearic acid and 1.5 g of accelerator CZ were added to 100 g of styrene-butadiene rubber, mixed evenly and then vulcanized at a vulcanization temperature of 155°C, a vulcanization time of 30 minutes and a vulcanization pressure of 15 MPa to finally obtain a vulcanized rubber (sheet).
[0042] The tensile strength and fracture energy of the sheet were tested according to the method described in Example 1, and the tensile strength of the sheet was 1.94 MPa and the fracture energy was 0.71 kJ / m 2 The test results show that the tensile strength and breaking energy of the diazo compound toughened vulcanized rubber prepared in Example 2 of the present application are increased compared with the traditional vulcanized rubber.
[0043] Example 3 Preparation of Diazo Compound Strengthened Vulcanized Rubber
[0044] On an open mixing mill, 3g of diazo compound, 5g of zinc oxide, 2g of stearic acid, 1.5g of accelerator CZ and 1.5g of sulfur were added to 100g of styrene-butadiene rubber, mixed evenly and then vulcanized at a vulcanization temperature of 155°C, a vulcanization time of 20 minutes and a vulcanization pressure of 15MPa to finally obtain diazo compound toughened vulcanized rubber (sheet).
[0045] Preparation method of diazo compound: 7.7g 2-hydroxyethyl disulfide and 8.7g pyridine are charged into a flat-bottomed flask, mixed evenly at room temperature with a magnetic stirrer at a speed of 400rpm, then 17.0g phenylacetyl chloride is slowly added, and the mixture is reacted at room temperature for 12 hours. The above product is then rotary evaporated and washed and charged into a flat-bottomed flask with 59.2g p-toluenesulfonyl azide, mixed evenly at room temperature with a magnetic stirrer at a speed of 400rpm, then 38.1g 1,8-dichloroheterobicyclo[5.4.0]undec-7-ene is slowly added, and the mixture is reacted at room temperature for 12 hours to obtain a diazo compound.
[0046] The tensile strength and fracture energy of the sheet were tested according to the method described in Example 1, and the tensile strength of the sheet was 2.33 MPa and the fracture energy was 1.43 kJ / m 2 .
[0047] Comparative Example 3
[0048] On an open mill, 1.5 g of sulfur, 5 g of zinc oxide, 2 g of stearic acid and 1.5 g of accelerator CZ were added to 100 g of styrene-butadiene rubber, mixed evenly and then vulcanized at a vulcanization temperature of 155°C, a vulcanization time of 30 minutes and a vulcanization pressure of 15 MPa to finally obtain a vulcanized rubber (sheet).
[0049] The tensile strength and fracture energy of the sheet were tested according to the method described in Example 1, and the tensile strength of the sheet was 1.90 MPa and the fracture energy was 0.70 kJ / m 2 The test results show that the tensile strength and breaking energy of the diazo compound toughened vulcanized rubber prepared in Example 3 of the present application are significantly increased compared with the traditional vulcanized rubber.
[0050] Example 4 Preparation of Diazo Compound Strengthened Vulcanized Rubber
[0051] On an open mixing mill, 4g of diazo compound, 5g of zinc oxide, 2g of stearic acid, 1.5g of accelerator CZ and 1.5g of sulfur were added to 100g of styrene-butadiene rubber, mixed evenly and then vulcanized at a vulcanization temperature of 155°C, a vulcanization time of 17 minutes and a vulcanization pressure of 15MPa to finally obtain diazo compound toughened vulcanized rubber (sheet).
[0052] Preparation method of diazo compound: 7.7g 2-hydroxyethyl disulfide and 8.7g pyridine are charged into a flat-bottomed flask, mixed evenly at room temperature with a magnetic stirrer at a speed of 400rpm, then 17.0g phenylacetyl chloride is slowly added, and the mixture is reacted at room temperature for 12 hours. The above product is then rotary evaporated and washed and charged into a flat-bottomed flask with 59.2g p-toluenesulfonyl azide, mixed evenly at room temperature with a magnetic stirrer at a speed of 400rpm, then 38.1g 1,8-dichloroheterobicyclo[5.4.0]undec-7-ene is slowly added, and the mixture is reacted at room temperature for 12 hours to obtain a diazo compound.
[0053] The tensile strength and fracture energy of the sheet were tested according to the method described in Example 1, and the tensile strength of the sheet was 2.39 MPa and the fracture energy was 1.20 kJ / m 2 .
[0054] Comparative Example 4
[0055] On an open mill, 1.5 g of sulfur, 5 g of zinc oxide, 2 g of stearic acid and 1.5 g of accelerator CZ were added to 100 g of styrene-butadiene rubber, mixed evenly and then vulcanized at a vulcanization temperature of 155°C, a vulcanization time of 30 minutes and a vulcanization pressure of 15 MPa to finally obtain a vulcanized rubber (sheet).
[0056] The tensile strength and fracture energy of the sheet were tested according to the method described in Example 1, and the tensile strength of the sheet was 1.99 MPa and the fracture energy was 0.74 kJ / m 2 The test results show that the tensile strength and breaking energy of the diazo compound toughened vulcanized rubber prepared in Example 4 of the present application are increased to a certain extent compared with the traditional vulcanized rubber.
[0057] In summary, the present application provides a diazo compound reinforced rubber, which uses a specific diazo compound as a cross-linking agent and modifier, can toughen the vulcanization network under a specific accelerator, and significantly improve the rubber strength and fracture energy, further expanding the application range of the rubber, and has good application prospects.
[0058] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.
Claims
1. A toughened vulcanized rubber based on CH activation strategy, characterized in that: The CH bond-based toughened vulcanized rubber is prepared from the following raw materials in the following weight ratio: 100 parts of rubber, 0.1-10 parts of CH bond activator, 1-5 parts of zinc oxide, 1-5 parts of stearic acid, 1-6 parts of accelerator, and 0.3-6 parts of sulfur.
2. The toughened vulcanized rubber based on CH activation strategy according to claim 1, characterized in that: The CH bond-based toughened vulcanized rubber is prepared from the following raw materials in the following weight ratio: 100 parts of rubber, 3 parts of CH bond activator, 5 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of accelerator, and 1.5 parts of sulfur.
3. The toughened vulcanized rubber based on CH activation strategy according to claim 1, characterized in that: The CH bond activator is a diazo compound.
4. The toughened vulcanized rubber based on CH activation strategy according to claim 3, characterized in that: The diazo compound is a diazo compound obtained by diazo transfer reaction.
5. The toughened vulcanized rubber based on CH activation strategy according to claim 4, characterized in that: The preparation process of the diazo compound is: 2-Hydroxyethyl disulfide, pyridine and phenylacetyl chloride are mixed and reacted at room temperature for 12 hours to obtain a primary product; the primary product, p-toluenesulfonyl azide and 1,8-dichloroheterobicyclo[5.4.0]undec-7-ene are then mixed and reacted at room temperature for 12 hours to obtain a diazo compound.
6. The toughened vulcanized rubber based on CH activation strategy according to claim 1, characterized in that: The rubber is natural rubber or synthetic rubber; and / or The accelerator is accelerator CZ.
7. The toughened vulcanized rubber based on CH activation strategy according to claim 6, characterized in that: The synthetic rubber is styrene-butadiene rubber.
8. A method for preparing toughened vulcanized rubber based on CH activation strategy according to any one of claims 1 to 7, characterized in that: The following steps are involved: The raw rubber, CH bond activator, zinc oxide, stearic acid, accelerator and sulfur are weighed according to the weight ratio; the raw materials are mixed evenly and then vulcanized to obtain the CH bond-strengthened vulcanized rubber.
9. The method for preparing toughened vulcanized rubber based on CH activation strategy according to claim 8, characterized in that: The vulcanization temperature is 150-160° C., the vulcanization time is 15-30 minutes, and the vulcanization pressure is 10-15 MPa.
10. Use of the toughened vulcanized rubber based on the CH activation strategy according to any one of claims 1 to 7 in the preparation of formulations or equipment for tires, seals, shock absorbers.