Fluororubber compound capable of bonding silicone rubber as well as preparation method and application of fluororubber compound

Abstract

The invention provides a fluororubber compound capable of bonding silicone rubber as well as a preparation method and application of the fluororubber compound, and belongs to the field of rubber materials. According to the fluororubber compound capable of being bonded with the silicone rubber, the fluororubber and the silicone rubber can achieve excellent bonding strength, and the bonding performance is still stable after the fluororubber and the silicone rubber are aged for 3 days in various sweat environments. And the preparation process is simple, easy to operate and easy to industrialize. Compared with traditional fluororubber, the fluororubber compound has the advantages that the bonding reliability and durability of fluororubber and silicone rubber in a sweat environment are remarkably improved, the layering sense of a fluorine-containing watchband is effectively enhanced, the cost is reduced, and a more reliable solution is provided for application of intelligent wearable rubber products.

Description

Technical Field

[0001] The invention belongs to the field of rubber materials, and in particular relates to a fluororubber compound capable of bonding silicone rubber, a preparation method and an application thereof. Background Art

[0002] Against the backdrop of technological advancements and improvements in quality of life, artificial intelligence and the concept of sports and health are gaining popularity. Smart wearable devices, such as watches and bracelets, are experiencing explosive growth in market demand due to their ability to combine traditional watch functions with health monitoring and interaction with smart devices. This has driven the development of materials for smart wearable wristbands and straps. These materials must meet basic requirements such as safety, environmental protection, durability, and comfort, while also possessing specific features such as resistance to pool water, sweat, artificial sebum, oleic acid, and dirt.

[0003] Fluororubber, with its sweat resistance, wide temperature stability, and biocompatibility, is an ideal choice for high-end watch straps. However, traditional fluororubber vulcanization requires high temperatures and long periods of time, making demolding difficult. This results in low production efficiency, a heavier watch strap, and high costs. By combining it with silicone rubber, vulcanization can be completed at relatively low temperatures and in a shorter time, making demolding easier and significantly improving production efficiency. The addition of silicone rubber also reduces the overall weight of the composite material, enhancing the layering and diversity of fluororubber-containing watch straps while reducing costs. Therefore, the development of fluororubber compounds that can be bonded to silicone rubber is urgent.

[0004] Although patent CN113817323B involves the bonding of fluororubber and silicone rubber, it is mainly used in the automotive field to achieve initial and high-temperature bonding performance, but the bonding performance is poor and needs further improvement, and it does not involve bonding in the field of smart wearables. Existing fluororubber and silicone rubber bonding technology has the following shortcomings: in terms of process, it requires strict surface treatment and strict curing conditions, otherwise the bonding strength will be greatly reduced; in terms of performance, the temperature resistance range is limited, and the adhesive is prone to softening, degradation, or brittle cracking at extreme temperatures. The bonding interface is easily damaged in chemical media, and long-term use faces aging problems, and the bonding strength decreases over time. In terms of materials and costs, there are few high-performance adhesives, high prices and unstable supply. The high cost of fluororubber itself leads to high costs for the overall bonding process. Summary of the Invention

[0005] To address the shortcomings of the prior art, the present invention aims to provide a fluororubber compound capable of bonding to silicone rubber, as well as its preparation method and application. This invention aims to address the existing problem of fluororubber and silicone rubber being unable to bond in sweat environments, achieving long-term, stable bonding between the two rubbers in a variety of sweat environments, thereby meeting the demand for high performance and sweat resistance in the smart wearable field.

[0006] The invention provides a fluororubber compound, which comprises the following raw materials in parts by weight: 100 parts of fluororubber raw rubber, 2-5 parts of an acid absorber, 5-50 parts of a filler, 0.5-8 parts of a colorant, 0.3-1.5 parts of a processing aid, 1-8 parts of an adhesive aid, 1-8 parts of a vulcanizing agent, and 0.5-6 parts of a vulcanization accelerator.

[0007] Furthermore, the fluororubber compound comprises the following raw materials in parts by weight: 100 parts of fluororubber raw rubber, 3 to 5 parts of acid absorbent, 10 to 30 parts of filler, 0.5 to 1.5 parts of colorant, 0.5 to 1.5 parts of processing aid, 3 to 5 parts of bonding agent, 2 to 3 parts of vulcanizing agent, and 4 to 6 parts of vulcanization accelerator.

[0008] Furthermore, the fluororubber compound includes the following raw materials in parts by weight: 100 parts of fluororubber raw rubber, 2 parts of acid absorbent, 20 parts of filler, 1 part of colorant, 1 part of processing aid, 3 parts of bonding aid, 2 parts of vulcanizing agent, and 4 parts of vulcanization accelerator.

[0009] Furthermore, the fluororubber raw rubber is one or a mixture of 246M type fluororubber and 26K2 type fluororubber; The acid scavenger is zinc oxide; The filler is any one of barium sulfate, calcium silicate, carbon black, diatomaceous earth, silica powder and white carbon black, or a mixture of any of the above; The colorant is any one of carbon black, titanium dioxide, halogen-free organic blue pigment, halogen-free organic yellow pigment, halogen-free organic red pigment, iron oxide red, iron oxide yellow and iron oxide green, or a mixture of any of the above; The processing aid is any one of octadecylamine, fluororubber internal release agent WS280 and rice bran wax, or a mixture of any two of them; The bonding agent is any one of trimethyltrivinylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, and pentamethylpentavinylcyclopentasiloxane, or a mixture of any two of them; The vulcanizing agent is bis-2,5 (2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane); The vulcanization accelerator is any one of triallyl isocyanurate and trimethylolpropane trimethacrylate, or a mixture of any two of them.

[0010] Furthermore, the fluororubber raw rubber is a mixture of 246M type fluororubber and 26K2 type fluororubber in a mass ratio of 1:1; The filler is diatomaceous earth; The colorant is carbon black; The processing aid is fluororubber internal release agent WS280; The bonding agent is tetramethyltetravinylcyclotetrasiloxane; The vulcanization accelerator is triallyl isocyanurate.

[0011] The present invention also provides a method for preparing the above-mentioned fluororubber compound, which comprises the following steps: mixing fluororubber raw rubber, an acid absorber, a filler, a colorant, a processing aid, an adhesive aid, a vulcanizing agent and a vulcanization accelerator, placing the mixture and then re-mixing the mixture to obtain the fluororubber compound.

[0012] Furthermore, the mixing temperature is 80-115° C., and the time is 2-10 min; the re-milling temperature is 60-95° C., and the number of thin passes is 3-12 times.

[0013] The present invention also provides use of the fluororubber compound in preparing fluororubber products.

[0014] The present invention also provides a rubber smart wearable material, which is a product obtained by gluing the above-mentioned fluororubber compound and silicone rubber compound and then subjecting the mixture to vulcanization treatment.

[0015] Furthermore, the vulcanization treatment is divided into one-stage vulcanization and two-stage vulcanization in sequence, the temperature of the one-stage vulcanization is 170°C~190°C, and the time is 120 seconds~600 seconds; the temperature of the second-stage vulcanization is 170°C~230°C, and the time is 1~4 hours; after the two-stage vulcanization, the rubber smart wearable material is obtained.

[0016] The present invention has achieved the following beneficial effects: The present invention has developed a fluororubber compound capable of bonding to silicone rubber. This compound achieves excellent bonding strength between the two materials, with the bonding performance remaining stable after three days of aging in various sweat environments. The preparation process is simple, easy to operate, and readily industrializable. Compared to conventional fluororubber, the fluororubber compound of the present invention significantly improves the bonding reliability and durability between the two materials in sweat environments, effectively enhancing the texture of fluorinated watchbands while reducing costs. This provides a more reliable solution for the application of rubber products in smart wearables.

[0017] Obviously, based on the above contents of the present invention, according to common technical knowledge and customary means in this field, without departing from the above basic technical ideas of the present invention, other various forms of modifications, replacements or changes can be made.

[0018] The following is a further detailed description of the present invention through specific embodiments in the form of examples. However, this should not be construed as limiting the scope of the present invention to the following examples. All technologies implemented based on the above-mentioned content of the present invention fall within the scope of the present invention. DETAILED DESCRIPTION

[0019] The raw materials and equipment used in the present invention are all known products and are obtained by purchasing commercially available products.

[0020] The raw materials used in the examples of the present invention are referred to as follows: Bis(2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane); TAIC: triallyl isocyanurate.

[0021] Example 1. Preparation of fluororubber compound Example 1 provides a fluororubber compound comprising the following raw materials in parts by weight: The preparation method of the above-mentioned fluororubber compound is: In a pressurized internal mixer, fluororubber raw rubber is added to the internal mixer together with acid absorber, filler, colorant, processing aid, bonding agent, vulcanizer and vulcanization accelerator for mixing for 5 minutes. The mixing temperature is 90°C and the mixing speed is controlled at 32 rpm. It is then left at room temperature for 24 hours. It is then returned to the open mixer in the form of a triangular bag and mixed 10 times at a mixing temperature of 70°C. It is then bonded to silicone rubber and vulcanized to make rubber smart wearable materials.

[0022] Example 2: Preparation of Fluororubber Compound Example 2 provides a fluororubber compound comprising the following raw materials in parts by weight: The preparation method of the fluororubber compound of this embodiment is the same as that of Example 1.

[0023] Example 3: Preparation of Fluororubber Compound Example 3 provides a fluororubber compound comprising the following raw materials in parts by weight: The preparation method of the fluororubber compound of this embodiment is the same as that of Example 1.

[0024] Example 4: Preparation of Fluororubber Compound Example 3 provides a fluororubber compound comprising the following raw materials in parts by weight: The preparation method of the fluororubber compound of this embodiment is the same as that of Example 1.

[0025] Example 5: Preparation of a composite watchband product Preparation of silicone rubber compound: In the kneader, the raw silicone rubber is added to the kneader together with silicone oil and reinforcing agent and mixed. After forming, the colorant and vulcanizer are added and mixed. The kneading temperature is 60°C and the kneading speed is controlled at 35 rpm. After that, it is ground 10 times on a three-roll grinder; then it is returned to the open mill for forming to obtain the silicone rubber compound.

[0026] The fluororubber compounds of Examples 1 to 4 were directly pasted together with the above-mentioned silicone rubber compound, then placed in a mold, and molded in a press at 180° C., 300 seconds, and a force of 10 to 15 MPa to obtain different composite watchband products.

[0027] The following comparative samples are prepared by comparative examples.

[0028] Comparative Example 1: Preparation of Fluororubber Compound Comparative Example 1 provides a fluororubber compound comprising the following raw materials in parts by weight: The preparation method of the fluororubber compound of this comparative example is the same as that of Example 1.

[0029] Comparative Example 2: Preparation of a composite watchband product Referring to the method of Example 5, the fluororubber compound and the silicone rubber compound of Comparative Example 1 were directly pasted together, then placed in a mold, and molded in a press at 180°C, 300 seconds, and a force of 10-15 MPa to obtain a composite watchband product.

[0030] The beneficial effects of the present invention are demonstrated by experimental examples below.

[0031] Experimental Example 1: Testing the bonding performance of fluororubber compound and silicone rubber 1. Experimental methods The bonding properties of the products obtained from the formulations of Examples 1 to 4 and Comparative Example 1 were tested using the national standard method, as follows: After two-stage vulcanization, the composite watchband products prepared in Example 5 and Comparative Example 2 were tested for peel strength of the two rubbers using a universal mechanical testing machine. If the peel strength was greater than 1.5 N / mm or cohesive failure of the rubber occurred, it indicated that the adhesion test had passed. The products were then immersed in oleic acid, lactic acid, and sweat, respectively, at a temperature of 25-60°C for 24-72 hours. After being taken out, the peel strength was tested again. If the peel strength was greater than 1.5 N / mm or cohesive failure of the rubber occurred, it indicated that the adhesion test had passed.

[0032] 2. Experimental results Table 1 Comparison of bonding performance of composite watch strap products Table 1 demonstrates that the fluororubber and silicone rubber compounds prepared using the methods of Examples 1-4 exhibit excellent bonding properties, and the resulting composite watchbands are resistant to various sweat environments. Compared to Comparative Example 1, the products of Examples 1-4, which incorporate an adhesive additive, all exhibit cohesive failure upon initial peeling (strength exceeding 2 N / mm). Furthermore, compared to Example 4, the product of Example 1, which incorporates a lower amount of adhesive additive, also exhibits cohesive failure upon both lactic acid and sweat peeling, and exhibits the highest strength upon oleic acid peeling. Therefore, Example 1 demonstrates the best overall performance, achieving unexpected technical benefits.

[0033] In summary, the present invention provides a fluororubber compound that can be bonded to silicone rubber, and its preparation method and application. The present invention has developed a fluororubber compound that can be bonded to silicone rubber, which can achieve excellent bonding strength between fluororubber and silicone rubber, and the bonding performance remains stable after aging for 3 days in various sweat environments. The preparation process is simple, easy to operate, and easy to industrialize. Compared with traditional fluororubber, the fluororubber compound of the present invention significantly improves the bonding reliability and durability between fluororubber and silicone rubber in a sweat environment, effectively enhances the layering of fluorine-containing watchbands, reduces costs, and provides a more reliable solution for the application of rubber products for smart wearables.

Claims

1. A fluororubber compound, characterized in that: The method comprises the following raw materials in parts by weight: 100 parts of fluororubber raw rubber, 2-5 parts of acid absorbent, 5-50 parts of filler, 0.5-8 parts of colorant, 0.3-1.5 parts of processing aid, 1-8 parts of bonding aid, 1-8 parts of vulcanizing agent and 0.5-6 parts of vulcanization accelerator.

2. The fluororubber compound according to claim 1, characterized in that: The fluororubber compound comprises the following raw materials in parts by weight: 100 parts of fluororubber raw rubber, 3-5 parts of acid absorbent, 10-30 parts of filler, 0.5-1.5 parts of colorant, 0.5-1.5 parts of processing aid, 3-5 parts of bonding aid, 2-3 parts of vulcanizing agent, and 4-6 parts of vulcanization accelerator.

3. The fluororubber compound according to claim 2, characterized in that: The fluororubber compound comprises the following raw materials in parts by weight: 100 parts of fluororubber raw rubber, 2 parts of acid absorbent, 20 parts of filler, 1 part of colorant, 1 part of processing aid, 3 parts of bonding aid, 2 parts of vulcanizing agent, and 4 parts of vulcanization accelerator.

4. The fluororubber compound according to any one of claims 1 to 3, characterized in that: The fluororubber raw rubber is one of 246M type fluororubber and 26K2 type fluororubber, or a mixture of the two; The acid scavenger is zinc oxide; The filler is any one of barium sulfate, calcium silicate, carbon black, diatomaceous earth, silica powder and white carbon black, or a mixture of any of the above; The colorant is any one of carbon black, titanium dioxide, halogen-free organic blue pigment, halogen-free organic yellow pigment, halogen-free organic red pigment, iron oxide red, iron oxide yellow and iron oxide green, or a mixture of any of the above; The processing aid is any one of octadecylamine, fluororubber internal release agent WS280 and rice bran wax, or a mixture of any two of them; The bonding agent is any one of trimethyltrivinylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, and pentamethylpentavinylcyclopentasiloxane, or a mixture of any two of them; The vulcanizing agent is bis-2,5 (2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane); The vulcanization accelerator is any one of triallyl isocyanurate and trimethylolpropane trimethacrylate, or a mixture of any two of them.

5. The fluororubber compound according to claim 4, characterized in that: The fluororubber raw rubber is a mixture of 246M fluororubber and 26K2 fluororubber in a mass ratio of 1:1; The filler is diatomaceous earth; The colorant is carbon black; The processing aid is fluororubber internal release agent WS280; The bonding agent is tetramethyltetravinylcyclotetrasiloxane; The vulcanization accelerator is triallyl isocyanurate.

6. A method for preparing the fluororubber compound according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: mixing fluororubber raw rubber, acid absorbent, filler, colorant, processing aid, bonding aid, vulcanizing agent and vulcanization accelerator, placing the mixture and then re-mixing the mixture to obtain the product.

7. The method according to claim 6, characterized in that The mixing temperature is 80-115° C., and the mixing time is 2-10 minutes; the re-mixing temperature is 60-95° C., and the number of thin passes is 3-12 times.

8. Use of the fluororubber compound according to any one of claims 1 to 5 in the preparation of fluororubber products.

9. A rubber smart wearable material, characterized in that: The product is obtained by gluing the fluororubber compound described in any one of claims 1 to 5 to the silicone rubber compound and then subjecting the mixture to vulcanization treatment.

10. The rubber smart wearable material according to claim 9, characterized in that: The vulcanization treatment is divided into a first-stage vulcanization and a second-stage vulcanization in sequence. The temperature of the first-stage vulcanization is 170°C to 190°C, and the time is 120 seconds to 600 seconds; the temperature of the second-stage vulcanization is 170°C to 230°C, and the time is 1 to 4 hours. After the second-stage vulcanization, the rubber smart wearable material is obtained.

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