A liquid metal-based composite latex, its preparation method, and its application
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-18
- Publication Date
- 2026-08-14
AI Technical Summary
此类方法存在以下技术缺陷：首先，高温、高黏度处理不仅能耗较高，且容易导致液态金属发生热氧化或结构破坏，易发生团聚或渗漏；其次，现有技术未涉及以天然胶乳为基底的液相复合方式，无法利用胶乳自身的胶体稳定性来实现液态金属的均匀负载；最后，现有方案最终产品多为传统的复合橡胶，仅能发挥物理共混的补强或导电功能，难以制备出兼具特定响应性、环境敏感性等功能特性的功能胶乳材料
[0017]镓基液态金属具有良好的导电、导热和可变形性等性能，然而高体积密度和界面张力使其难以稳定分散在柔性基体，在制备过程中易发生填料融合。因此借助天然胶乳自身胶体稳定性可实现液态金属粒子均匀负载。本申请所采用的硫化体系利用过氧化氢叔丁醇与铁离子的氧化还原反应，低温硫化可制备高强韧性复合薄膜，此外预硫化体系不含硫磺等交联助剂，属于环保型的胶乳硫化体系。
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Figure CN122563183A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of polymer composite materials technology, and in particular to a liquid metal-based composite latex, its preparation method, and its application. Background Technology
[0002] Currently, most existing technologies for rubber-liquid metal composites employ high-temperature mixing or high-viscosity matrix mixing processes. This approach typically involves first mixing solid rubber at high temperatures or preparing a high-viscosity solution, followed by mechanical blending of the liquid metal. These methods suffer from the following technical drawbacks: First, the high-temperature, high-viscosity processing not only consumes a lot of energy but also easily leads to thermal oxidation or structural damage of the liquid metal, resulting in agglomeration or leakage. Second, existing technologies do not address liquid-phase composites based on natural latex, failing to utilize the colloidal stability of the latex itself to achieve uniform loading of the liquid metal. Finally, the final products of existing solutions are mostly traditional composite rubbers, only capable of providing physical reinforcement or conductivity, and are difficult to prepare functional latex materials with specific responsiveness, environmental sensitivity, and other functional properties. Summary of the Invention
[0003] In view of this, this application provides a liquid metal-based composite latex, its preparation method, and its application. This method can achieve submicron-level uniform dispersion of liquid metal in the latex, and can also be cured and molded at room temperature to prepare a functional composite flexible film with high mechanical strength. It can effectively overcome the problems of easy agglomeration of existing liquid metals and high energy consumption caused by traditional high-viscosity and violent mixing.
[0004] The first aspect of this application provides a liquid metal-based composite latex, comprising the following components by mass percentage: 17.36-45.65 wt% liquid metal and 54.35-82.64 wt% pre-vulcanized natural latex.
[0005] Preferably, the pre-vulcanized natural rubber latex comprises the following components by weight percentage: 44.39-69.30 wt% natural rubber latex, 0.40-0.63 wt% sodium dodecyl sulfate solution, 0.40-0.63 wt% hydrogen peroxide tert-butanol solution, 2.73-4.27 wt% fructose solution, 7.28-11.36 wt% ferric pyrophosphate solution, with the balance being deionized water.
[0006] Preferably, the liquid metal is a gallium-based liquid metal.
[0007] A second aspect of this application also provides a method for preparing the above-mentioned liquid metal-based composite latex, comprising the following steps:
[0008] (1) Dissolve a certain amount of ferric pyrophosphate in deionized water and stir at room temperature for 5 h to prepare a ferric pyrophosphate solution with a concentration of 0.92 wt%; dissolve a certain amount of sodium dodecyl sulfate in deionized water and stir at room temperature for 20 min to prepare a sodium dodecyl sulfate solution with a concentration of 20 wt%; dissolve a certain amount of fructose in deionized water and stir at room temperature for 20 min to prepare a fructose solution with a concentration of 25 wt%;
[0009] (2) At room temperature, deionized water, sodium dodecyl sulfate solution, hydrogen peroxide tert-butanol solution, fructose solution and ferric pyrophosphate solution are added sequentially to natural latex to obtain a mixture. Then, the mixture is subjected to a pre-vulcanization reaction to obtain pre-vulcanized natural latex.
[0010] (3) The pre-vulcanized natural latex and liquid metal are ultrasonically dispersed to obtain a composite latex.
[0011] Preferably, in step (2), the stirring time after each additive is added is 5 min.
[0012] Preferably, in step (2), the specific process of the pre-vulcanization reaction is as follows: the mixture is transferred to a water bath at 50-60°C and stirred for 20 min-6 h.
[0013] Preferably, in step (3), the specific process of ultrasonic dispersion is as follows: ultrasonic dispersion is performed in an ice-water bath using an ultrasonic disperser.
[0014] Preferably, in step (3), the ultrasonic dispersion time is 10 min, the ultrasonic dispersion power is 600 W, and the frequency is 25 kHz.
[0015] The third aspect of this application also provides the application of the above-mentioned liquid metal-based composite latex in the preparation of high-strength and tough flexible films.
[0016] Compared with the prior art, this application has the following advantages:
[0017] Gallium-based liquid metals possess excellent electrical and thermal conductivity and deformability; however, their high bulk density and interfacial tension make them difficult to disperse stably in flexible substrates, and filler fusion easily occurs during preparation. Therefore, the colloidal stability of natural latex can be utilized to achieve uniform loading of liquid metal particles. The vulcanization system used in this application utilizes the redox reaction between hydrogen peroxide and tert-butanol with iron ions. Low-temperature vulcanization can prepare high-strength and tough composite films. Furthermore, the pre-vulcanization system does not contain sulfur or other crosslinking aids, making it an environmentally friendly latex vulcanization system. Attached Figure Description
[0018] To more clearly illustrate the technical solutions in this application or the prior art, the drawings used in the description of this application or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0019] Figure 1 The stress-strain curves of the composite latex films obtained in Examples 1-6 are shown below.
[0020] Figure 2 The stress-strain curves of the composite latex films obtained in Examples 7-10 are shown.
[0021] Figure 3 SEM images of the composite latex films obtained in Examples 1 and 11-12. Detailed Implementation
[0022] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions in this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0023] Unless otherwise specified, the experimental methods used in the embodiments of this application are all conventional methods.
[0024] Unless otherwise specified, all raw materials used in the following examples and comparative examples were prepared commercially or by conventional methods. Natural latex (60 wt% dry rubber content) was purchased from Maoming Zhengmao Petrochemical Co., Ltd.; tert-butanol peroxide (70 wt%) and D-fructose (99 wt%) were purchased from Aladdin Biotechnology Co., Ltd. (Shanghai, China); sodium dodecyl sulfate (99 wt%) was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.; and ferric pyrophosphate (98 wt%) was purchased from Shanghai Mairui Chemical Technology Co., Ltd.
[0025] Example 1
[0026] The liquid metal-based composite latex of this embodiment comprises the following components by mass percentage: 45.65 wt% liquid metal and 54.35 wt% pre-vulcanized natural latex.
[0027] The pre-vulcanized natural latex comprises the following components by weight percentage: 69.30 wt% natural latex, 0.63 wt% sodium dodecyl sulfate solution, 0.63 wt% hydrogen peroxide tert-butanol solution, 4.27 wt% fructose solution, 11.36 wt% ferric pyrophosphate solution, and the balance being deionized water.
[0028] The preparation method of the above-mentioned liquid metal-based composite latex includes the following steps:
[0029] (1) Dissolve 0.1g of ferric pyrophosphate in deionized water and stir at room temperature for 5 h to prepare a ferric pyrophosphate solution with a concentration of 0.92 wt%; dissolve 3g of sodium dodecyl sulfate in deionized water and stir at room temperature for 20 min to prepare a sodium dodecyl sulfate solution with a concentration of 20 wt%; dissolve 3g of fructose in deionized water and stir at room temperature for 20 min to prepare a fructose solution with a concentration of 25 wt%.
[0030] At room temperature, 27.7 ml of deionized water was added to 139 g of natural rubber latex, followed by 1.27 ml of sodium dodecyl sulfate solution. After taking out 80 g of the above solution, 0.65 ml of hydrogen peroxide tert-butanol solution, 3.77 ml of fructose solution, and 10.85 ml of ferric pyrophosphate solution were added in sequence to obtain a mixture. The stirring time was 5 min after each additive was added. The mixture was transferred to a water bath at 60 °C and stirred for 20 min to obtain pre-vulcanized natural rubber latex.
[0031] (2) Take 12.5 g of the pre-vulcanized natural latex and 10.5 g of liquid metal, and use an ultrasonic disperser to disperse them in an ice-water bath for 10 min. The ultrasonic dispersion power is 600 W and the frequency is 25 kHz to obtain liquid metal-based composite latex.
[0032] Example 2
[0033] The liquid metal-based composite latex and its preparation method provided in this embodiment can be referred to in Embodiment 1. The difference is that in step (1), the mixture is transferred to a water bath at 60°C and stirred for 30 min to obtain pre-vulcanized natural latex.
[0034] Example 3
[0035] The liquid metal-based composite latex and its preparation method provided in this embodiment can be referred to in Embodiment 1. The difference is that in step (1), the mixture is transferred to a water bath at 60°C and stirred for 1 h to obtain pre-vulcanized natural latex.
[0036] Example 4
[0037] The liquid metal-based composite latex and its preparation method provided in this embodiment can be referred to in Embodiment 1. The difference is that in step (1), the mixture is transferred to a water bath at 60°C and stirred for 2 hours to obtain pre-vulcanized natural latex.
[0038] Example 5
[0039] The liquid metal-based composite latex and its preparation method provided in this embodiment can be referred to in Embodiment 1. The difference is that in step (1), the mixture is transferred to a water bath at 60°C and stirred for 3 hours to obtain pre-vulcanized natural latex.
[0040] Example 6
[0041] The liquid metal-based composite latex and its preparation method provided in this embodiment can be referred to in Embodiment 1. The difference is that in step (1), the mixture is transferred to a water bath at 60°C and stirred for 6 hours to obtain pre-vulcanized natural latex.
[0042] Example 7
[0043] The liquid metal-based composite latex and its preparation method provided in this embodiment can be referred to in Embodiment 1. The difference is that in step (1), the mixture is transferred to a water bath at 50°C and stirred for 30 min to obtain pre-vulcanized natural latex.
[0044] Example 8
[0045] The liquid metal-based composite latex and its preparation method provided in this embodiment can be referred to in Embodiment 1. The difference is that in step (1), the mixture is transferred to a water bath at 50°C and stirred for 1 h to obtain pre-vulcanized natural latex.
[0046] Example 9
[0047] The liquid metal-based composite latex and its preparation method provided in this embodiment can be referred to in Embodiment 1. The difference is that in step (1), the mixture is transferred to a water bath at 50°C and stirred for 3 hours to obtain pre-vulcanized natural latex.
[0048] Example 10
[0049] The liquid metal-based composite latex and its preparation method provided in this embodiment can be referred to in Embodiment 1. The difference is that in step (1), the mixture is transferred to a water bath at 50°C and stirred for 6 hours to obtain pre-vulcanized natural latex.
[0050] Example 11
[0051] The composite latex and its preparation method in this comparative example can be referred to Example 1, except that in step (2), the added mass of liquid metal is 2.62 g. The liquid metal-based composite latex includes the following components by mass percentage: 17.36 wt% liquid metal and 82.64 wt% pre-vulcanized natural latex. The pre-vulcanized natural latex includes the following components by mass percentage: 69.30 wt% natural latex, 0.63 wt% sodium dodecyl sulfate solution, 0.63 wt% hydrogen peroxide tert-butanol solution, 4.27 wt% fructose solution, 11.36 wt% ferric pyrophosphate solution, and the balance being deionized water.
[0052] Example 12
[0053] The composite latex and its preparation method in this comparative example can be referred to Example 1, except that in step (3), the added mass of liquid metal is 5.25 g. The liquid metal-based composite latex includes the following components by mass percentage: 29.58 wt% liquid metal and 70.42 wt% pre-vulcanized natural latex. The pre-vulcanized natural latex includes the following components by mass percentage: 69.30 wt% natural latex, 0.63 wt% sodium dodecyl sulfate solution, 0.63 wt% hydrogen peroxide tert-butanol solution, 4.27 wt% fructose solution, 11.36 wt% ferric pyrophosphate solution, and the balance being deionized water.
[0054] Examples of implementations are shown in Table 1.
[0055] Table 1
[0056]
[0057] Examples 1 and 11-12 are shown in Table 2.
[0058] Table 2
[0059]
[0060] Test case
[0061] The liquid metal-based composite latex from Examples 1 and 11-12 was coated onto a glass plate using a 400 μm coater to form a film, and the composite latex film was obtained at room temperature.
[0062] Figure 1 and Figure 2 Table 1 shows the mechanical properties of the composite latex films obtained under different embodiments. As can be seen from the figure, the mechanical properties are better in embodiments 2, 3, 4, and 10. Among them, the mechanical properties of embodiment 2 are the best, with a stress of about 9 MPa and a strain of about 1100%.
[0063] Figure 3The diagram shows the microscopic images of the composite latex films obtained using the examples and comparative examples in Table 2 under SEM. It can be seen that under the conditions of Example 1, the liquid metal has the best distribution effect in natural rubber.
[0064] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.
Claims
1. A liquid metal-based composite latex, characterized in that, It includes the following components by weight percentage: 17.36-45.65 wt% liquid metal and 54.35-82.64 wt% pre-vulcanized natural latex.
2. The liquid metal-based composite latex according to claim 1, characterized in that, The pre-vulcanized natural latex comprises the following components by weight percentage: 44.39-69.30 wt% natural latex, 0.40-0.63 wt% sodium dodecyl sulfate solution, 0.40-0.63 wt% hydrogen peroxide tert-butanol solution, 2.73-4.27 wt% fructose solution, 7.28-11.36 wt% ferric pyrophosphate solution, with the balance being deionized water.
3. The liquid metal-based composite latex according to claim 1, characterized in that, The liquid metal is a gallium-based liquid metal.
4. A method for preparing the liquid metal-based composite latex according to any one of claims 1 to 3, characterized in that, Includes the following steps: (1) Dissolve a certain amount of ferric pyrophosphate in deionized water and stir at room temperature for 5 h to prepare a ferric pyrophosphate solution with a concentration of 0.92 wt%; dissolve a certain amount of sodium dodecyl sulfate in deionized water and stir at room temperature for 20 min to prepare a sodium dodecyl sulfate solution with a concentration of 20 wt%; dissolve a certain amount of fructose in deionized water and stir at room temperature for 20 min to prepare a fructose solution with a concentration of 25 wt%; (2) At room temperature, deionized water, sodium dodecyl sulfate solution, hydrogen peroxide tert-butanol solution, fructose solution and ferric pyrophosphate solution are added sequentially to natural latex to obtain a mixture. Then, the mixture is subjected to a pre-vulcanization reaction to obtain pre-vulcanized natural latex. (3) The pre-vulcanized natural latex and liquid metal are ultrasonically dispersed to obtain a composite latex.
5. The preparation method according to claim 4, characterized in that, In step (2), the stirring time is 5 min after each additive is added.
6. The preparation method according to claim 4, characterized in that, In step (2), the specific process of the pre-vulcanization reaction is as follows: the mixture is transferred to a water bath at 50-60°C and stirred for 20 min-6 h.
7. The preparation method according to claim 4, characterized in that, In step (3), the specific process of ultrasonic dispersion is as follows: ultrasonic dispersion is performed in an ice-water bath using an ultrasonic disperser.
8. The preparation method according to claim 4, characterized in that, In step (3), the ultrasonic dispersion time is 10 min, the ultrasonic dispersion power is 600 W, and the frequency is 25 kHz.
9. The application of the liquid metal-based composite latex according to any one of claims 1 to 3 in the preparation of high-strength and tough flexible films.