Hierarchical pore conjugated microporous polymer waterproof breathable material and preparation method thereof
The preparation of hierarchical conjugated microporous polymers by the Pickering emulsion template method solves the problems of insufficient pore structure stability and air permeability in the preparation of existing porous materials, and achieves a balance between high air permeability and high hydrostatic pressure, which is suitable for the encapsulation and protection of outdoor electronic devices.
Patent Information
- Application Number
- CN202511191600.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-25
- Publication Date
- 2025-11-11
AI Technical Summary
Existing porous material preparation processes suffer from problems such as easy collapse of pore structure, poor water pressure resistance, insufficient mechanical strength, high requirements for material compatibility, and health hazards from fluorinated chemicals, making it difficult to achieve a balance between high air permeability and high hydrostatic pressure.
Using the Pickering emulsion template method, bromobenzene and ethynylbenzene are used as reactants to polymerize in an emulsion via a Sonogashira coupling reaction to form a conjugated microporous polymer. Combined with nano-TiO2, SiO2 and other solid particles as stabilizers, a hierarchical porous conjugated microporous polymer is prepared, forming a three-level pore structure of micron-sized macropores, conjugated micropores and emulsion template macropores, avoiding the use of fluorine-containing finishing agents.
It achieves high air permeability, high hydrostatic pressure and high hydrophobicity. The material maintains good waterproof and breathable properties even after being contaminated by chemical reagents, making it suitable for the encapsulation and protection of outdoor electronic devices.
Smart Images
Figure CN120923740A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of porous material preparation technology, and particularly relates to a waterproof and breathable material prepared by the Pickering emulsion template method. Background Technology
[0002] Exposed to dynamic weather conditions and harsh outdoor environments, electronic components are susceptible to performance degradation due to liquid water penetration and particulate contamination. With the rapid development of the electronics industry, the next generation of outdoor electronic devices urgently requires novel packaging materials that combine protection and breathability. Among these, waterproof and breathable materials based on microporous structures achieve synergistic control of liquid water barrier and gas molecule transport through precise regulation of pore topology. These materials can be used for the encapsulation and protection of electronic devices while maintaining the balance of gas exchange inside and outside the device, demonstrating significant value in precision electronic equipment and outdoor energy devices. They are widely used in the protection of wearable electronic devices, gas sensor arrays, outdoor lighting, photovoltaic power generation, new energy vehicles, and electronic communication equipment. Currently developed methods for preparing porous materials mainly include phase separation, foaming, electrospinning, interfacial polymerization, and emulsion template methods. However, traditional waterproof and breathable membrane manufacturing processes have various problems. For example, the pore structure of foamed membranes is prone to collapse, resulting in poor water pressure resistance; membranes prepared by interfacial polymerization lack mechanical strength and cannot achieve self-supporting structures; electrospinning has extremely high requirements for material compatibility, needing to consider the viscosity, solubility, or other physicochemical properties of the polymer matrix, and the uneven pores between fibers are easily permeated by liquid water. Furthermore, regardless of the manufacturing process, fluorides are often introduced to enhance waterproofness and improve hydrostatic pressure resistance; however, fluorinated chemicals exhibit long-distance migration, bioaccumulation, and biodegradability, ultimately posing a serious threat to human health through the food chain.
[0003] Based on Young's Laplace equation and Fick's law, improving the breathability of materials is often achieved by adjusting porosity, pore size, and the interconnectivity of pores, but this reduces the hydrostatic pressure of the material. Therefore, an ideal waterproof and breathable material should have a suitable pore structure to achieve a balance between hydrostatic pressure and breathability. Pickering emulsions refer to metastable systems using solid particles as stabilizers, where the solid particles can replace surfactants to stabilize the emulsion. Due to its unique solid particle stabilization mechanism, the pickering emulsion template method allows for a narrower droplet size distribution in the oil-water interface, significantly improving pore uniformity after polymerization. This directly generates self-supporting porous masses. Furthermore, by controlling the hydrophilicity and hydrophobicity of the solid particles, submicron-level interconnected pores and highly hydrophobic surfaces can be synergistically achieved, overcoming the bottleneck of drastic reduction in breathability caused by pore size reduction in traditional technologies. In summary, the industry urgently needs to develop a new waterproof and breathable material preparation process that can achieve precise control of pore size / porosity, self-supporting mechanical strength, environmental friendliness (fluorine-free), and a membrane material size sufficient for the needs of various application scenarios. Summary of the Invention
[0004] The purpose of this invention is to provide a multi-level porous conjugated microporous polymer waterproof and breathable material with high air permeability, high hydrostatic pressure and high hydrophobicity, and its preparation method.
[0005] The waterproof and breathable material provided by this invention is prepared by the following steps:
[0006] Step 1: Preparation of the oil phase
[0007] Bromobenzene and ethynylbenzene were dissolved in a mixture of toluene and organic amines, a catalyst was added, and the mixture was thoroughly shaken and dispersed to obtain an oil phase.
[0008] Step 2: Emulsion Preparation
[0009] Ultrapure water, Pickering stabilizer, and surfactant were added sequentially to the oil phase, and the mixture was emulsified at high speed using a homogenizer to form a W / O type Pickering emulsion.
[0010] Step 3: Emulsion polymerization to prepare conjugated microporous polymer bulk materials
[0011] The W / O type Pickering emulsion was heated to completely polymerize bromobenzene and ethynylbenzene. After cooling to room temperature, the resulting product was washed sequentially with methanol, acetone and dichloromethane, and dried to obtain a conjugated microporous polymer block.
[0012] Step 4: Preparation of multi-level porous conjugated microporous polymer waterproof and breathable material
[0013] The conjugated microporous polymer block is processed into a membrane with uniform thickness and smooth surface. The debris on the membrane surface is cleaned with deionized water to obtain a multi-level pore conjugated microporous polymer waterproof and breathable material.
[0014] In step 1 above, the bromobenzene is selected from any one or more of 1,3,5-tribromobenzene, 1,3-dibromobenzene, and 1,4-dibromobenzene; the ethynylbenzene is selected from any one or more of 1,4-diethynbenzene and 1,3,5-triethynbenzene; the organic amine is selected from any one of triethylamine, diethylamine, and diisopropylethylamine; and the catalyst is selected from any group of Pd(OAc)2 / PPh3 / CuI, Pd(PPh3)4 / CuI, and PdCl2(PPh3)2 / CuI.
[0015] In step 1 above, it is further preferred that the mass ratio of bromobenzene to acetylenol is 1:2 to 2:1, and the total concentration of bromobenzene and acetylenol in the oil phase is 0.12 to 0.4 g / mL.
[0016] In step 1 above, it is further preferred that the volume ratio of toluene to organic amine is 2:1 to 4:1.
[0017] In step 1 above, it is further preferred that the amount of each component added in the catalyst is 5% to 10% of the total mass of bromobenzene and ethynylbenzene.
[0018] In step 2 above, the Pickering stabilizer is selected from any one of nano TiO2, nano SiO2, and graphene nanosheets; the surfactant is selected from any one or more of Span 20, Span 80, Span 85, and Tween 60.
[0019] In step 2 above, it is further preferred that the volume ratio of the oil phase to the ultrapure water is 2:1 to 1:2, and the amount of Pickering stabilizer and surfactant added is 2% to 10% of the total mass of bromobenzene and ethynylbenzene, respectively.
[0020] In step 2 above, it is further preferred that the stirring speed of the homogenizer is 20,000 to 28,000 rpm.
[0021] In step 3 above, it is further preferred that the W / O type Pickering emulsion is reacted at 50-90°C for 24-72 hours to completely polymerize bromobenzene and ethynylbenzene.
[0022] In step 3 above, it is further preferred that the drying is first performed at 20-30°C for 24 hours, and then at 80-100°C for 4-10 hours.
[0023] In step 4 above, it is further preferred that the thickness of the membrane is 200-1000 μm.
[0024] The beneficial effects of this invention are as follows:
[0025] 1. This invention uses bromobenzene and ethynylbenzene as reactive monomers to polymerize a conjugated microporous polymer with its own microporous structure and a permanent rigid π-conjugated backbone in an emulsion via a Sonogashira coupling reaction. By changing the ratio of the two monomers, polymer backbones with different degrees of crosslinking can be obtained, thereby forming interconnected micron-sized macropores on the backbone. These macropores, together with the conjugated micropores and the macropores of the emulsion template, form a tertiary pore structure (micropores, secondary pores, and macropores), which significantly enhances the air permeability of the material.
[0026] 2. The emulsion stabilizer used in this invention can better maintain the oil-water interface, keep the emulsion droplets stable, and help provide hydrophobicity after the conjugated microporous polymer polymer is polymerized. It can achieve hydrophobicity of the membrane surface without adding fluorinated finishing agents. The co-surfactant is beneficial to the stability of the emulsion. The secondary channels left in the emulsion template and polymer skeleton after elution increase the degree of opening and the degree of interconnection between the multi-level pore structures, and also improve the overall roughness of the material, thereby improving the air permeability and water resistance of the material at the same time, and making the material have good stability.
[0027] 3. The multi-level porous conjugated microporous polymer waterproof and breathable material prepared by this invention has high air permeability, high hydrostatic pressure, and high hydrophobicity. It can block liquid water while enabling the transport of gas molecules, balancing internal and external humidity and pressure differences. It is worth noting that the waterproof and breathable material prepared by this invention can maintain good waterproof and breathable properties even after exposure to various chemical reagents, such as organic solvents like chloroform, N,N-dimethylformamide, and dimethyl sulfoxide, as well as aqueous solutions of NaOH and HCl, with no significant change in surface morphology. Attached Figure Description
[0028] Figure 1 This is an appearance diagram of the waterproof and breathable materials processed into different thicknesses in Example 1.
[0029] Figure 2 These are the results of air permeability and hydrostatic pressure tests on the 600μm thick waterproof and breathable materials in Examples 1-6.
[0030] Figure 3 This is a graph showing the static water contact angle test results of the waterproof and breathable material in Example 1.
[0031] Figure 4 These are scanning electron microscope (SEM) images of the surface morphology of the waterproof and breathable materials in Examples 1-6. Detailed Implementation
[0032] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.
[0033] Example 1
[0034] Step 1: Preparation of the oil phase
[0035] Dissolve 0.2 g of 1,4-dibromobenzene and 0.2 g of 1,3,5-triethynylbenzene in 1 mL of a mixture of toluene and triethylamine in a volume ratio of 4:1, and add 0.04 g of Pd(OAc)2, 0.02 g of PPh3 and 0.02 g of CuI. Shake thoroughly to disperse evenly and obtain the oil phase.
[0036] Step 2: Emulsion Preparation
[0037] 1 mL of ultrapure water, 0.03 g of nano TiO2, and 0.02 g of Span80 were added sequentially to 1 mL of oil phase, and the mixture was homogenized at 26000 rpm using a homogenizer to form a W / O type Pickering emulsion.
[0038] Step 3: Emulsion polymerization to prepare conjugated microporous polymer bulk materials
[0039] The W / O type Pickering emulsion was reacted at 80℃ for 72h to allow the monomers to fully polymerize. After cooling to room temperature, the resulting product was washed sequentially with methanol, acetone, and dichloromethane. After washing, it was dried at 25℃ for 24h and then at 80℃ for 4h to obtain CMP blocks.
[0040] Step 4: Preparation of multi-level porous CMP waterproof and breathable material
[0041] CMP blocks are processed into membranes with a thickness of 200–1000 μm and a smooth surface. Deionized water is used to clean the debris from the membrane surface to obtain a multi-level porous CMP waterproof and breathable material.
[0042] Figure 1 These are the appearance images of waterproof and breathable materials processed into different thicknesses in this embodiment. The waterproof and breathable materials with thicknesses of 300μm and 600μm were tested for breathability, hydrostatic pressure, static water contact angle, and surface morphology by scanning electron microscopy. Figure 2 The results showed that the air permeability of the 600μm thick waterproof and breathable material was 203.3 mL / min. -1 cm -2 The hydrostatic pressure is 37.2 kPa, and the static water contact angle on the surface is 148.37° (see...). Figure 3 ).Depend on Figure 4(a) It can be seen that the waterproof and breathable material skeleton forms interconnected micron-sized macropores, and the three-level pore structure formed by the conjugate micropores and the emulsion template macropores can enhance the breathability of the material.
[0043] Example 2
[0044] In step 1 of this embodiment, 0.15g of 1,3,5-tribromobenzene and 0.25g of 1,4-diethynylbenzene are dissolved in 1mL of a mixture of toluene and triethylamine in a volume ratio of 4:1. Then, 0.04g of Pd(OAc)₂, 0.02g of PPh₃, and 0.02g of CuI are added and thoroughly dispersed by shaking to obtain an oil phase. In step 4, the CMP block is processed into a film with a thickness of 600μm and a smooth surface. The other steps are the same as in Example 1, resulting in a multi-level porous CMP waterproof and breathable material.
[0045] Figure 2 The results showed that the air permeability of the 600μm thick waterproof and breathable material in this embodiment was 205.2 mL / min. - 1 cm -2 The hydrostatic pressure is 43.1 kPa, and the scanning electron microscope image of its surface morphology is as follows: Figure 4 As shown in (b).
[0046] Example 3
[0047] In step 2 of this embodiment, nano-TiO2 is replaced with an equal mass of nano-SiO2, and the amount of Span80 used is reduced to 0.01g. In step 4, the CMP block is processed into a film with a thickness of 600μm and a smooth surface. The other steps are the same as in Example 1, and a multi-level porous CMP waterproof and breathable material is obtained.
[0048] Figure 2 The results showed that the air permeability of the 600μm thick waterproof and breathable material in this embodiment was 96.11 mL / min. - 1 cm -2 The hydrostatic pressure is 73.7 kPa, and the scanning electron microscope image of its surface morphology is as follows: Figure 4 As shown in (c).
[0049] Example 4
[0050] In step 1 of this embodiment, 1,4-dibromobenzene in Example 1 is replaced with an equal mass of 1,3-dibromobenzene, and 1,3,5-triacetylene in Example 1 is replaced with an equal mass of 1,4-diacetylene. In step 2, nano-TiO2 in Example 1 is replaced with an equal mass of nano-SiO2, and Span80 in Example 1 is replaced with 0.01g Span20 and 0.01g Tween60. In step 4, the CMP block is processed into a film with a thickness of 600μm and a smooth surface. The other steps are the same as in Example 1, and a multi-level porous CMP waterproof and breathable material is obtained.
[0051] Figure 2 The results showed that the air permeability of the 600μm thick waterproof and breathable material in this embodiment was 283.0 mL / min. - 1 cm -2 The hydrostatic pressure is 57.8 kPa, and the scanning electron microscope image of its surface morphology is as follows: Figure 4 As shown in (d).
[0052] Example 5
[0053] In step 2 of this embodiment, 0.06g of graphene nanosheets are used to replace the nano-TiO2 in Example 1. In step 4, the CMP block is processed into a film with a thickness of 600μm and a smooth surface. The other steps are the same as in Example 1, and a multi-level porous CMP waterproof and breathable material is obtained.
[0054] Figure 2 The results showed that the air permeability of the 600μm thick waterproof and breathable material in this embodiment was 115.6 mL / min. - 1 cm -2 The hydrostatic pressure is 108.2 kPa. Scanning electron microscope images of its surface morphology are shown below. Figure 4 As shown in (e).
[0055] Example 6
[0056] In step 1 of this embodiment, 0.1g of 1,4-dibromobenzene and 0.1g of 1,3,5-triethynylbenzene are dissolved in 1mL of a mixture of toluene and triethylamine in a volume ratio of 4:1, and 0.02g of Pd(PPh3)4 and 0.01g of CuI are added. The mixture is then thoroughly shaken and dispersed to obtain an oil phase. In step 4, the CMP block is processed into a film with a thickness of 600μm and a smooth surface. The other steps are the same as in Example 1, resulting in a multi-level porous CMP waterproof and breathable material.
[0057] Figure 2 The results showed that the air permeability of the 600μm thick waterproof and breathable material in this embodiment was 397.5 mL / min. -1 cm -2The hydrostatic pressure is 54.2 kPa, and the scanning electron microscope image of its surface morphology is as follows. Figure 4 As shown in (f).
[0058] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing a multi-level porous conjugated microporous polymer waterproof and breathable material, characterized in that: The preparation method includes the following steps: Step 1: Preparation of the oil phase Bromobenzene and ethynylbenzene were dissolved in a mixture of toluene and organic amines, a catalyst was added, and the mixture was thoroughly shaken and dispersed to obtain an oil phase. The bromobenzene is selected from any one or more of 1,3,5-tribromobenzene, 1,3-dibromobenzene, and 1,4-dibromobenzene; The acetylenylbenzene is selected from any one or more of 1,4-diethynbenzene and 1,3,5-triacetylenbenzene; The organic amine is selected from any one of triethylamine, diethylamine, and diisopropylethylamine; The catalyst is selected from any one of Pd(OAc)2 / PPh3 / CuI, Pd(PPh3)4 / CuI, and PdCl2(PPh3)2 / CuI; Step 2: Emulsion Preparation Ultrapure water, Pickering stabilizer and surfactant were added sequentially to the oil phase, and the mixture was emulsified into a W / O type Pickering emulsion using a homogenizer with high-speed shearing. The Pickering stabilizer is selected from any one of nano-TiO2, nano-SiO2, and graphene nanosheets; The surfactant is selected from any one or more of Span 20, Span 80, Span 85, and Tween 60; Step 3: Emulsion polymerization to prepare conjugated microporous polymer bulk materials The W / O type Pickering emulsion was heated to completely polymerize bromobenzene and ethynylbenzene. After cooling to room temperature, the resulting product was washed sequentially with methanol, acetone and dichloromethane, and dried to obtain a conjugated microporous polymer block. Step 4: Preparation of multi-level porous conjugated microporous polymer waterproof and breathable material The conjugated microporous polymer block is processed into a membrane with uniform thickness and smooth surface. The debris on the membrane surface is cleaned with deionized water to obtain a multi-level pore conjugated microporous polymer waterproof and breathable material.
2. The method for preparing the multi-level porous conjugated microporous polymer waterproof and breathable material according to claim 1, characterized in that: In step 1, the mass ratio of bromobenzene to acetylenol is 1:2 to 2:1, and the total concentration of bromobenzene and acetylenol in the oil phase is 0.12 to 0.4 g / mL.
3. The method for preparing the multi-level porous conjugated microporous polymer waterproof and breathable material according to claim 1, characterized in that: In step 1, the volume ratio of toluene to organic amine is 2:1 to 5:
1.
4. The method for preparing the multi-level porous conjugated microporous polymer waterproof and breathable material according to claim 1, characterized in that: In step 1, the amount of each component added to the catalyst is 5% to 10% of the total mass of bromobenzene and ethynylbenzene.
5. The method for preparing the multi-level porous conjugated microporous polymer waterproof and breathable material according to claim 1, characterized in that: In step 2, the volume ratio of the oil phase to ultrapure water is 2:1 to 1:2, and the amount of Pickering stabilizer and surfactant added is 2% to 10% of the total mass of bromobenzene and ethynylbenzene, respectively.
6. The method for preparing the multi-level porous conjugated microporous polymer waterproof and breathable material according to claim 1, characterized in that: In step 2, the stirring speed of the homogenizer is 20,000 to 28,000 rpm.
7. The method for preparing the multi-level porous conjugated microporous polymer waterproof and breathable material according to claim 1, characterized in that: In step 3, the W / O type Pickering emulsion is reacted at 50-90°C for 24-72 hours to completely polymerize bromobenzene and ethynylbenzene.
8. The method for preparing the multi-level porous conjugated microporous polymer waterproof and breathable material according to claim 1, characterized in that: In step 3, the drying process involves first drying at 20–30°C for 24 hours, and then drying at 80–100°C for 4–10 hours.
9. The method for preparing the multi-level porous conjugated microporous polymer waterproof and breathable material according to claim 1, characterized in that: In step 4 above, the thickness of the membrane is 200-1000 μm.
10. The multi-level porous conjugated microporous polymer waterproof and breathable material obtained by any one of the preparation methods of claims 1 to 9.