Selectively permeable protective clothing material as well as preparation method and application thereof
Through electrospinning technology and double-layer network cross-linking structure, selective permeable protective clothing made of flexible polymer materials is prepared, which solves the problem of high hardness and poor breathability of protective clothing, and achieves high breathability and improvement of self-perceived protective performance.
Patent Information
- Application Number
- CN202510885784.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-30
- Publication Date
- 2025-10-10
AI Technical Summary
Existing selective breathable protective clothing materials are hard and have poor breathability, which reduces the physiological comfort of the protective clothing.
The fluorine-containing fiber membrane is prepared by electrospinning technology, and by regulating the active groups in the gas molecule channel and introducing a double-layer network cross-linking structure, combined with high molecular polymer materials, a flexible and gas-sensitive selective permeable protective material is formed.
It has achieved significant improvements in the breathability and comfort of protective clothing while ensuring protective performance, and has the ability to self-sense and respond to deformation of toxic and harmful gases, thereby improving the wearing experience and reliability of protective clothing.
Smart Images
Figure CN120759100A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of protective materials, and in particular to a selectively permeable protective material, specifically a selectively permeable protective clothing material and a preparation method and application thereof. Background Art
[0002] Selectively breathable protective clothing is typically made of a selectively permeable membrane material, which only allows water vapor molecules to pass through, blocking the infiltration of other liquids, gases, and aerosols. Water vapor molecules are allowed to pass through through a dissolution or diffusion mechanism, while also protecting against toxic substances. Current selectively breathable protective clothing has significant drawbacks: To provide adequate protection, the membrane requires a high protective thickness, resulting in high membrane hardness and poor breathability, reducing the physiological comfort of the protective clothing.
[0003] In order to solve the above problems, those skilled in the art have made various attempts, but all have not been effective, as follows: First, graphene oxide (GO) is partially reduced to reduced graphene oxide (rGO), creating an asymmetric structure. Graphene oxide sheets contain numerous oxygen-containing functional groups, which facilitate the infiltration of water molecules between the sheets and their adsorption on the surface. This causes the GO layers to expand, while the rGO layers remain unchanged, exhibiting bending and deformation. However, GO as a water vapor-responsive material is difficult to implement in protective clothing because GO-based materials are not washable, and the oxygen-containing functional groups on their surface are less than ideally stable. Long-term exposure to air will gradually degrade their water vapor responsiveness.
[0004] Second, natural fibers are surface treated to remove grease and then twisted into yarn. When water penetrates the fibers, it binds to the hydrophilic groups, causing the yarn to expand radially and contract axially. Natural fibers are more readily applicable to protective clothing products than GO, but they must be wetted to deform, making them less sensitive.
[0005] Third, the perfluorosulfonic acid resin membrane (Nafion membrane), composed of a hydrophobic polytetrafluoroethylene backbone and hydrophilic sulfonic acid groups, has numerous water molecule transport channels within the membrane. In high humidity environments, water molecules enter the backbone, causing the surface to swell. Research has found that the sulfonic acid groups on the side chains of the Nafion backbone are responsive to a variety of polar gases, including ethanol, n-propanol, and acetone. However, to meet protective requirements, the Nafion membrane also requires a high barrier thickness to provide adequate protection. This results in high membrane hardness and poor air permeability, reducing the physiological comfort of protective clothing. Summary of the Invention
[0006] In order to solve the problems of high hardness and poor air permeability of current selective permeable membrane materials, the present invention provides a selective permeable protective clothing material and a preparation method and application thereof.
[0007] The present invention is implemented by the following technology: a method for preparing a selectively permeable protective clothing material, comprising the following steps: a. Preparation of spinning solution A fluorocarbon polymer material is dissolved in a polar organic solvent, wherein the weight average molecular weight of the fluorocarbon polymer material is 1.5×10 5 , adding 2 wt % polyethylene glycol and 0.5 wt % chain extender, stirring for 30 min to prepare a 20 wt % spinning solution precursor; b. Electrospinning The prepared spinning solution precursor was controlled to a temperature of 160-230°C, a spinning voltage of 20 KV, and a spinning distance of 15 cm for electrospinning to produce a fluorine-containing fiber membrane. c. Regulation of active groups inside gas molecule channels The fluorine-containing fiber membrane prepared in step b was immersed in an alcohol solution containing kaolin, and 10 wt % perfluorovinyl ether and 0.5 wt % initiator were added, and the reaction was carried out at 80 ° C for 8 h; d, Cross-linking of polymer double-layer network The membrane material soaked in step c was taken out at low temperature and soaked in 5 wt % N, N-dimethylacrylamide monomer, initiator and accelerator to complete solution replacement to obtain a selective permeable membrane material.
[0008] The implementation includes the following steps: a. Preparation of spinning solution The fluorinated sulfonic acid resin particles are converted into fiber materials. By introducing a chain extender into the fluorinated sulfonic acid resin spinning solution, the crosslinking degree of the molecular chain network is regulated, and the three-dimensional crosslinked polymer network is transformed into a linear polymer chain. A fluorocarbon polymer material is dissolved in a polar organic solvent, wherein the weight average molecular weight (Mw) of the fluorocarbon polymer material is 1.5×10 5 The fluorocarbon polymer material is any one of polyvinylidene fluoride (PVDF) and polyvinylidene fluoride-trifluoroethylene copolymer, the polar organic solvent is any one of acetone and dimethylformamide (DMF), 2 wt% polyethylene glycol and 0.5 wt% chain extender are added, stirred for 30 minutes, and prepared into 20wt%. Preferably, the chain extender is any one of alicyclic alcohol chain extender, aromatic alcohol chain extender, and diamine chain extender, more preferably, the chain extender is propylene glycol, to prepare a spinning solution precursor.
[0009] b. Electrospinning The temperature of the prepared spinning solution precursor was controlled to 160~230 ℃ to transform the three-dimensional cross-linked polymer network into linear polymer chains, and electrospinning was carried out with a spinning voltage of 20KV and a spinning distance of 15cm. By adjusting the concentration of the fluorinated sulfonic acid resin to 20wt%, the fiber forming and spinnability of the nanofibers were improved, thereby preparing fibers with highly sensitive performance and producing fluorinated fiber membranes, realizing the fiberization of fluorinated materials and obtaining a fiber substrate with potential responsiveness.
[0010] During the spinning process, a thin stream of perfluorosulfonic acid resin spinning solution is continuously extruded from the spinneret or slit. After the die expands due to extrusion, the spinning stream is stretched and thinned under the axial force provided by the winding device. At the same time, a phase transition occurs due to energy exchange with the cooling medium. The molecules of the perfluorosulfonic acid resin stream tend to be arranged axially, thereby obtaining an excellent structure after solidification.
[0011] c. Regulation of active groups inside gas molecule channels Since the response performance of the material is greatly affected by the gas molecule transport channel, the internal molecular channel skeleton of the fluorine-containing fiber membrane is modified; Targeting specific functional groups within the toxic and hazardous gas molecules that require protection, corresponding active groups are selected and introduced into the molecular channels. Gas molecule transmission channels are abundant in the fluorinated fiber membrane. When the gas concentration is high, the gas molecules enter the skeleton, causing the surface to expand. When there is a gas concentration gradient in the environment, the fluorinated fiber membrane will bend toward the side with lower humidity. The fluorinated fiber membrane prepared in step b is immersed in an alcohol solution containing kaolin to form an "island structure", i.e., a hydrophobic resin phase (fluorinated carbon chain) + a hydrophilic oxide phase (hydroxyl network). The formation of the hydroxyl network can adsorb water molecules through hydrogen bonds, increasing the permeation flux of water vapor. 10 wt% perfluorovinyl ether and 0.5 wt% initiator azobisisobutyronitrile are added and reacted at 80°C for 8 h to give the fiber membrane sensitivity and selectivity to specific gases (such as poisons containing phosphorus and sulfur functional groups); d, Cross-linking of polymer double-layer network A second layer of a cross-linked network with self-healing function is added to the fluorine-containing resin skeleton network. The membrane material soaked in step c is taken out at low temperature and immersed in a monomer solution of 5 wt% N, N-dimethylacrylamide (DMAA) monomer, initiator potassium persulfate (KPS) and accelerator N, N, N', N'-tetramethylethylenediamine (TMEDA) to complete solution replacement. After initiating the polymerization reaction at room temperature or under light or heat stimulation, a double-cross-linked self-healing polymer network is obtained to prepare a selectively permeable membrane material.
[0012] The present invention also discloses a selectively permeable protective clothing material, including the selectively permeable protective clothing material prepared by the method.
[0013] The invention also discloses an application of the selectively permeable protective clothing material in the preparation of protective clothing.
[0014] Compared with the prior art, the present invention has the following beneficial effects: The present invention designs a selectively permeable protective clothing material and its preparation method and application. It utilizes a polymer material with intrinsic flexibility, introduces inorganic / organic functional components with gas sensitivity and their nanochannels, and performs composite optimization on the micro-nano scale structure by regulating the active groups in the nanochannel. By combining the intrinsically flexible polymer material and a specific fiberization process, a gas-sensitive thin film material with low hardness, high flexibility and low modulus is obtained, thereby realizing the Wiener structure design and controllable preparation of intelligent response thin film materials. In order to further improve the response deformation sensitivity, the type, distribution density and other parameters of the active groups inside the channel are regulated to realize adaptive adjustment of the molecular transport rate in different environments, realize effective protection against toxic and harmful gaseous substances, improve the wearing comfort of protective clothing, significantly improve the wearing experience of protective clothing, and take into account protective performance.
[0015] By self-sensing polar toxic and hazardous gases, this invention effectively increases water vapor permeability while simultaneously preventing harmful gases from penetrating, achieving selective permeability protection. While strictly ensuring protection against toxic and hazardous gases, it significantly improves the breathability and comfort of protective clothing. This design, based on a gas-responsive sensitive film, achieves selective permeability protection and enhanced comfort, a first of its kind.
[0016] The invention achieves intelligent response to environmental changes and adaptive regulation of molecular transport rates. The introduction of a double-layer network structure, particularly oxime-urethane self-healing materials, ensures that the material can quickly restore airtightness after deformation, thereby improving the reliability and service life of the protective suit. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 Schematic diagram showing the preparation principle of selective permeable membrane. DETAILED DESCRIPTION
[0018] The specific embodiments of the present invention are described in detail below. Example
[0019] A method for preparing a selectively permeable protective clothing material, such as Figure 1 As shown, the following steps are included: a. Preparation of spinning solution Polyvinylidene fluoride (PVDF) was dissolved in dimethylformamide (DMF), wherein the weight average molecular weight of the polyvinylidene fluoride was 1.5×10 5 , adding polyethylene glycol and chain extender propylene glycol to prepare a 20wt% fluorocarbon polymer spinning solution precursor; b. Electrospinning The prepared spinning solution precursor is temperature controlled to 160~230℃ and electrospun to obtain fluorine-containing fiber membrane. c. Regulation of active groups inside gas molecule channels The fluorine-containing fiber membrane prepared in step b was immersed in an alcohol solution containing kaolin, and 10 wt % perfluorovinyl ether and 0.5 wt % azobisisobutyronitrile were added, and the mixture was reacted at 80 °C for 8 h; d, Cross-linking of polymer double-layer network The membrane material soaked in step c is taken out at low temperature and soaked in a monomer solution of 5 wt % N, N-dimethylacrylamide (DMAA) monomer, potassium persulfate and N, N, N', N'-tetramethylethylenediamine (TMEDA) to complete solution replacement to obtain a selective permeable membrane material.
[0020] The selective permeation membrane prepared was compared with the commercial Nafion membrane in data selective permeation. The comparison results are as follows:
[0021] As can be seen from the table above, the selectivity of the selective permeable membrane of this embodiment case for H2O / DMMP is 1.73, and the selectivity for H2O / 2-CEES is 8.47, and both selectivities are better than those of commercial Nafion membranes.
[0022] The scope of protection claimed by the present invention is not limited to the above specific embodiments. For those skilled in the art, the present invention may have various variations and modifications. Any modifications, improvements and equivalent substitutions made within the concept and principle of the present invention should be included in the scope of protection of the present invention.
Claims
1. A method for preparing a selectively permeable protective clothing material, characterized by: The following steps are involved: a. Preparation of spinning solution A fluorocarbon polymer material is dissolved in a polar organic solvent, wherein the weight average molecular weight of the fluorocarbon polymer material is 1.5×10 5 , adding 2 wt % polyethylene glycol and 0.5 wt % chain extender, stirring for 30 min to prepare a 20 wt % fluorocarbon polymer spinning solution precursor; b. Electrospinning The prepared spinning solution precursor was controlled to a temperature of 160-230°C, a spinning voltage of 20 KV, and a spinning distance of 15 cm for electrospinning to produce a fluorine-containing fiber membrane. c. Regulation of active groups inside gas molecule channels The fluorine-containing fiber membrane prepared in step b was immersed in an alcohol solution containing kaolin, and 10 wt % perfluorovinyl ether and 0.5 wt % initiator were added, and the reaction was carried out at 80 ° C for 8 h; d, Polymer double-layer network cross-linking The membrane material soaked in step c was taken out at low temperature and soaked in 5 wt % N, N-dimethylacrylamide monomer, initiator and accelerator to complete solution replacement to obtain a selective permeable membrane material.
2. The method for preparing a selectively permeable protective clothing material according to claim 1, characterized in that: In step a, the chain extender is any one of an alicyclic alcohol chain extender, an aromatic alcohol chain extender, and a diamine chain extender.
3. The method for preparing a selectively permeable protective clothing material according to claim 1, characterized in that: In step a, the fluorocarbon polymer material is any one of polyvinylidene fluoride and polyvinylidene fluoride-trifluoroethylene copolymer, the polar organic solvent is any one of acetone and dimethylformamide, and the chain extender is propylene glycol.
4. The method for preparing a selectively permeable protective clothing material according to claim 1, wherein: In step c, the initiator is azobisisobutyronitrile.
5. The method for preparing a selectively permeable protective clothing material according to claim 1, characterized in that: In step d, the initiator is potassium persulfate and the accelerator is a monomer solution of N, N, N', N'-tetramethylethylenediamine.
6. A selectively permeable protective clothing material prepared according to the method according to any one of claims 1 to 5.
7. Use of the selectively permeable protective clothing material according to claim 6 in the preparation of protective clothing.