Sponge material containing nano-copper and preparation method

Abstract

The invention discloses a sponge material containing nano-copper and a preparation method of the sponge material, and the sponge material is prepared from the following components in parts by mass: 15 to 25 parts of p-tert-octylphenol, 25 to 35 parts of polyether, 10 to 20 parts of polyether polyol, 15 to 20 parts of toluene diisocyanate, 1 to 5 parts of modified polyether polyol, 1 to 1.5 parts of water, 0.2 to 0.8 part of silicone oil, 0.02 to 0.08 part of triethylene diamine solution, 0.05 to 0.1 part of stannous octoate and 0.5 to 1.5 parts of nano-copper. The nano copper is nano copper with the particle size of 3 to 100 nm or a mixture of nano copper with the particle size of 3 to 50 nm and nano copper with the particle size of 50 to 100 By precisely regulating and controlling the adding mode and process parameters of the nano-copper, collaborative optimization of the antibacterial performance, the mechanical performance and the thermal stability of the sponge material is achieved, and the problem that the function and the basic performance of traditional functional sponge cannot be achieved at the same time is solved.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and relates to a sponge foaming process, specifically to a sponge material containing nano-copper and its preparation method. Background Technology

[0002] Due to its lightweight, porous, and highly elastic properties, sponge materials are widely used in household goods, medical dressings, and industrial sealing. With the expansion of application scenarios, the demand for functional modification of sponges is becoming increasingly urgent; for example, imparting antibacterial and long-lasting stability properties has become a key focus of industry research and development.

[0003] CN108440737B discloses a sponge containing negative ions and its foaming method. This method involves adding tourmaline powder and rare earth elements (mass ratio 4-5:5-6) to the sponge raw material, utilizing the released negative ions to achieve air purification and mild antibacterial functions. The ideal chemical formula of the core component of the negative ion generator (tourmaline powder) is NaMg3Al6(BO3)3Si6O. 18 (OH)4 has the following two-dimensional structure:

[0004] (Note: Tourmaline releases negative ions through ion exchange in its crystal structure, achieving its function through physical processes.) However, the negative ion sponge has the following technical defects: (1) poor functional sustainability and obvious performance decay: the negative ion sponge relies on the release of negative ions to achieve the modification effect, but the negative ion emission components are easy to adsorb environmental dust and impurities. Long-term use will lead to a decrease in ionization efficiency and a significant decrease in negative ion concentration, making it impossible to maintain stable efficacy; (2) narrow antibacterial range and low efficiency: negative ions can only play a weak inhibitory role on some microorganisms through neutralization. The effect on pathogenic bacteria with thick cell walls, such as Gram-negative bacteria, is limited, and there is no direct bactericidal effect; (3) single function and no additional performance gain: the negative ion sponge only focuses on the function related to the release of negative ions and does not improve the basic properties of the sponge itself, such as mechanical properties and thermal stability.

[0005] Therefore, in order to solve the above-mentioned technical pain points, it is urgent to develop a new type of sponge material that combines high-efficiency antibacterial properties, long-term functional stability, and excellent basic performance.

[0006] Copper nanoparticles (particle size 1~1000nm) are nanomaterials with excellent physicochemical properties. Their chemical composition is Cu, and they not only have a large specific surface area and high chemical activity, but also... 2+ It can achieve efficient sterilization by disrupting the cell membrane structure of microorganisms, and at the same time, it can form a stable interface bond with the polymer matrix, providing an ideal modified carrier for the functional upgrading and performance enhancement of sponge materials, and becoming a key direction for breaking through the existing technical bottlenecks. Summary of the Invention

[0007] In order to solve the technical problems of poor function persistence, low antibacterial efficiency and insufficient basic performance of existing negative ion sponge, the application provides a sponge material containing nano copper and a preparation method. Through precise regulation of the adding mode and process parameters of nano copper, the application realizes the synergistic optimization of the antibacterial performance, mechanical property and thermal stability of the sponge material, and expands the application scenarios of the sponge material.

[0008] The purpose of the application is realized by the following technical solutions: A sponge material containing nano copper, consisting of the following components in parts by mass: p-tert-octylphenol (C 14 H 22 O) 15-25 parts, polyether 25-35 parts, polyether polyol 10-20 parts, toluene diisocyanate (C9H6N2O2) 15-20 parts, modified polyether polyol 1-5 parts, water 1-1.5 parts, silicone oil 0.2-0.8 parts, 33% triethylene diamine solution 0.02-0.08 parts, stannous octoate 0.05-0.1 parts, and nano copper 1-1.5 parts. The nano copper is 3-100 nm nano copper or a mixture of 3-50 nm nano copper and 50-100 nm nano copper. For fine pore sponge with a pore size of 60 ppi or more, 3-100 nm nano copper is used. For macroporous sponge with a pore size of less than 60 ppi, a mixture of 3-50 nm nano copper and 50-100 nm nano copper is used. The mass ratio of 3-50 nm nano copper to 50-100 nm nano copper is 4-5:5-6. The two-dimensional structure of the nano copper is as follows:

[0009] (Note: it is a simplified two-dimensional unit cell structure of nano copper particles. The actual structure is face-centered cubic packing. Cu atoms are combined by metal bonds. Surface active sites are easy to release Cu 2+ ).

[0010] A preparation method of the above-mentioned sponge material containing nano copper, comprising the following steps: Step 1, soaking and decomposing: The nano copper is added to the polyether, and soaked at a temperature of 23-25 DEG C for 10 minutes to 6 hours to obtain a mixture A; Step 2, mixing and forming: Step 2-1, p-tert-octylphenol, polyether polyol and modified polyether polyol are added to the mixture A to obtain a mixture B; Step 2-2, the well-mixed mixture B is slowly poured into a foaming barrel and stirred; Steps 2-3: When stirring for 1-2 minutes, add water, silicone oil, triethylenediamine solution, and stannous octoate. Turn off the stirring and allow air to escape. After completion, add toluene diisocyanate and stir. Steps 2-4: After mixing, quickly pour the mixture into the foaming box within 3-5 seconds.

[0011] The modification mechanism of this invention is as follows: ① Antibacterial mechanism: Nano copper (Cu) slow-release Cu 2+ ① It disrupts the integrity of bacterial cell membranes, induces the generation of reactive oxygen species (ROS), oxidizes bacterial nucleic acids and proteins, and achieves broad-spectrum sterilization; ② Interface enhancement mechanism: The high specific surface area and surface activity of nano-copper form a stable bond with the sponge matrix (polyether polyol-TDI crosslinking system) through coordination, filling microscopic defects; ③ Catalytic stabilization mechanism: Nano-copper inhibits the oxidative degradation of the matrix, delays aging, and achieves dual stability of function and structure.

[0012] Unlike the single mechanism of "physical release-indirect action" in negative ion sponges, this invention overcomes the technical limitations of negative ion sponges that "rely solely on physical release" through a multi-synergistic mechanism of "chemical sterilization + interface enhancement + catalytic stabilization." By leveraging the chemical interaction between nano-copper and the sponge matrix, it achieves a technological leap in "enhanced functionality, comprehensive performance, and sustained efficacy." Compared to existing technologies, this invention has the following advantages: (1) Broad-spectrum and highly effective antibacterial (Table 1): Nano copper has a direct killing effect on Gram-positive / negative bacteria such as Staphylococcus aureus and Escherichia coli (Table 1). 2+ The slow-release effect can create a long-lasting antibacterial environment, solving the problems of narrow antibacterial range, low efficiency, and easy bacterial growth in negative ion sponges; (2) Long-lasting and stable efficacy: Nano-copper is chemically bonded to the sponge matrix, Cu 2+ The controlled release rate avoids the drawback of negative ions easily decaying, and the efficacy does not decrease with long-term use; (3) Synergistic improvement of basic performance (Table 1): As an inorganic reinforcing phase, nano-copper can be uniformly dispersed in the pores of the sponge and the matrix, reducing stress concentration inside the matrix, improving the sponge's compression resilience, tear strength and thermal stability, and breaking through the limitation of negative ion sponge having only a single function. (4) Biosafety compatibility: The bactericidal concentration of nano copper is far below the toxic threshold to human cells, and Cu is an essential trace element for the human body. It has excellent biocompatibility and no byproducts such as ozone that may be generated by negative ion sponges. (5) Broad market prospects: The nano copper sponge of the present invention can be widely used in medical dressings (antibacterial and anti-infection), food preservation packaging (antibacterial and anti-corrosion), maternal and infant products (safe and antibacterial), sofas and mattresses (antibacterial and anti-mite), industrial sealing materials (wear-resistant and anti-aging), purification and filtration, etc., solving the limitation that negative ion sponges are only applicable to ordinary civilian scenarios, and has a broader market prospect.

[0013] In summary, this invention achieves synergistic optimization of "antibacterial efficiency, mechanical properties, and thermal stability" by precisely controlling the dispersion concentration and binding mode of nano-copper: ① It breaks through the technical bottleneck of easy aggregation of traditional nanomaterials, achieving an antibacterial rate of over 99% with low addition amount (0.5~1.5 parts), which is far superior to the antibacterial effect of negative ion sponges; ② For the first time, the antibacterial properties of nano-copper are combined with the structural modification of sponges, solving the problem of "incompatibility between function and basic performance" in traditional functional sponges; ③ The experimental data in Table 1 confirm that the nano-copper sponge prepared by this invention has a longer efficacy duration and better overall performance than negative ion sponges, and its application scenarios can be expanded from ordinary civilian use to fields with higher requirements for material performance, such as medical dressings and food preservation, demonstrating significant technological progress.

[0014] Table 1 Attached Figure Description

[0015] Figure 1 A visual schematic diagram of the microstructure of the combination of nano-copper and sponge (polyurethane) matrix. Detailed Implementation

[0016] The technical solution of the present invention will be further described below with reference to the accompanying drawings, but it is not limited thereto. Any modifications or equivalent substitutions to the technical solution of the present invention that do not depart from the spirit and scope of the technical solution of the present invention should be covered within the protection scope of the present invention.

[0017] Example 1 This embodiment provides a nano-copper sponge, which is composed of the following components: 20 kg of p-tert-octylphenol, 30 kg of polyether, 15 kg of polyether polyol (Y-1030), 18 kg of TDI (toluene diisocyanate), 3 kg of modified polyether polyol (Y-1900), 1.3 kg of water, 0.5 kg of silicone oil (5810), 0.05 kg of triethylenediamine solution (A33), 0.08 kg of stannous octoate (T-9), and 1.2 kg of a mixture of 3-50 nm and 50-100 nm nano-copper, with a mass ratio of 4:6. The specific preparation steps are as follows: Step 1, Soaking and Decomposition: Step 1-1: Add 1.2 kg of nano copper to 20 kg of polyether and soak for 6 hours at 23°C. During the soaking process, stir with a high-speed mixer every 2 hours. The first stirring speed is 5000 r / min and the stirring time is 5 minutes. The second stirring speed is 2000 r / min and the stirring time is 2 minutes. The last stirring is done by hand for 2 minutes. Steps 1-2: Add 10 kg of polyether and continue stirring for 3 minutes to allow it to blend and complete the soaking process. At this point, the nano-copper has fully fused, resulting in mixture A.

[0018] Step 2, Mixing and Molding: Step 2-1: Add 20 kg of p-tert-octylphenol, 15 kg of Y-1030, and 3 kg of Y-1900 to mixture A to obtain mixture B; Step 2-2: Slowly pour the well-blended mixture B into the foaming tank and stir it at a speed of 60 r / min or 133 r / min. Steps 2-3: When stirring for 2 minutes, add 1.3 kg of water, 0.5 kg of silicone oil, 0.05 kg of 33% triethylenediamine solution, and 0.08 kg of stannous octoate. Turn off the stirring and allow it to purge air for 30 seconds. After that, add 18 kg of toluene diisocyanate and stir for 30 seconds at a speed of 100 r / s. Steps 2-4: After stirring, quickly pour the mixture into the foaming box within 3 seconds to complete the chain growth, foaming, cross-linking, and curing reactions.

[0019] In this embodiment, the polyether polyol fragment (simplified): HO—(CH2CH2O) n —H, TDI (toluene diisocyanate) molecular formula: C9H6N2O2, the chemical reaction structure of the combination of nano-copper and sponge matrix (polyether polyol-TDI crosslinking system) is as follows: Step 1: Formation of the polyurethane backbone O=C=N—C6H4—N=C=O + HO—(CH2CH2O) n —H → HO—(CH2CH2O) n —O—CO—NH—C6H4—NH—CO—N=C=O Step 2: Cu² + Coordination with the main chain [—O—CO—NH—C6H4—NH—CO—O—(CH2CH2O) n —] m +Cu 2+ →[—O—CO—NH→Cu 2+←NH—CO—O—(CH2CH2O) n —] m Cu in the middle 2+ It is stably dispersed between the two main chains through coordination, so it will not be easily lost (ensuring long-lasting efficacy) and can continuously exert antibacterial effects. At the same time, it fills the microscopic gaps between the main chains and improves the stability of the sponge structure.

[0020] The above chemical reaction structure shows that, unlike the physical dispersion of tourmaline powder in negative ion sponges (which is prone to detachment and reduced effectiveness), nano-copper, through Cu... 2+ Coordination with polymer chains achieves "chemical anchoring," ensuring both antibacterial activity (Cu) 2+ (Slow-release) also solves the industry pain points of nanomaterials being prone to aggregation and loss.

[0021] Figure 1 This visually demonstrates the bonding and interaction between nano-copper ions and sponge polymer chains. In the image: the yellow porous sponge-like substrate is the sponge matrix (polyurethane polymer chain segments), and the colored chain-like structures are the polyurethane polymer backbone constituting the sponge (labeled "sponge polymer lines"), forming the core of the sponge's skeleton. The orange Cu... 2+ This is the active form of nano-copper in the system, which is "anchored" to the N, O, and other atomic sites of the polyurethane polymer chain through coordination (dashed lines / chemical bond connections in the figure), corresponding to "Cu" in the previous chemical formula. 2+ The reaction principle is "coordination and binding with polymer chains." Through... Figure 1 It can be seen that nano-copper is not simply physically mixed in the sponge, but rather forms a chemical bond with the sponge's polymer chains, thus achieving Cu... 2+ The stable and sustained release (exerting antibacterial effects) and the enhancement of sponge structural stability by filling the gaps between polymer chains directly demonstrate the core technology of "stable combination of nano-copper and sponge matrix" in this invention.

[0022] Example 2: The difference between this embodiment and Embodiment 1 is that the nano-copper sponge is composed of the following components: 15 kg of p-tert-octylphenol, 25 kg of polyether, 10 kg of polyether polyol (Y-1030), 15 kg of TDI (toluene diisocyanate), 1 kg of modified polyether polyol (Y-1900), 1 kg of water, 0.2 kg of silicone oil (5810), 0.03 kg of triethylenediamine solution (A33), 0.05 kg of stannous octoate (T-9), and 1 kg of a mixture of 3-50 nm nano-copper and 50-100 nm nano-copper, with a mass ratio of 5:5.

[0023] Example 3: The difference between this embodiment and Embodiment 1 is that the nano-copper sponge is composed of the following components: 25 kg of p-tert-octylphenol, 35 kg of polyether, 20 kg of polyether polyol (Y-1030), 20 kg of TDI (toluene diisocyanate), 5 kg of modified polyether polyol (Y-1900), 1.5 kg of water, 0.8 kg of silicone oil (5810), 0.08 kg of triethylenediamine solution (A33), 0.1 kg of stannous octoate (T-9), and 1.5 kg of a mixture of 3-50 nm nano-copper and 50-100 nm nano-copper, with a mass ratio of 6:4.

[0024] Example 4: The difference between this embodiment and Embodiment 1 is that the nano-copper sponge is composed of the following components: p-tert-octylphenol: 25kg, polyether: 35kg, polyether polyol (Y-1030): 20kg, TDI (toluene diisocyanate): 20kg, modified polyether polyol (Y-1900): 5kg, water: 1.5kg, silicone oil (5810): 0.8kg, triethylenediamine solution (A33) 0.08kg, stannous octoate (T-9) 0.1kg, 3~50nm nano-copper: 1.2kg, and the soaking time is 10 minutes.

Claims

1. A sponge material containing nano-copper, characterized in that... The sponge material is composed of the following components by mass parts: 15-25 parts of p-tert-octylphenol, 25-35 parts of polyether, 10-20 parts of polyether polyol, 15-20 parts of toluene diisocyanate, 1-5 parts of modified polyether polyol, 1-1.5 parts of water, 0.2-0.8 parts of silicone oil, 0.02-0.08 parts of triethylenediamine solution, 0.05-0.1 parts of stannous octoate, and 0.5-1.5 parts of nano-copper.

2. The sponge material containing nano-copper according to claim 1, characterized in that... The nano-copper is 3~100nm nano-copper or a mixture of 3~50nm nano-copper and 50~100nm nano-copper.

3. The sponge material containing nano-copper according to claim 2, characterized in that... The mass ratio of the 3-50nm copper nanoparticles to the 50-100nm copper nanoparticles is 4-5:5-6.

4. The sponge material containing nano-copper according to claim 1, characterized in that... The mass concentration of the triethylenediamine solution is 33%.

5. The sponge material containing nano-copper according to claim 1, characterized in that... The sponge material is composed of the following components: 20 kg of p-tert-octylphenol, 30 kg of polyether, 15 kg of polyether polyol, 18 kg of toluene diisocyanate, 3 kg of modified polyether polyol, 1.3 kg of water, 0.5 kg of silicone oil, 0.05 kg of triethylenediamine solution, 0.08 kg of stannous octoate, and 1.2 kg of a mixture of 3-50 nm and 50-100 nm copper nanoparticles, with a mass ratio of 4:

6.

6. The sponge material containing nano-copper according to claim 1, characterized in that... The sponge material is composed of the following components: p-tert-octylphenol: 15 kg, polyether: 25 kg, polyether polyol: 10 kg, toluene diisocyanate: 15 kg, modified polyether polyol: 1 kg, water: 1 kg, silicone oil: 0.2 kg, triethylenediamine solution: 0.03 kg, stannous octoate: 0.05 kg, and a mixture of 3-50 nm and 50-100 nm copper nanoparticles: 1 kg, with the mass ratio of 3-50 nm and 50-100 nm copper nanoparticles being 5:

5.

7. The sponge material containing nano-copper according to claim 1, characterized in that... The sponge material is composed of the following components: p-tert-octylphenol: 25kg, polyether: 35kg, polyether polyol: 20kg, toluene diisocyanate: 20kg, modified polyether polyol: 5kg, water: 1.5kg, silicone oil: 0.8kg, triethylenediamine solution: 0.08kg, stannous octoate: 0.1kg, and a mixture of 3-50nm and 50-100nm copper nanoparticles: 1.5kg, with a mass ratio of 6:

4.

8. The sponge material containing nano-copper according to claim 1, characterized in that... The sponge material is composed of the following components: p-tert-octylphenol: 25kg, polyether: 35kg, polyether polyol: 20kg, toluene diisocyanate: 20kg, modified polyether polyol: 5kg, water: 1.5kg, silicone oil: 0.8kg, triethylenediamine solution: 0.08kg, stannous octoate: 0.1kg, and 3~50nm nano copper: 1.2kg.

9. A method for preparing a sponge material containing nano-copper as described in any one of claims 1-8, characterized in that... The method includes the following steps: Step 1, Soaking and Decomposition: Nano-copper is added to polyether and soaked at a temperature of 23~25℃ for 10 minutes to 6 hours to obtain mixture A; Step 2, Mixing and Molding: Step 2-1: Add p-tert-octylphenol, polyether polyol and modified polyether polyol to mixture A to obtain mixture B; Step 2-2: Slowly pour the well-blended mixture B into the foaming bucket and stir. Steps 2-3: When stirring for 1-2 minutes, add water, silicone oil, triethylenediamine solution, and stannous octoate. Turn off the stirring and allow air to escape. After completion, add toluene diisocyanate and stir. Steps 2-4: After mixing, quickly pour the mixture into the foaming box within 3-5 seconds.

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