A rare earth metal-based functional material and its application in preparing medical rubber material

Abstract

The present invention provides a rare earth metal-based functional material and its application in the preparation of medical rubber materials. The rare earth metal-based functional material is prepared by coprecipitation of rare earth chloride and L-lactic acid in an alkaline environment, and the mass ratio of L-lactic acid to rare earth chloride is 1: (0.5-2). The rare earth metal-based functional material of the present invention is assembled into a sheet structure unit through charge action, and the rare earth metal-based functional material with a sheet structure is added to the rubber raw material, thereby improving the anti-puncture ability of the rubber material, and can also play an efficient antibacterial role, which not only protects medical staff but also effectively plays a positive role in the health of patients.

Description

Technical Field

[0001] The invention belongs to the field of medical devices, and in particular relates to a rare earth metal-based functional material and an application thereof in preparing a medical rubber material. Background Art

[0002] Medical rubber materials are indispensable protective equipment in the medical field. Their development has gone through a century. The materials have evolved from natural rubber to various synthetic materials, and the designs have evolved from single functions to multifunctional composites. This not only demonstrates the progress of science and technology, but also reflects the evolution of the concept of medical protection. In early medical practice, medical staff often had direct contact with patients and lacked effective protection, resulting in frequent cross-infection. With the establishment of germ theory and the introduction of aseptic techniques, people began to pay attention to hand hygiene and protection.

[0003] In today's medical field, the importance of protective equipment is becoming increasingly prominent, especially in the fields of medicine, laboratories and public health. Medical rubber gloves, as a basic protective equipment, are not only limited to physical isolation, but also include anti-pollution and antibacterial.

[0004] Rare earth elements have similar electronic configurations, most of which are +3 valent cations with large ionic radius and high charge. These characteristics give them unique application advantages in materials and biology. Rare earth elements have excellent optical, electrical, magnetic and other properties, and have strong complexing ability. They are easy to be compounded with polymers to prepare materials with excellent properties. They are currently widely used in chemical industry, agriculture, and many other fields, and have broad development prospects.

[0005] Rare earth elements, with their unique physical and chemical properties, currently play a vital role in the rubber industry. They are widely used in the modification of various rubber products, significantly improving the comprehensive performance of the materials. For example, in tire manufacturing, rare earth modified rubber introduces nano-scale rare earth powder, which not only enhances the cross-linking density of the rubber molecular chain, but also improves wear resistance and aging resistance. This modification technology greatly extends the service life of the tire while reducing maintenance costs. In addition, rare earth modified rubber also exhibits excellent high temperature resistance, low temperature resistance and wear resistance in the fields of aviation, aerospace and cables, greatly expanding its application prospects in high-end fields.

[0006] In recent years, medical personnel and medical institutions have paid more and more attention to the prevention of needlestick injuries, and related research has gradually increased. In the actual nursing operation process, it is sometimes difficult for medical personnel to concentrate on prevention awareness or fully follow the prevention regulations of needlestick injuries. When the layer of protection of prevention awareness and response regulations fails, the only protective equipment that can protect medical personnel is medical gloves and other protective equipment. Therefore, the development of an effective anti-puncture medical rubber material will greatly reduce the incidence of needlestick injuries among medical personnel, effectively protect medical personnel from blood-borne diseases, and vigorously promote the healthy development of my country's medical industry. The emergence of rare earth anti-puncture rubber materials can change this current phenomenon.

[0007] Therefore, the application of rare earth rubber materials in the field of medical devices has shown great potential. This study aims to invent and prepare a needle-proof medical rubber material with good antibacterial and puncture-proof capabilities. This makes them have broad application prospects in the medical field, especially in cases where rubber materials need to be worn for a long time for surgery or other medical operations, which can provide safer and more reliable protection. Summary of the invention

[0008] In view of this, the present invention aims to overcome the defects in the prior art and proposes a rare earth metal-based functional material and its application in the preparation of medical rubber materials.

[0009] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0010] In a first aspect, the present invention provides a rare earth metal-based functional material prepared by co-precipitation of rare earth chloride and L-lactic acid in an alkaline environment, wherein the mass ratio of L-lactic acid to rare earth chloride is 1:(0.5-2).

[0011] Preferably, the rare earth chloride is one or a mixture of two or more of lanthanum chloride heptahydrate, cerium chloride heptahydrate, gadolinium chloride heptahydrate, and yttrium chloride heptahydrate.

[0012] In a second aspect, the present invention also provides a method for preparing the above-mentioned rare earth metal-based functional material, comprising the following steps:

[0013] (1) dissolving rare earth chloride, L-lactic acid and ammonium bicarbonate in deionized water to obtain a rare earth chloride solution, an L-lactic acid solution and an ammonium bicarbonate solution, respectively, and adding the L-lactic acid solution dropwise to the rare earth chloride solution to obtain a mixed solution;

[0014] (2) When the pH value of the mixed solution reaches 3.0, start to add ammonium bicarbonate solution to the mixed solution, stop adding when the pH value reaches 5, and filter out the precipitate in the mixed solution;

[0015] (3) Recovering the filtered mother liquor, adding L-lactic acid solution dropwise thereto, and repeating step (2) until precipitation is complete;

[0016] (4) Collect all the precipitated products, wash them with water for multiple times, and filter them to obtain filter cakes. After drying and calcining, rare earth metal-based functional materials are obtained. The calcination temperature is 600°C-1200°C.

[0017] Preferably, the concentration of rare earth chloride in the mixed solution is 0.4-2.0 mol / L.

[0018] In a third aspect, the present invention also provides a medical rubber material prepared using the above rare earth metal-based functional material.

[0019] In a fourth aspect, the present invention further provides a method for preparing the above-mentioned medical rubber material, comprising the following steps:

[0020] The nano rare earth suspension slurry is mixed with natural rubber latex and poured into a latex pool, a mold coated with a coagulant is hung and immersed in the glue, and after keeping for 1-2 hours, the mold is dried to obtain a medical rubber material. The nano rare earth suspension slurry is prepared by mixing rare earth metal-based functional materials and deionized water and grinding.

[0021] Preferably, the particle size of the rare earth metal-based functional material after sand grinding is 100-200 nm.

[0022] Preferably, the solid content of the nano rare earth suspension slurry is 25%-35%.

[0023] Preferably, the added mass of the rare earth metal-based functional material in the natural rubber latex is 1%-2%.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] (1) The present invention uses L-lactic acid and rare earth chloride to prepare a supramolecular precursor, introduces an organic acid monomer into the middle of a rare earth monomer, and polymerizes with the rare earth chloride to obtain a rare earth complex, and subjecting the intermediate compound to heat treatment (i.e., high-temperature calcination at a temperature of 600°C-1200°C), peeling and polycondensation while the solvent evaporates, thereby obtaining a rare earth metal-based functional material with a lamellar structure.

[0026] (2) Rare earth ions have rich electronic energy levels and strong complexing ability. In the application of medical rubber materials, rare earth metal-based functional materials are assembled into lamellar structure units through charge action. The rare earth metal-based functional materials with lamellar structure are incorporated into rubber raw materials, thereby improving the puncture resistance of rubber materials.

[0027] (3) The medical rubber material prepared by the present invention, by introducing nano rare earth metal-based functional materials, can not only improve the tensile mechanical properties of the rubber material and the puncture resistance of the material, but also have a strong inhibitory and killing effect on common Escherichia coli. Therefore, during the operation, the medical rubber material not only effectively prevents injuries caused by sharp instruments, but also has a highly effective antibacterial effect. While protecting medical staff, it also effectively plays a positive role in the health of patients. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 SEM scanning electron microscope for rare earth metal-based functional materials;

[0029] Figure 2 To test the puncture force / thickness performance of rare earth antibacterial gloves against needle puncture;

[0030] Figure 3 This is the antibacterial zone test of rare earth anti-stab rubber. DETAILED DESCRIPTION

[0031] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.

[0032] Ammonium bicarbonate, L-lactic acid, lanthanum chloride heptahydrate, cerium chloride heptahydrate, gadolinium chloride heptahydrate, yttrium chloride heptahydrate, sodium chloride, tryptone, yeast extract, and agar were purchased from Aladdin Chemical Co., Ltd.

[0033] All chemicals were used without further treatment, and deionized water was prepared in the laboratory.

[0034] Escherichia coli E. coli Purchased from Guangdong Huankai Microbiology Technology Co., Ltd.

[0035] The invention provides a rare earth metal-based functional material, which is prepared by a coprecipitation method of rare earth chloride and L-lactic acid in an alkaline environment, wherein the mass ratio of L-lactic acid to rare earth chloride is 1:(0.5-2).

[0036] Preferably, the rare earth chloride is one or a mixture of two or more of lanthanum chloride heptahydrate, cerium chloride heptahydrate, gadolinium chloride heptahydrate, and yttrium chloride heptahydrate.

[0037] The present invention also provides a method for preparing the above rare earth metal-based functional material, comprising the following steps:

[0038] Rare earth chloride, L-lactic acid and ammonium bicarbonate are respectively dissolved in deionized water to obtain a rare earth chloride solution, an L-lactic acid solution and an ammonium bicarbonate solution, and the L-lactic acid solution is added dropwise to the rare earth chloride solution to obtain a mixed solution; preferably, the concentration of the rare earth chloride in the mixed solution is 0.4-2.0 mol / L.

[0039] When the pH value of the mixed solution reaches 3.0, start to add ammonium bicarbonate solution to the mixed solution, and use pH test paper to monitor the pH value continuously. When the pH reaches 4-5, precipitation begins to appear in the solution. With the continued addition of ammonium bicarbonate solution, the pH value gradually reaches 5, and the addition is stopped. The precipitate in the solution is filtered out by suction to obtain a lactic acid rare earth compound, and the mother liquor is recovered. The pH value is tested to be 5 at this time, and L-lactic acid solution is continued to be added dropwise. When the pH value reaches 3.0, start to continuously add ammonium bicarbonate solution to the heptahydrate rare earth chloride solution, and continuously monitor the pH value. When the pH value reaches 4, precipitation begins to appear in the solution again, but with the continuous addition of ammonium bicarbonate solution, the pH value will gradually increase again. This step must strictly control the reaction environment. Once the pH value is greater than 6, the obtained product will be converted into a rare earth hydroxide, so it needs to be repeated many times until the precipitation is complete.

[0040] The obtained precipitated product is washed with water for multiple times and filtered to obtain a filter cake, and the modified rare earth compound that can significantly improve the puncture force is screened out. After drying and high-temperature calcination, excess organic matter and impurities are removed, and finally rare earth metal-based functional materials are obtained.

[0041] The present invention will be described in detail below with reference to the embodiments.

[0042] Example 1

[0043] (1) Rare earth metal-based functional materials NHLO

[0044] Weigh 500 g of lanthanum chloride heptahydrate and 600 g of L-lactic acid and dissolve them in 500 mL of deionized water respectively, then weigh 1000 g of ammonium bicarbonate and dissolve them in 1000 mL of deionized water. After the lanthanum chloride is completely dissolved, use a separatory funnel to slowly and continuously add the L-lactic acid solution to the lanthanum chloride. When the pH value reaches 3.0 using a pH test paper, start to continuously add the ammonium bicarbonate solution to the lanthanum chloride. As the ammonium bicarbonate solution continues to be added, the pH gradually exceeds 5 and then the addition is stopped. The precipitate in the solution is filtered out by suction to obtain lanthanum lactate, and the mother liquor is recovered. The pH value at this time is about 5, and the L-lactic acid solution is continued to be added, and the above steps are repeated until the precipitation is complete.

[0045] The precipitated material was collected, concentrated to a dry sample in an oven at 110°C, ground into powder in a mortar, and then calcined in a muffle furnace at 1200°C to obtain the rare earth metal-based functional material NHLO with a nanosheet structure.

[0046] SEM scanning test of rare earth metal-based functional material NHLO (hereinafter referred to as NHLO) was performed. Figure 1 As shown in the SEM scan of NHLO, it can be seen that NHLO is a stacked structure with interlaced layers. The surface of the layers is smooth and the thickness is about 200nm-nm, but the plane size can reach hundreds of nanometers to several microns, providing a large surface area, which is conducive to absorbing impact energy and reducing the kinetic energy of the penetrating object.

[0047] (2) Preparation of NHLO nano-slurry by wet sand grinding

[0048] The obtained NHLO was added to deionized water at a solid content of 35%, and then wet sand milled using a NETZSCH MINIFER sand mill with a single machine circulation process. The main machine speed was 3100 rpm, and the sand milling was performed for 6-10 h to obtain a nano rare earth suspension slurry with a particle distribution of 100-200 nm.

[0049] (3) Preparation of needle puncture-proof rare earth antibacterial gloves. The specific operations are as follows:

[0050] First, the 35% solid content nano rare earth suspension slurry prepared in the previous step is mixed with natural rubber latex, and the rare earth slurry is accurately weighed according to the NHLO addition amount of 2%. Then the mixed solution is poured into the latex pool, and then the glove mold with a coagulant on the surface is hung and immersed in the glue liquid, and the dipping liquid is ensured to be completely and evenly attached to the glove mold by continuous movement. After keeping it for 1 hour, the glove mold after dipping is dried at 80℃ to evaporate the water inside the glove and make the glove dry. Then the hardened and dried glove mold is cleaned to remove impurities, and after further drying, the latex gloves on the mold are removed to obtain rare earth anti-acupuncture antibacterial gloves.

[0051] Example 2

[0052] The difference from Example 1 is that the rare earth chloride is cerium chloride heptahydrate, the added amount of cerium chloride heptahydrate is 300 g, and the rare earth metal-based functional material NHCO is obtained.

[0053] Example 3

[0054] The difference from Example 1 is that the rare earth chloride is gadolinium chloride heptahydrate, and the added amount of gadolinium chloride heptahydrate is 600 g, thereby obtaining a rare earth metal-based functional material NHGO.

[0055] Example 4

[0056] The difference from Example 1 is that the rare earth chloride is yttrium chloride heptahydrate, and the added amount of yttrium chloride heptahydrate is 1200 g, thereby obtaining a rare earth metal-based functional material NHYO.

[0057] Comparative Example 1

[0058] The difference from Example 1 is that L-lactic acid is replaced by oleic acid, and the added amount of oleic acid is 500 mL, thereby obtaining a rare earth metal-based functional material OA-NHLO.

[0059] Comparative Example 2

[0060] The difference from Example 1 is that L-lactic acid is replaced by n-butyric acid, and the amount of n-butyric acid added is 500 mL, thereby obtaining a rare earth metal-based functional material OT-NHLO.

[0061] Comparative Example 3

[0062] The difference from Example 1 is that the pH of the reaction environment during precipitation is controlled to be greater than 6, thereby obtaining the rare earth metal-based functional material NHLO-1.

[0063] Comparative Example 4

[0064] The difference from Example 1 is that the amount of lanthanum chloride heptahydrate added is adjusted to 250 g, and the rare earth metal-based functional material NHLO-2 is obtained.

[0065] Comparative Example 5

[0066] The difference from Example 1 is that the addition amount of lanthanum chloride heptahydrate is adjusted to 1300 g, and the rare earth metal-based functional material NHLO-3 is obtained.

[0067] Test Example 1: Puncture force / thickness index test of needle puncture-proof rare earth antibacterial gloves

[0068] Cut the gloves to be tested into specimens with a diameter of 100 mm, and then clamp them in the upper and lower fixtures of the universal mechanical testing machine respectively. Install the puncture needle and specimen fixture, adjust the equipment parameters to set the speed for puncturing the specimen, conduct three sets of parallel experimental tests, and simultaneously test the thickness of the experimental rubber samples. Calculate the puncture force / thickness results, and take the average value as the puncture resistance of the gloves. The results are as follows: Figure 2 shown.

[0069] Figure 2 It can be seen that NHLO rubber has the highest puncture force / thickness index. Compared with ordinary rubber, the puncture force / thickness index can be increased from 16.22 N / mm to 22.82 N / mm, indicating that NHLO rubber has stronger puncture resistance and can enhance the anti-puncture effect of rubber when added to rubber gloves.

[0070] Test Example 2 Antibacterial Zone Test of Rare Earth Anti-Stab Rubber

[0071] The specific steps for preparing the culture medium are as follows:

[0072] Liquid LB medium: Add 10 g NaCl, 10 g peptone and 5 g yeast extract to 1 L pure water, stir well and divide into 4 conical flasks, sterilize in a high pressure steam sterilizer at 121°C for 25 min and set aside.

[0073] Solid LB medium: add 10 g NaCl, 10 g peptone, 5 g yeast extract and 15 g agar powder to 1 L pure water, sterilize in a high pressure steam autoclave at 121°C for 25 min, then pour into a disposable culture dish while hot, wait for it to cool and solidify, seal with sealing film and place in a 4°C refrigerator for later use.

[0074] Escherichia coli ( E. coli ) were recovered and passaged as follows:

[0075] Will buy E. coli After the freeze-dried powder and the resuscitation solution were mixed evenly, they were transferred to the LB culture medium prepared in advance and incubated in a constant temperature shaker for 6 h. Then, 500 μL of the second generation cultured cells were taken out in the clean bench. E. coli Then take 500 μL of 50% glycerol, mix well in a 2 mL EP tube, and store in a -80℃ refrigerator. E. coli The breeding method of the strain is the same as that of the second generation.

[0076] The specific operation of the antibacterial zone test of rare earth anti-stab rubber is as follows:

[0077] First, freeze the third generation E. coli Transfer to the prepared LB culture medium and incubate in a constant temperature shaker for 5 hours. Dilute the E. coli culture solution 104 times on the clean bench, then aspirate 80 μL to evenly spread on the plate, cut a 1 cm × 1 cm rubber sample and spread it in the middle of the medium after the plate is spread. Then, place it in a constant temperature incubator and incubate it for 12 hours. Observe and measure the radius of the inhibition zone on the next day.

[0078] according to Figure 3 The comparison of the inhibition zones in the medium shows that the LB medium with NHLO rubber samples has a positive effect on E. coli It has a significant inhibitory effect, and the radius of the inhibition zone can reach 4mm, while the blank group is full of E. coli colonies, which can prove that NHLO rare earth anti-stab rubber is E. coli Has strong antibacterial properties.

[0079] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A rare earth metal-based functional material, characterized in that: It is prepared by co-precipitation of rare earth chloride and L-lactic acid, wherein the mass ratio of L-lactic acid to rare earth chloride is 1:(0.5-2); The rare earth chloride includes one or a mixture of two or more of lanthanum chloride heptahydrate, cerium chloride heptahydrate, gadolinium chloride heptahydrate, and yttrium chloride heptahydrate; The method for preparing the rare earth metal-based functional material comprises the following steps: (1) dissolving rare earth chloride, L-lactic acid and ammonium bicarbonate in deionized water to obtain a rare earth chloride solution, an L-lactic acid solution and an ammonium bicarbonate solution, respectively, and adding the L-lactic acid solution dropwise to the rare earth chloride solution to obtain a mixed solution; (2) When the pH value of the mixed solution reaches 3.0, start to add ammonium bicarbonate solution to the mixed solution, stop adding when the pH value reaches 5, and filter out the precipitate in the mixed solution; (3) Recovering the filtered mother liquor, adding L-lactic acid solution dropwise thereto, and repeating step (2) until precipitation is complete; (4) All the precipitated products are collected, washed with water for multiple times, and filtered to obtain a filter cake, which is then dried and calcined to obtain a rare earth metal-based functional material at a calcination temperature of 600°C-1200°C.

2. The rare earth metal-based functional material according to claim 1, characterized in that: The rare earth chloride is lanthanum chloride heptahydrate.

3. The rare earth metal-based functional material according to claim 1, characterized in that: The concentration of rare earth chloride in the mixed solution is 0.4-2.0 mol / L.

4. A medical rubber material prepared using the rare earth metal-based functional material according to any one of claims 1 to 3.

5. The method for preparing the medical rubber material according to claim 4, characterized in that: The steps include: The nano rare earth suspension slurry is mixed with natural rubber latex and poured into a latex pool, a mold coated with a coagulant is hung and immersed in the glue, and after keeping for 1-2 hours, the mold is dried to obtain a medical rubber material. The nano rare earth suspension slurry is prepared by mixing rare earth metal-based functional materials and deionized water and grinding.

6. The method for preparing the medical rubber material according to claim 5, characterized in that: The particle size of the rare earth metal-based functional material after sand grinding is 100-200 nm.

7. The method for preparing the medical rubber material according to claim 5, characterized in that: The solid content of the nano rare earth suspension slurry is 25%-35%.

8. The method for preparing the medical rubber material according to claim 5, characterized in that: The added mass of the rare earth metal-based functional material in the natural rubber latex is 1%-2%.

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