A rare earth functional material containing cerium and its application in preparing rubber products

Abstract

The present invention provides a cerium-containing rare earth functional material and its application in the preparation of rubber products, comprising the following steps: step 1 is to mix anhydrous ethanol, diammonium cyanide and hydrochloric acid solution uniformly, add modified rare earth nitrate, deionized water and tetraethyl silicate thereto, react under heating conditions, and obtain an intermediate system after the reaction is completed; step 2 is to dry, calcine and grind the intermediate system, then add sodium hydroxide solution thereto, react under heating conditions, and filter, wash and dry after the reaction is completed to obtain the cerium-containing rare earth functional material. The cerium-containing rare earth functional material described in the present invention is a nano-scale material. When used as an additive to prepare rubber products, it not only increases the puncture resistance of the rubber, but also gives the rubber excellent antibacterial ability.

Description

Technical Field

[0001] The invention belongs to the field of rubber products, and in particular relates to a cerium-containing rare earth functional material and application of the material in preparing rubber products. Background Art

[0002] In the modern medical field, the complexity of surgical operations and the strict requirements for a sterile environment make hand protection for medical staff particularly important. Although traditional medical rubber products can provide protection to a certain extent, their puncture resistance is often insufficient when facing sharp medical devices (such as scalpels and suture needles), increasing the risk of infection for medical staff. During medical operations, medical staff often need to directly contact various medical devices and patients' body fluids, which places extremely high demands on the protective performance of rubber products. On the one hand, rubber products need to have good puncture resistance to prevent accidental punctures by sharp medical devices, leading to the spread of pathogens; on the other hand, rubber products must also maintain a high degree of sterility and chemical stability to ensure the safety of the surgical process and the health of the patient. However, traditional medical rubber products often have deficiencies in these aspects and are difficult to meet the needs of modern medical operations.

[0003] As a class of metal elements with unique physical and chemical properties, rare earth elements have shown broad application prospects in the field of materials science. Rare earth elements can significantly enhance the strength, hardness, wear resistance and corrosion resistance of materials. These characteristics make rare earth materials have unique advantages in the preparation of high-performance protective equipment, especially in the manufacture of puncture-proof rubber products. The addition of rare earth elements can significantly improve the protective performance of rubber products and meet the special needs of protective equipment in the medical field. Rare earth puncture-proof rubber products significantly improve the puncture resistance, wear resistance and chemical stability of rubber products by incorporating rare earth elements into polymer materials. Specifically, the addition of rare earth elements can improve the crystal structure and microstructure of the material, making it more dense and tough, thereby effectively resisting the puncture of sharp objects. At the same time, rare earth compounds can also form a protective film on the surface of the material to improve the corrosion resistance and antibacterial properties of rubber products. These excellent properties make rare earth puncture-proof rubber products have broad application prospects in the medical field. In surgical operations, medical staff often need to operate sharp surgical instruments such as scalpels and suture needles. Rare earth puncture-proof rubber products can provide higher puncture-proof performance and reduce the risk of infection caused by accidental punctures for medical staff. At the same time, medical surgery has extremely high requirements for a sterile environment. Rare earth puncture-proof rubber products can effectively inhibit the growth of microorganisms such as bacteria and viruses through their excellent chemical stability and antibacterial properties, and maintain the sterile environment of the operating room, which is of great significance for reducing surgical infection rates and improving patient recovery rates. Summary of the invention

[0004] In view of this, the present invention aims to overcome the defects in the prior art and proposes a cerium-containing rare earth functional material and its application in the preparation of rubber products.

[0005] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0006] A method for preparing a cerium-containing rare earth functional material comprises the following steps:

[0007] Step 1 is to mix anhydrous ethanol, diammonium cyanide and hydrochloric acid solution uniformly, add modified rare earth nitrate, deionized water and tetraethyl silicate thereto, react under heating conditions, and obtain an intermediate system after the reaction is completed;

[0008] Step 2 is to dry, calcine and grind the intermediate system, then add sodium hydroxide solution thereto, react under heating conditions, and after the reaction is completed, filter, wash and dry to obtain the cerium-containing rare earth functional material.

[0009] Furthermore, the solid-to-liquid ratio of the anhydrous ethanol, diammonium cyanide, hydrochloric acid solution, modified rare earth nitrate, deionized water, tetraethyl silicate in step 1 and the sodium hydroxide solution in step 2 is 3-5 mL: 1-2 g: 2-3 mL: 2-3 g: 2-3 mL: 1-2 mL: 15-25 mL.

[0010] Furthermore, the concentration of the hydrochloric acid solution in step 1 is 5.0-7.0 mol / L; the concentration of the sodium hydroxide solution in step 2 is 4.0-6.0 mol / L.

[0011] Furthermore, the temperature of the heating step in step 1 is 70-90°C, and the time is 0.5-1.0 hour; the temperature of the drying step before the calcination step in step 2 is 70-90°C, and the time is 18-26 hours; the temperature of the calcination step in step 2 is 550-650°C, and the time is 2.5-3.5 hours; the temperature of the heating step in step 2 is 70-90°C, and the time is 18-26 hours; the temperature of the drying step after the filtration step in step 2 is 70-90°C, and the time is 18-26 hours.

[0012] Furthermore, the preparation method of the modified rare earth nitrate in step 1 comprises the following steps: mixing cellulose ether and rare earth nitrate evenly and dissolving them in deionized water, transferring the mixed system into a hydrothermal reactor for reaction after magnetic stirring, and drying, grinding and sieving after the reaction to obtain the modified rare earth nitrate.

[0013] Furthermore, the mass ratio of the cellulose ether to the rare earth nitrate is 1-2:4-6; the rare earth nitrate is at least one of cerium nitrate hexahydrate, cerium chloride hexahydrate or cerium sulfate tetrahydrate.

[0014] Furthermore, the temperature of the magnetic stirring step is 65-75°C and the time is 30-60 minutes; the temperature of the hydrothermal reaction kettle is 140-180°C and the time is 10-15 hours.

[0015] Furthermore, the temperature of the drying step is 70-90° C. and the time is 18-26 hours; the mesh size of the sieve in the sieving step is 200-300 meshes.

[0016] The invention provides a cerium-containing rare earth functional material prepared by using the preparation method.

[0017] The invention provides an application of a cerium-containing rare earth functional material in the preparation of rubber products.

[0018] Compared with the prior art, the present invention has the following advantages:

[0019] The cerium-containing rare earth functional material of the present invention is a nano-grade material. When used as an additive to prepare rubber products, it not only increases the anti-puncture performance of the rubber, but also gives the rubber excellent antibacterial ability.

[0020] The modified rare earth nitrate of the present invention is prepared by using cellulose ether. The molecular chains of the dissolved cellulose ether interact with water molecules by forming hydrogen bonds to form a network structure. This structure can increase the connection force between molecules in rubber products, thereby improving the toughness and anti-puncture performance of the material. The two form a coordination compound with cerium ions as the center and hydroxyl groups, ether groups and ester groups in the cellulose ether molecules as side chains under heating and stirring conditions. The cerium ions in the cerium nitrate are oxidizing. After combining with the cellulose ether, they undergo redox reactions with reducing functional groups (such as incompletely etherified hydroxyl groups, etc.) in the cellulose ether molecules. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is an electron microscope image of the rare earth functional material containing cerium as described in Example 1 of the present invention;

[0022] Figure 2 It is a bar graph of the puncture force of the rubber products described in Example 1 of the present invention and Comparative Examples 1-3. DETAILED DESCRIPTION

[0023] 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.

[0024] The present invention will be described in detail below with reference to the embodiments.

[0025] Example 1

[0026] A method for preparing a rubber product using a rare earth functional material containing cerium comprises the following steps:

[0027] (1) Weigh 40 g of cellulose ether and 200 g of cerium nitrate hexahydrate, add 1.0 L of deionized water and stir to dissolve, then place the above system on a magnetic stirrer, adjust the temperature to 70 ° C, and set the stirring time to 45 min. After the stirring is completed, transfer the system to a hydrothermal reactor, set the conditions: 150 ° C, 12 h. After the reaction is completed, transfer the system to an evaporating dish, and then transfer it as a whole to an oven, set the conditions: 80 ° C, 24 h. After drying, a white powder is obtained, which is transferred to a mortar, ground and passed through a 200-mesh sieve to obtain a modified rare earth nitrate;

[0028] (2) Measure 20 mL of anhydrous ethanol, 5 g of diammonium cyanide, and 10 mL of 6 mol / L hydrochloric acid solution, mix them and set aside, then add 10 g of modified rare earth nitrate, 10 mL of deionized water, and 5 mL of tetraethyl silicate, place the above reaction system in an oil bath, set the conditions: 80°C, 0.5 h, after the reaction is completed, pour each system into different polytetrafluoroethylene liners, and then transfer to an oven, set the conditions: 80°C, 800 rpm, 24 h, to obtain a gel-like solid;

[0029] (3) The solid is placed in a crucible and transferred to a muffle furnace for calcination at 580°C for 3 h. The calcined material is ground into powder and added to a polytetrafluoroethylene liner. 100 mL of 5 mol / L sodium hydroxide solution is added for desiliconization. The material is placed in an oil bath again at 80°C and 800 rpm for 24 h. The system after the reaction is filtered. The white solid obtained after filtration is repeatedly washed with deionized water and ethanol and then transferred to an oven for drying at 80°C for 24 h. The dried solid is ground into fine white powder to obtain a cerium-containing rare earth functional material.

[0030] (4) Take 5 L of natural rubber latex, add 200 mL of curing agent 8530, 150 mL of dispersant 2120, and 50 g of cerium-containing rare earth functional material, add the above materials into a mixer and heat to 120 °C, and use high-speed stirring to form a uniformly dispersed mixed liquid. The rubber product is completely immersed in the mixed liquid and kept rotating horizontally for 30 min to ensure that the mixed liquid covers the rubber product mold. Then the mold is transferred to an oven and set the conditions: 80 °C, 24 h. The dried mold is transferred to a vulcanization chamber for vulcanization treatment, and then the moisture inside the rubber product is completely evaporated by infrared treatment. Then, the surface of the rubber product is treated with deionized water and then transferred to an oven for drying again. Finally, the mold is manually demolded to obtain a rubber product.

[0031] Comparative Example 1

[0032] A method for preparing a rubber product using a rare earth functional material containing cerium comprises the following steps:

[0033] (1) Weigh 40 g of cellulose ether and 200 g of cerium nitrate hexahydrate, add 1.0 L of deionized water and stir thoroughly to dissolve, then place the above system on a magnetic stirrer, adjust the temperature to 70°C, and set the stirring time to 45 min. After the stirring is completed, transfer the system to an evaporating dish, and then transfer the whole system to an oven at 80°C for 24 h. After drying, a white powder is obtained, which is transferred to a mortar and ground and passed through a 200-mesh sieve to obtain a modified rare earth nitrate;

[0034] (2) Measure 20 mL of anhydrous ethanol, 5 g of diammonium cyanide, and 10 mL of 6 mol / L hydrochloric acid solution, mix them and set aside, then add 10 g of modified rare earth nitrate, 10 mL of deionized water, and 5 mL of tetraethyl silicate, place the above reaction system in an oil bath, set the conditions: 80°C, 0.5 h, after the reaction is completed, pour each system into different polytetrafluoroethylene liners, and then transfer to an oven, set the conditions: 80°C, 800 rpm, 24 h, to obtain a gel-like solid;

[0035] (3) The solid is placed in a crucible and transferred to a muffle furnace for calcination at 580°C for 3 h. The calcined material is ground into powder and added to a polytetrafluoroethylene liner. 100 mL of 5 mol / L sodium hydroxide solution is added for desiliconization. The material is placed in an oil bath again at 80°C and 800 rpm for 24 h. The system after the reaction is filtered. The white solid obtained after filtration is repeatedly washed with deionized water and ethanol and then transferred to an oven for drying at 80°C for 24 h. The dried solid is ground into fine white powder to obtain a cerium-containing rare earth functional material.

[0036] (4) Take 5 L of natural rubber latex, add 200 mL of curing agent 8530, 150 mL of dispersant 2120, and 50 g of cerium-containing rare earth functional material, add the above materials into a mixer and heat to 120 °C, and use high-speed stirring to form a uniformly dispersed mixed liquid. The rubber product is completely immersed in the mixed liquid and kept rotating horizontally for 30 min to ensure that the mixed liquid covers the rubber product mold. Then the mold is transferred to an oven and set the conditions: 80 °C, 24 h. The dried mold is transferred to a vulcanization chamber for vulcanization treatment, and then the moisture inside the rubber product is completely evaporated by infrared treatment. Then, the surface of the rubber product is treated with deionized water and then transferred to an oven for drying again. Finally, the mold is manually demolded to obtain a rubber product.

[0037] Comparative Example 2

[0038] A method for preparing a rubber product using a rare earth functional material containing cerium comprises the following steps:

[0039] (1) Weigh 20 g of cellulose ether and 200 g of cerium nitrate hexahydrate, add 1.0 L of deionized water and stir to dissolve, then place the above system on a magnetic stirrer, adjust the temperature to 70 ° C, and set the stirring time to 45 min. After the stirring is completed, transfer the system to a hydrothermal reactor, set the conditions: 150 ° C, 12 h. After the reaction is completed, transfer the system to an evaporating dish, and then transfer the whole system to an oven, set the conditions: 80 ° C, 24 h. After drying, a white powder is obtained, which is transferred to a mortar, ground and passed through a 200-mesh sieve to obtain a modified rare earth nitrate;

[0040] (2) Measure 20 mL of anhydrous ethanol, 5 g of diammonium cyanide, and 10 mL of 6 mol / L hydrochloric acid solution, mix them and set aside, then add 10 g of modified rare earth nitrate, 10 mL of deionized water, and 5 mL of tetraethyl silicate, place the above reaction system in an oil bath, set the conditions: 80°C, 0.5 h, after the reaction is completed, pour each system into different polytetrafluoroethylene liners, and then transfer to an oven, set the conditions: 80°C, 800 rpm, 24 h, to obtain a gel-like solid;

[0041] (3) The solid is placed in a crucible and transferred to a muffle furnace for calcination at 580°C for 3 h. The calcined material is ground into powder and added to a polytetrafluoroethylene liner. 100 mL of 5 mol / L sodium hydroxide solution is added for desiliconization. The material is placed in an oil bath again at 80°C and 800 rpm for 24 h. The system after the reaction is filtered. The white solid obtained after filtration is repeatedly washed with deionized water and ethanol and then transferred to an oven for drying at 80°C for 24 h. The dried solid is ground into fine white powder to obtain a cerium-containing rare earth functional material.

[0042] (4) Take 5 L of natural rubber latex, add 200 mL of curing agent 8530, 150 mL of dispersant 2120, and 50 g of cerium-containing rare earth functional material, add the above materials into a mixer and heat to 120 °C, and use high-speed stirring to form a uniformly dispersed mixed liquid. The rubber product is completely immersed in the mixed liquid and kept rotating horizontally for 30 min to ensure that the mixed liquid covers the rubber product mold. Then the mold is transferred to an oven and set the conditions: 80 °C, 24 h. The dried mold is transferred to a vulcanization chamber for vulcanization treatment, and then the moisture inside the rubber product is completely evaporated by infrared treatment. Then, the surface of the rubber product is treated with deionized water and then transferred to an oven for drying again. Finally, the mold is manually demolded to obtain a rubber product.

[0043] Comparative Example 3

[0044] A method for preparing a rubber product using a rare earth functional material containing cerium comprises the following steps:

[0045] (1) 20 mL of anhydrous ethanol, 5 g of diammonium cyanide, and 10 mL of 6 mol / L hydrochloric acid solution were mixed and set aside. Then, 10 g of cerium nitrate hexahydrate, 10 mL of deionized water, and 5 mL of tetraethyl silicate were added thereto. The reaction system was placed in an oil bath and the conditions were set at 80°C for 0.5 h. After the reaction was completed, each system was poured into different polytetrafluoroethylene liners, and then transferred to an oven and the conditions were set at 80°C, 800 rpm, for 24 h to obtain a gel-like solid.

[0046] (2) The solid is placed in a crucible and transferred to a muffle furnace for calcination at 580°C for 3 h. The calcined material is ground into powder and added to a polytetrafluoroethylene liner. 100 mL of 5 mol / L sodium hydroxide solution is added for desiliconization. The material is placed in an oil bath again at 80°C and 800 rpm for 24 h. The system after the reaction is filtered. The white solid obtained after filtration is repeatedly washed with deionized water and ethanol and then transferred to an oven for drying at 80°C for 24 h. The dried solid is ground into fine white powder to obtain a cerium-containing rare earth functional material.

[0047] (3) Take 5 L of natural rubber latex, add 200 mL of curing agent 8530, 150 mL of dispersant 2120, and 50 g of cerium-containing rare earth functional material, add the above materials into a mixer and heat to 120 °C, and use high-speed stirring to form a uniformly dispersed mixed liquid. The rubber product is completely immersed in the mixed liquid and kept rotating horizontally for 30 min to ensure that the mixed liquid covers the rubber product mold. Then the mold is transferred to an oven and set the conditions: 80 °C, 24 h. The dried mold is transferred to a vulcanization chamber for vulcanization treatment, and then the moisture inside the rubber product is completely evaporated by infrared treatment. Then, the surface of the rubber product is treated with deionized water and then transferred to an oven for drying again. Finally, the mold is manually demolded to obtain a rubber product.

[0048] Figure 1 This is a picture of the cerium-containing rare earth functional material prepared in Example 1 under a scanning electron microscope, and the material has a lamellar structure; Figure 2 The puncture resistance performance index of the rubber product finally prepared in Example 1 and Comparative Examples 1-3. The rubber product obtained in Example 1 has the best puncture resistance performance, with a puncture force / thickness (N / mm) of 32.61. The rubber products obtained in Comparative Examples 1-3 have the following indexes: 28.00, 27.32, and 21.50, respectively, all lower than Example 1. The modification method in Comparative Example 1 does not have a heating step, because the molecular collision frequency and speed when the cellulose ether reacts with the rare earth nitrate are insufficient, and the reaction rate is slow, so the hydrogen bonds between the molecular chains in the cellulose ether and the water molecules cannot form a dense network structure, resulting in poor puncture resistance performance of the final rubber product; in Comparative Example 2, the amount of cellulose ether added is small, and it is also unable to react fully with the rare earth nitrate, so it is unable to form a sufficiently dense network structure, resulting in a decrease in puncture resistance performance; Comparative Example 3 does not use cellulose ether for modification, so the rubber product prepared in this comparative example relies solely on the lamellar structure of the rare earth element to achieve a certain puncture resistance effect, so the effect is poor.

[0049] 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 method for preparing a cerium-containing rare earth functional material, characterized in that: The steps include: Step 1 is to mix anhydrous ethanol, diammonium cyanide and hydrochloric acid solution uniformly, add modified rare earth nitrate, deionized water and tetraethyl silicate thereto, react under heating conditions, and obtain an intermediate system after the reaction is completed; Step 2 is to dry, calcine and grind the intermediate system, then add sodium hydroxide solution thereto, react under heating conditions, and after the reaction is completed, filter, wash and dry to obtain the cerium-containing rare earth functional material; The solid-to-liquid ratio of the anhydrous ethanol, diammonium cyanide, hydrochloric acid solution, modified rare earth nitrate, deionized water, tetraethyl silicate in step 1 to the sodium hydroxide solution in step 2 is 3-5 mL: 1-2 g: 2-3 mL: 2-3 g: 2-3 mL: 1-2 mL: 15-25 mL; The preparation method of the modified rare earth nitrate in step 1 comprises the following steps: uniformly mixing cellulose ether and rare earth nitrate and dissolving them in deionized water, transferring the mixed system into a hydrothermal reactor for reaction after magnetic stirring, and drying, grinding and sieving after the reaction to obtain the modified rare earth nitrate; The mass ratio of the cellulose ether to the rare earth nitrate is 1-2:4-6; the rare earth nitrate is cerium nitrate hexahydrate; The temperature of the hydrothermal reaction kettle is 140-180° C., and the time is 10-15 hours.

2. The method for preparing the cerium-containing rare earth functional material according to claim 1, characterized in that: The concentration of the hydrochloric acid solution in step 1 is 5.0-7.0 mol / L; the concentration of the sodium hydroxide solution in step 2 is 4.0-6.0 mol / L.

3. The method for preparing the cerium-containing rare earth functional material according to claim 1, characterized in that: The temperature of the heating step in step 1 is 70-90°C, and the time is 0.5-1.0 hour; the temperature of the drying step before the calcination step in step 2 is 70-90°C, and the time is 18-26 hours; the temperature of the calcination step in step 2 is 550-650°C, and the time is 2.5-3.5 hours; the temperature of the heating step in step 2 is 70-90°C, and the time is 18-26 hours; the temperature of the drying step after the filtration step in step 2 is 70-90°C, and the time is 18-26 hours.

4. The method for preparing the cerium-containing rare earth functional material according to claim 1, characterized in that: The temperature of the magnetic stirring step is 65-75° C. and the time is 30-60 minutes.

5. The method for preparing the cerium-containing rare earth functional material according to claim 1, characterized in that: The temperature of the drying step in the preparation method of the modified rare earth nitrate is 70-90° C. and the time is 18-26 hours; the mesh number of the sieve in the screening step is 200-300 meshes.

6. A cerium-containing rare earth functional material prepared by the preparation method according to any one of claims 1 to 5.

7. Use of the cerium-containing rare earth functional material according to claim 6 in the preparation of rubber products.

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