CN111218039A - Antibacterial natural rubber and preparation method and application thereof - Google Patents
Antibacterial natural rubber and preparation method and application thereof Download PDFInfo
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- CN111218039A CN111218039A CN202010222628.1A CN202010222628A CN111218039A CN 111218039 A CN111218039 A CN 111218039A CN 202010222628 A CN202010222628 A CN 202010222628A CN 111218039 A CN111218039 A CN 111218039A
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- natural rubber
- hydrotalcite
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- antibacterial
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The invention provides an antibacterial natural rubber and a preparation method and application thereof, and belongs to the technical field of rubber materials.
Description
Technical Field
The invention relates to the technical field of rubber materials, and particularly relates to antibacterial natural rubber as well as a preparation method and application thereof.
Background
Natural Rubber (NR) as an elastomer has the characteristics of high elasticity, high strength, high definite elongation, wear resistance, tear resistance and the like, and is widely applied to various industries. Daily necessities of people such as nipples, condoms and medical and sanitary articles such as medical rubber gloves, patient ureters, blood transfusion bags and the like not only require the material to have good service performance, but also require the material to be environment-friendly and sanitary and have a certain antibacterial function. In the prior art, titanium dioxide and nano silver are generally utilized to endow rubber products with an antibacterial function, but the problems of low mechanical property and high heat generation property exist.
Disclosure of Invention
The invention aims to provide antibacterial natural rubber as well as a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an antibacterial natural rubber which comprises the following preparation raw materials in parts by weight:
the dry rubber accounts for 100 parts of natural rubber latex;
1-10 parts of hydrotalcite;
0.2-3 parts of silver nitrate;
β -0.1-3 parts of cyclodextrin;
and 0.2-2 parts of milky epoxidized natural rubber in terms of dry rubber.
Preferably, the solid content of the natural rubber latex is 10-25%.
Preferably, the average particle size of the hydrotalcite is 0.5-1.2 mm.
Preferably, the epoxidation degree of the milky epoxidized natural rubber is 10-40, and the solid content is 15-25%.
The invention provides a preparation method of the antibacterial natural rubber in the technical scheme, which comprises the following steps:
mixing hydrotalcite, silver nitrate and water, and then carrying out first modification treatment to obtain a silver-loaded hydrotalcite feed liquid;
mixing the silver-loaded hydrotalcite feed liquid with β -cyclodextrin, and then carrying out second modification treatment to obtain β -cyclodextrin modified silver-loaded hydrotalcite feed liquid;
and mixing the β -cyclodextrin modified silver-loaded hydrotalcite feed liquid, the milky epoxidized natural rubber and the natural rubber latex, and then sequentially performing coagulation treatment and drying to obtain the antibacterial natural rubber.
Preferably, the hydrotalcite and the silver nitrate are mixed with water in a manner that the hydrotalcite is mixed with a silver nitrate aqueous solution; the mass concentration of the silver nitrate water solution is 5-10%.
Preferably, the temperature of the first modification treatment is 30-50 ℃, and the time is 0.5-2 h.
Preferably, the temperature of the second modification treatment is 60-80 ℃, and the time is 1-6 h.
Preferably, the coagulation treatment mode is formic acid coagulation or acetic acid coagulation; the drying temperature is 50-70 ℃, and the drying time is 20-48 h.
The invention provides application of the antibacterial natural rubber in the technical scheme or the antibacterial natural rubber prepared by the preparation method in the technical scheme in medical latex products or sports rubber products.
The invention provides an antibacterial natural rubber which comprises, by mass, 100 parts of natural rubber latex based on dry rubber, 1-10 parts of hydrotalcite, 0.2-3 parts of silver nitrate, 0.1-3 parts of β -cyclodextrin and 0.2-2 parts of emulsion epoxidized natural rubber based on dry rubber, wherein silver ions in the silver nitrate can be inserted into an intercalation layer of the hydrotalcite, the hydrotalcite is used as a carrier to load the silver ions, β -cyclodextrin contains a large number of hydroxyl groups, and the hydroxyl groups can chemically react with hydroxyl groups on the surface of the hydrotalcite, so that modification of the hydrotalcite is realized, the dispersibility of the hydrotalcite in the finally obtained antibacterial natural rubber is favorably improved, epoxy groups in the epoxidized natural rubber latex can react with the hydroxyl groups on the surface of the hydrotalcite, the dispersibility of the hydrotalcite in the natural rubber latex is favorably improved, the dispersibility of the hydrotalcite in the finally obtained antibacterial natural rubber is further improved, and the antibacterial natural rubber has good mechanical properties and low heat generation properties while having good antibacterial properties.
In addition, the method provided by the invention is simple to operate, low in production cost and easy for large-scale production.
Detailed Description
The invention provides an antibacterial natural rubber which comprises the following preparation raw materials in parts by weight:
the dry rubber accounts for 100 parts of natural rubber latex;
1-10 parts of hydrotalcite;
0.2-3 parts of silver nitrate;
β -0.1-3 parts of cyclodextrin;
and 0.2-2 parts of milky epoxidized natural rubber in terms of dry rubber.
The raw materials for preparing the antibacterial natural rubber are not particularly limited, and commercially available products known to those skilled in the art can be used.
The raw materials for preparing the antibacterial natural rubber comprise, by mass, 100 parts of natural rubber latex in terms of dry rubber. In the present invention, the solid content of the natural rubber latex is preferably 10 to 25%, and more preferably 23 to 27%. The invention adopts the natural rubber latex as the base material, compared with the natural rubber, the invention is easier to realize the uniform mixing with each component (such as hydrotalcite), and is beneficial to ensuring that the finally obtained antibacterial natural rubber has better antibacterial effect, mechanical property and lower heat generation property.
On the basis of the mass parts of the natural rubber latex in dry rubber, the raw materials for preparing the antibacterial natural rubber comprise 1-10 parts of hydrotalcite, preferably 3-7 parts of hydrotalcite, and more preferably 4-6 parts of hydrotalcite. In the present invention, the average particle size of the hydrotalcite is preferably 0.5 to 1.2 mm. The invention uses hydrotalcite to load silver ion.
Based on the mass parts of the natural rubber latex in dry rubber, the raw materials for preparing the antibacterial natural rubber comprise 0.2-3 parts of silver nitrate, preferably 0.5-2 parts of silver nitrate, and more preferably 1-1.5 parts of silver nitrate. In the invention, silver ions in the silver nitrate can be inserted into an intercalation layer in hydrotalcite, and the hydrotalcite is used as a carrier to load the silver ions, so that the finally obtained antibacterial natural rubber has a good antibacterial effect.
The preparation raw materials of the antibacterial natural rubber provided by the invention comprise, based on the mass parts of the natural rubber latex counted by dry rubber, 0.1-3 parts of β -cyclodextrin, preferably 0.5-2.5 parts of the antibacterial natural rubber, and more preferably 1-2 parts of the antibacterial natural rubber, wherein β -cyclodextrin contains a large amount of hydroxyl groups, and the hydroxyl groups can form hydrogen bonds with hydroxyl groups on the surface of hydrotalcite, so that modification of the hydrotalcite is realized, the dispersibility of the hydrotalcite in the finally obtained antibacterial natural rubber is favorably improved, and the antibacterial natural rubber has good antibacterial property and good mechanical property and low heat generation property.
Based on the mass parts of the natural rubber latex in terms of dry rubber, the raw materials for preparing the antibacterial natural rubber comprise 0.2-2 parts of milky epoxidized natural rubber in terms of dry rubber, preferably 0.5-1.5 parts, and more preferably 0.7-1.2 parts. In the invention, the epoxidation degree of the epoxidized natural rubber latex is preferably 10-40, and more preferably 15-30; the solid content is preferably 15-25%, and more preferably 17-22%. In the invention, the epoxy group in the epoxidized natural rubber latex can react with the hydroxyl group on the surface of the hydrotalcite, so that the dispersibility of the hydrotalcite in the natural rubber latex is improved, the dispersibility of the hydrotalcite in the finally obtained antibacterial natural rubber is further improved, and the antibacterial natural rubber has good antibacterial property and also has good mechanical property and low heat generation property.
The invention provides a preparation method of the antibacterial natural rubber in the technical scheme, which comprises the following steps:
mixing hydrotalcite, silver nitrate and water, and then carrying out first modification treatment to obtain a silver-loaded hydrotalcite feed liquid;
mixing the silver-loaded hydrotalcite feed liquid with β -cyclodextrin, and then carrying out second modification treatment to obtain β -cyclodextrin modified silver-loaded hydrotalcite feed liquid;
and mixing the β -cyclodextrin modified silver-loaded hydrotalcite feed liquid, the milky epoxidized natural rubber and the natural rubber latex, and then sequentially performing coagulation treatment and drying to obtain the antibacterial natural rubber.
In the invention, the process of preparing the antibacterial natural rubber is preferably carried out under the condition of stirring, and the stirring speed is preferably 200-400 r/min, and more preferably 300-350 r/min.
According to the invention, hydrotalcite, silver nitrate and water are mixed and then subjected to first modification treatment to obtain the silver-loaded hydrotalcite feed liquid. In the present invention, the hydrotalcite and silver nitrate are preferably mixed with water by mixing the hydrotalcite with an aqueous solution of silver nitrate; the mass concentration of the silver nitrate water solution is preferably 5-10%. In the invention, the temperature of the first modification treatment is preferably 30-50 ℃, and the time is preferably 0.5-2 h. In the invention, in the first modification process, silver ions in silver nitrate are inserted into the intercalation layer of hydrotalcite, i.e. the hydrotalcite is used as a carrier to load the silver ions, so that the finally obtained antibacterial natural rubber has a good antibacterial effect.
In the invention, after the first modification treatment is finished, the obtained system is a silver-loaded hydrotalcite feed liquid, and can be directly mixed with β -cyclodextrin without post-treatment to carry out second modification treatment to obtain β -cyclodextrin modified silver-loaded hydrotalcite feed liquid, wherein the temperature of the second modification treatment is preferably 60-80 ℃, and the time is preferably 1-6 h.
According to the invention, after the second modification treatment is completed, β -cyclodextrin modified silver-loaded hydrotalcite feed liquid can be directly mixed with milky epoxidized natural rubber and natural rubber latex without post-treatment, and then the milky epoxidized natural rubber and the natural rubber latex are sequentially subjected to solidification treatment and drying to obtain the antibacterial natural rubber, the β -cyclodextrin modified silver-loaded hydrotalcite feed liquid and the milky epoxidized natural rubber are preferably stirred and mixed for 10-30 min, then the obtained system and the natural rubber latex are stirred and mixed for 5-20 min, and finally the solidification treatment and the drying are sequentially performed to obtain the antibacterial natural rubber.
The invention provides application of the antibacterial natural rubber in the technical scheme or the antibacterial natural rubber prepared by the preparation method in the technical scheme in medical latex products or sports rubber products. In the present invention, the medical latex product may be a medical glove or catheter; the sports rubber product can be specifically a rubber ball or a yoga mat.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing 1 part of hydrotalcite (with the average particle size of 0.5mm and silver nitrate aqueous solution (with the mass concentration of 5% and the amount of silver nitrate of 0.2 part)) by mass at the stirring speed of 200r/min, and stirring at 30 ℃ for 0.5h to obtain silver-loaded hydrotalcite feed liquid;
mixing the silver-loaded hydrotalcite feed liquid with 0.1 part of β -cyclodextrin, stirring for 0.5h at 60 ℃, then mixing with 0.2 part of milky epoxidized natural rubber (the epoxidation degree is 10, and the solid content is 15%) in terms of dry rubber, stirring for 10min, then adding 100 parts of natural rubber latex (the solid content is 10%) in terms of dry rubber, stirring for 5min, performing formic acid solidification treatment for 1h, and drying for 48h by hot air at 50 ℃ to obtain the antibacterial natural rubber.
Example 2
According to the mass parts, 10 parts of hydrotalcite (with the average particle size of 1.2mm) and silver nitrate aqueous solution (with the mass concentration of 10% and the amount of silver nitrate of 3 parts) are mixed under the condition that the stirring speed is 400r/min, and the mixture is stirred for 2 hours at the temperature of 50 ℃ to obtain silver-loaded hydrotalcite feed liquid;
mixing the silver-loaded hydrotalcite feed liquid with 3 parts of β -cyclodextrin, stirring for 6 hours at 70 ℃, then mixing with 2 parts of milky epoxidized natural rubber (the epoxidation degree is 40 and the solid content is 25%) in terms of dry rubber, stirring for 30 minutes, then adding 100 parts of natural rubber latex (the solid content is 25%) in terms of dry rubber, stirring for 20 minutes, then carrying out formic acid coagulation treatment for 6 hours, and drying with hot air at 70 ℃ for 20 hours to obtain the antibacterial natural rubber.
Example 3
According to the mass parts, 5 parts of hydrotalcite (with the average particle size of 1mm) and silver nitrate aqueous solution (with the mass concentration of 8% and the amount of silver nitrate of 2 parts) are mixed under the condition that the stirring speed is 300r/min, and the mixture is stirred for 1h at the temperature of 40 ℃ to obtain silver-loaded hydrotalcite feed liquid;
mixing the silver-loaded hydrotalcite feed liquid with 2 parts of β -cyclodextrin, stirring for 3 hours at 70 ℃, then mixing with 1 part of milky epoxidized natural rubber (the epoxidation degree is 30 and the solid content is 20%) in terms of dry rubber, stirring for 20 minutes, then adding 100 parts of natural rubber latex (the solid content is 20%) in terms of dry rubber, stirring for 10 minutes, then carrying out formic acid coagulation treatment for 4 hours, and drying with hot air at 60 ℃ for 30 hours to obtain the antibacterial natural rubber.
Example 4
According to the mass parts, under the condition that the stirring rotating speed is 350r/min, 4 parts of hydrotalcite (the average particle size is 0.8mm) and silver nitrate aqueous solution (the mass concentration is 7 percent, and the using amount of silver nitrate is 0.25 part) are mixed, and the mixture is stirred for 1 hour at the temperature of 30 ℃ to obtain silver-loaded hydrotalcite feed liquid;
mixing the silver-loaded hydrotalcite feed liquid with 1.5 parts of β -cyclodextrin, stirring for 2 hours at 60 ℃, then mixing with 1.6 parts of milky epoxidized natural rubber (the epoxidation degree is 25, and the solid content is 18%) in terms of dry rubber, stirring for 25 minutes, then adding 100 parts of natural rubber latex (the solid content is 18%) in terms of dry rubber, stirring for 15 minutes, then carrying out formic acid solidification treatment for 3 hours, and drying with hot air at 65 ℃ for 28 hours to obtain the antibacterial natural rubber.
Example 5
Mixing 6 parts of hydrotalcite (with the average particle size of 0.8mm) and silver nitrate aqueous solution (with the mass concentration of 6% and the amount of silver nitrate of 1 part) according to the mass parts under the condition that the stirring speed is 250r/min, and stirring for 55min at the temperature of 30 ℃ to obtain silver-loaded hydrotalcite feed liquid;
mixing the silver-loaded hydrotalcite feed liquid with 1.2 parts of β -cyclodextrin, stirring for 5 hours at 65 ℃, then mixing with 1.1 parts of milky epoxidized natural rubber (the epoxidation degree is 35, and the solid content is 21%) in terms of dry rubber, stirring for 25 minutes, then adding 100 parts of natural rubber latex (the solid content is 19%) in terms of dry rubber, stirring for 20 minutes, then carrying out formic acid solidification treatment for 5 hours, and drying for 45 hours by hot air at 55 ℃ to obtain the antibacterial natural rubber.
Comparative example 1
And (3) performing formic acid coagulation treatment on the natural rubber latex with the solid content of 20% for 5 hours, and drying the natural rubber latex with hot air at the temperature of 60 ℃ for 40 hours to obtain the natural rubber.
The natural rubbers obtained in examples 1 to 5 and comparative example 1 and the vulcanization processing aid (3.5 parts of sulfur, 0.5 part of accelerator M, 6 parts of zinc oxide and 0.5 part of stearic acid) were kneaded in an open mill, and after standing for 12 hours, an optimum vulcanization time T90 was measured, and then vulcanization was performed on a flat plate vulcanizing machine (vulcanization condition 145 ℃ c.. times.t 90), and the mechanical properties and heat buildup properties of the rubber materials prepared in examples 1 to 5 and comparative example 1 were measured in accordance with GB/T528-2009 (measurement of tensile stress strain properties of a vulcanized rubber or a thermoplastic rubber), GB/T1687-1993 (measurement of temperature rise and fatigue resistance of a vulcanized rubber in a flexing test, part 2 compression flexing test), and the test results are shown in table 1.
The antibacterial properties of the natural rubbers obtained in examples 1 to 5 and comparative example 1 were measured according to "method for testing antibacterial properties of QBT2591-2003 antibacterial plastic", and the test results are shown in Table 1.
TABLE 1 results of antibacterial property test of natural rubbers prepared in examples 1 to 5 and comparative example 1
As can be seen from Table 1, the natural rubber provided by the invention has good mechanical properties, low heat generation performance and excellent antibacterial effect which is more than 95%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The antibacterial natural rubber is characterized by comprising the following preparation raw materials in parts by weight:
the dry rubber accounts for 100 parts of natural rubber latex;
1-10 parts of hydrotalcite;
0.2-3 parts of silver nitrate;
β -0.1-3 parts of cyclodextrin;
and 0.2-2 parts of milky epoxidized natural rubber in terms of dry rubber.
2. The antibacterial natural rubber according to claim 1, wherein the natural rubber latex has a solid content of 10 to 25%.
3. The antibacterial natural rubber according to claim 1, wherein the hydrotalcite has an average particle diameter of 0.5 to 1.2 mm.
4. The antibacterial natural rubber according to claim 1, wherein the epoxidized milky natural rubber has an epoxidation degree of 10 to 40 and a solid content of 15 to 25%.
5. A method for preparing the antibacterial natural rubber according to any one of claims 1 to 4, which comprises the following steps:
mixing hydrotalcite, silver nitrate and water, and then carrying out first modification treatment to obtain a silver-loaded hydrotalcite feed liquid;
mixing the silver-loaded hydrotalcite feed liquid with β -cyclodextrin, and then carrying out second modification treatment to obtain β -cyclodextrin modified silver-loaded hydrotalcite feed liquid;
and mixing the β -cyclodextrin modified silver-loaded hydrotalcite feed liquid, the milky epoxidized natural rubber and the natural rubber latex, and then sequentially performing coagulation treatment and drying to obtain the antibacterial natural rubber.
6. The method according to claim 5, wherein the hydrotalcite, silver nitrate and water are mixed by mixing the hydrotalcite with an aqueous solution of silver nitrate; the mass concentration of the silver nitrate water solution is 5-10%.
7. The preparation method according to claim 5 or 6, wherein the temperature of the first modification treatment is 30-50 ℃ and the time is 0.5-2 h.
8. The preparation method according to claim 5, wherein the temperature of the second modification treatment is 60 to 80 ℃ and the time is 1 to 6 hours.
9. The production method according to claim 5, wherein the coagulation treatment is performed by formic acid coagulation or acetic acid coagulation; the drying temperature is 50-70 ℃, and the drying time is 20-48 h.
10. Use of the antibacterial natural rubber according to any one of claims 1 to 4 or the antibacterial natural rubber obtained by the production method according to any one of claims 5 to 9 in a medical latex product or a sports rubber product.
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| JPH119681A (en) * | 1997-06-23 | 1999-01-19 | Toyobo Co Ltd | Antimicrobial urethral catheterization catheter |
| US20170296554A1 (en) * | 2013-05-02 | 2017-10-19 | Medical Technology Research Inc | Antimicrobial compositions and methods of making the same |
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