CN108976768B - Antibacterial modifier and preparation method thereof, antibacterial modified thermoplastic elastomer and preparation method thereof - Google Patents
Antibacterial modifier and preparation method thereof, antibacterial modified thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN108976768B CN108976768B CN201810731914.3A CN201810731914A CN108976768B CN 108976768 B CN108976768 B CN 108976768B CN 201810731914 A CN201810731914 A CN 201810731914A CN 108976768 B CN108976768 B CN 108976768B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention provides an antibacterial modifier and a preparation method thereof, an antibacterial modified thermoplastic elastomer and a preparation method thereof. The antibacterial modifier provided by the invention is a polyguanylate-fatty acid salt compound formed by combining polyguanylate and fatty acid salt. The antibacterial modifier provided by the invention has good compatibility with a thermoplastic elastomer matrix, is uniformly dispersed, is not easy to precipitate, has good antibacterial property and lasting antibacterial performance, and can remarkably improve the antibacterial efficiency; in addition, the antibacterial modifier is high-temperature resistant, so that side reactions such as pyrolysis and the like can be avoided in the process of preparing the antibacterial material, and the problem of antibacterial inactivation is further avoided; moreover, the antibacterial agent has no toxic or side effect, and can be better used in the field of medical instruments. In addition, the preparation method is simple and easy to implement, has no pollution to the environment, and is easy to realize large-scale continuous production.
Description
Technical Field
The invention relates to the technical field of thermoplastic materials, and particularly relates to an antibacterial modifier and a preparation method thereof, an antibacterial modified thermoplastic elastomer and a preparation method thereof.
Background
Thermoplastic elastomers (TPE) are a class of high polymer materials that exhibit rubber elasticity at normal temperature and can be plasticized at high temperature, and have the characteristics of both rubber and Thermoplastic; the macromolecule chain forging is composed of a plastic section (namely a hard section) and a rubber section (namely an elastic soft section). Compared with rubber, TPE does not need to be vulcanized, can adopt the processing technology of injection molding or extrusion molding of thermoplastic plastics, and even can be subjected to secondary injection molding on some base materials, so that the production process is simplified, and the cost is reduced. Besides the advantages of the processing performance, the TPE also has excellent chemical, physical and biological properties, such as good oxidation resistance, wide hardness range, no toxicity and the like, makes up the defects of plastics and rubber, integrates the advantages of the plastics and the rubber, and makes the TPE become a novel high polymer material between the plastics and the rubber, which is often called third-generation rubber. Due to the advantages, the thermoplastic elastomer becomes the preferred material in the manufacturing industry of medical appliances, and is widely applied to medical packaging, liquid medicine and blood storage and infusion, various catheters, medical equipment accessories and the like.
However, when these medical devices contact with human body, bacteria are easy to adhere to the surface of the material or the device, grow and form a biofilm, which further causes bacterial infection, so that it is very important to prepare the thermoplastic elastomer material with antibacterial function.
Some antibacterial thermoplastic elastomer materials are provided in the prior art, and as disclosed in patent application No. 201510833780.2, an antibacterial polyurethane comprises 60 parts of polyurethane and 0.1-0.25 part of composite antibacterial agent; the composite antibacterial agent is prepared from the following raw materials: 40% of organic bacteriostatic agent, 35% of nano silver oxide and 25% of chitosan; the organic antibacterial agent includes: 48% of chinaberry oil, 22% of dandelion extract and 30% of dark plum extract. The patent application with application number 201610592133.1 discloses an antibacterial thermoplastic polyurethane, which comprises the following raw materials: 35-50 phr of polyol, 4-9 phr of chain extender, 35-40 phr of isocyanate, 1-5phr of antibacterial agent, 0.03-2.00 phr of catalyst and 0.01-0.10 phr of coupling agent; the antibacterial agent is a nano zirconium phosphate silver-loaded antibacterial agent. However, the antibacterial materials provided by the schemes have poor antibacterial effect and poor antibacterial durability, and in addition, the addition of the small-molecule silver-containing antibacterial agent also generates larger cytotoxicity, so that the antibacterial materials are not suitable for being applied to the field of medical appliances.
Disclosure of Invention
In view of the above, the present invention aims to provide an antibacterial modifier and a preparation method thereof, an antibacterial modified thermoplastic elastomer and a preparation method thereof. The antibacterial modifier provided by the invention can enable the thermoplastic elastomer to have excellent antibacterial property and better antibacterial durability, thereby improving the sterilization efficiency.
The invention provides an antibacterial modifier, which is a polyguanylate-fatty acid salt compound formed by combining polyguanylate and fatty acid salt.
Preferably, the polyguanidine acid salt is selected from one or more of polyguanidine hydrochloride, polyguanidine phosphate and polyguanidine gluconate;
the fatty acid salt is selected from one or more of C5-C31 fatty acid potassium and C5-C31 fatty acid sodium.
Preferably, the guanidine in the polyguanidine hydrochloride is selected from one or more of alkyl guanidine of C4-C22 and substituted alkyl guanidine of C4-C22;
the fatty acid salt is selected from one or more of C12-C18 fatty acid potassium and C12-C18 fatty acid sodium.
Preferably, the number average molecular weight of the polyguanylate is 150-3000;
the substituent of the substituted C4-C22 alkylguanidine is selected from amino, phenyl and substituted phenyl.
Preferably, the polyguanylate is selected from one or more of polyhexamethylene biguanide hydrochloride, polyhexamethylene biguanide phosphate, polyaminopropyl biguanide hydrochloride, polyaminopropyl biguanide phosphate, polyaminopropyl monoguanidine hydrochloride, polyaminopropyl monoguanidine phosphate, poly 1, 6-bis (p-chloroben) n-hexane digluconate and poly 1, 6-bis (p-chloroben) n-hexane digluconate;
the fatty acid salt is selected from one or more of sodium stearate, potassium stearate, sodium palmitate, potassium palmitate, sodium myristate, potassium myristate, sodium laurate and potassium laurate.
Preferably, the mass ratio of the polyguanylate to the fatty acid salt is 1: 0.1-2.
The invention also provides a preparation method of the antibacterial modifier, which is characterized by comprising the following steps:
mixing the aqueous polyguanylate solution with the aqueous fatty acid salt solution to form a polyguanylate-fatty acid salt complex.
Preferably, the mass percentage concentration of the polyguanylate aqueous solution is 0.1-5%;
the mass percentage concentration of the fatty acid salt water solution is 0.1-5%.
The invention also provides an antibacterial modified thermoplastic elastomer, which comprises an antibacterial modifier and a thermoplastic elastomer;
the antibacterial modifier is the antibacterial modifier in the technical scheme.
The invention also provides a preparation method of the antibacterial modified thermoplastic elastomer, which comprises the following steps:
and mixing the antibacterial modifier with the thermoplastic elastomer, and performing melt extrusion to obtain the antibacterial modified thermoplastic elastomer.
The invention provides an antibacterial modifier, which is a polyguanylate-fatty acid salt compound formed by combining polyguanylate and fatty acid salt. The antibacterial modifier provided by the invention has good compatibility with a thermoplastic elastomer matrix, is uniformly dispersed, is not easy to precipitate, has good antibacterial property and lasting antibacterial performance, and can remarkably improve the antibacterial efficiency; in addition, the antibacterial modifier is high-temperature resistant, so that side reactions such as pyrolysis and the like can be avoided in the process of preparing the antibacterial material, and the problem of antibacterial inactivation is further avoided; moreover, the antibacterial agent has no toxic or side effect, and can be better used in the field of medical instruments. In addition, the preparation method is simple and easy to implement, has no pollution to the environment, and is easy to realize large-scale continuous production.
Test results show that the antibacterial modifier provided by the invention can enable the initial antibacterial property of the thermoplastic elastomer to reach more than 95%, and the antibacterial property after being soaked for one month is still maintained at more than 95%, so that the antibacterial modifier has excellent antibacterial property and antibacterial durability.
Detailed Description
The invention provides an antibacterial modifier, which is a polyguanylate-fatty acid salt compound formed by combining polyguanylate and fatty acid salt.
The antibacterial modifier provided by the invention is a polyguanylate-fatty acid salt compound, polyguanylate and fatty acid salt in the compound are combined by electrostatic acting force, and the polyguanylate-fatty acid salt compound is used as an antibacterial agent, so that a thermoplastic elastomer has excellent antibacterial property and better antibacterial durability, and the sterilization efficiency is further improved; in addition, the antibacterial modifier is high-temperature resistant, and can avoid side reactions such as pyrolysis and the like in the process of preparing the antibacterial material, thereby avoiding the problem of antibacterial inactivation.
In the invention, the polyguanidine acid salt is preferably one or more of polyguanidine hydrochloride, polyguanidine phosphate and polyguanidine gluconate. More preferably, the guanidine in the polyguanidine hydrochloride is selected from one or more of alkyl guanidine of C4-C22 and substituted alkyl guanidine of C4-C22; wherein the guanidine in the polyguanylate is mono-or biguanide. The substituent of the substituted C4-C22 alkylguanidine is preferably amino, phenyl or substituted phenyl. More preferably, the polyguanylate has a number average molecular weight of 150 to 3000, and if the molecular weight is less than 150, a polyguanylate-fatty acid salt complex is difficult to form. The source of the polyguanylate is not particularly limited in the present invention, and it may be a general commercial product or obtained according to a preparation method well known to those skilled in the art.
In some embodiments, the polyguanylate is selected from one or more of polyhexamethylene biguanide hydrochloride, polyhexamethylene biguanide phosphate, polyaminopropyl biguanide hydrochloride, polyaminopropyl biguanide phosphate, polyaminopropyl monoguanidine hydrochloride, polyaminopropyl monoguanidine phosphate, poly 1, 6-bis (p-chlorobiguanide) n-hexane digluconate and poly 1, 6-bis (p-chlorobenzenemonoguanidine) n-hexane digluconate. In a preferred embodiment, the polyguanylate is selected from one or more of polyhexamethylene biguanide hydrochloride, polyhexamethylene monoguanidine phosphate and polyaminopropyl biguanide hydrochloride, and the three polyguanylates can further remarkably improve the antibacterial property and antibacterial durability of the thermoplastic elastomer compared with other polyguanylates.
In the invention, the fatty acid salt is preferably one or more of C5-C31 fatty acid potassium and C5-C31 fatty acid sodium; more preferably, the antibacterial thermoplastic elastomer is one or more of C12-C18 fatty acid potassium and C12-C18 fatty acid sodium, and compared with other fatty acid salts, the selected C12-C18 fatty acid salt can be better combined and mutually synergistic with polyguanylate, so that the compatibility and the combination stability with the thermoplastic elastomer matrix are improved, and the antibacterial property and the antibacterial durability of the thermoplastic elastomer are further improved. In some embodiments, the fatty acid salt is one or more of sodium stearate, potassium stearate, sodium palmitate, potassium palmitate, sodium myristate, potassium myristate, sodium laurate and potassium laurate, and the specific stearate selected from the fatty acid salts of C12-C18 has the best effect on improving the antibacterial property and antibacterial durability of the thermoplastic elastomer.
In the polyguanylate-fatty acid salt composite, the mass ratio of polyguanylate to fatty acid salt is preferably 1: 0.1-2, and more preferably 1: 0.5-1.5.
The compound formed by combining the polyguanylate and the fatty acid salt through electrostatic attraction is used as the antibacterial agent, the antibacterial agent has good compatibility with a thermoplastic elastomer matrix, is uniformly dispersed in the matrix and is difficult to separate out; in addition, compared with the antibacterial substances such as antibiotics, antibacterial peptides, halamine and the like in the prior art, the antibacterial modifier provided by the invention is high-temperature resistant, can avoid side reactions such as high-temperature decomposition and the like in the process of preparing an antibacterial material, further avoids the problem of antibacterial inactivation, and overcomes the problem that the antibacterial agent is difficult to process and prepare; moreover, the antibacterial agent provided by the invention has no toxic or side effect, and can be better used in the field of medical instruments. In addition, the preparation method is simple and easy to implement, has no pollution to the environment, and is easy to realize large-scale continuous production.
The invention also provides a preparation method of the antibacterial modifier, which comprises the following steps: mixing the aqueous polyguanylate solution with the aqueous fatty acid salt solution to form a polyguanylate-fatty acid salt complex.
The types, proportions, sources and the like of the polyguanylate in the polyguanylate aqueous solution and the fatty acid salt in the fatty acid salt aqueous solution are consistent with those in the technical scheme, and are not described in detail herein.
In the present invention, the mass percentage concentration of the polyguanylate aqueous solution is preferably 0.1% to 5%, and more preferably 0.5% to 3%. In the present invention, the concentration of the aqueous solution of a fatty acid salt is preferably 0.1% to 5%, more preferably 0.5% to 3%. Controlling the concentrations of the two solutions within the above ranges results in good water solubility of the two acid salts and successful and high yield precipitation of the polyguanylate-fatty acid salt complex upon mixing of the two solutions.
In the invention, after the aqueous solution of polyguanylate and the aqueous solution of fatty acid salt are mixed, the positively charged polyguanide substance and the negatively charged fatty acid salt are rapidly combined to form a water-insoluble polyguanylate-fatty acid salt compound through electrostatic interaction, and a compound precipitate is formed in the mixed solution.
In the invention, the mixing temperature is preferably 0-50 ℃; the mixing time is preferably 10 seconds to 10 minutes.
In the present invention, it is preferable to further perform solid-liquid separation after the mixing. The solid-liquid separation method is not particularly limited, and the polyguanylate-fatty acid salt complex precipitate in the mixed solution can be sufficiently separated, for example, solid-liquid separation by centrifugation. In the present invention, after the solid-liquid separation, it is preferable to further perform washing with water and drying, thereby obtaining a polyguanylate-fatty acid salt complex.
The invention also provides an antibacterial modified thermoplastic elastomer, which comprises an antibacterial modifier and a thermoplastic elastomer; the antibacterial modifier is the antibacterial modifier in the technical scheme.
The kind of the thermoplastic elastomer is not particularly limited in the present invention, and may be a conventional thermoplastic elastomer well known to those skilled in the art, and is preferably one or more of a styrenic thermoplastic elastomer, a polyurethane elastomer, a nylon elastomer, a polyester elastomer, and a polyolefin elastomer. The present invention has no special limitation on the specific types of each type of thermoplastic elastomer, and is a material well known to those skilled in the art, wherein, the new styrene-based thermoplastic elastomer includes but is not limited to one or more of SEBS, SBS, SEPS, SIBS; the polyurethane elastomer comprises one or more of polyether polyurethane elastomer and polyester polyurethane elastomer; the nylon elastomer comprises but is not limited to one or more of PEBAX series nylon elastomers; the polyester elastomer comprises but is not limited to one or more of TPEE polyester elastomer; the polyolefin elastomer includes but is not limited to one or more of POE polyolefin elastomers.
In the invention, the mass ratio of the antibacterial modifier to the thermoplastic elastomer is preferably 0.1-10%, more preferably 0.5-5%, and the antibacterial modifier and the thermoplastic elastic matrix can be combined to an optimal state within the range of the ratio, and the antibacterial modifier is uniformly distributed in the thermoplastic elastic matrix and forms a dominant dispersion structure with the thermoplastic elastic matrix, so that not only can better antibacterial performance be ensured, but also the physical and mechanical properties of an elastomer product can be ensured.
The invention also provides a preparation method of the antibacterial modified thermoplastic elastomer, which comprises the following steps: and mixing the antibacterial modifier with the thermoplastic elastomer, and performing melt extrusion to obtain the antibacterial modified thermoplastic elastomer.
The types, the usage amounts, the sources and the like of the antibacterial modifier and the thermoplastic elastomer are consistent with those in the technical scheme, and are not described again.
In the invention, the temperature of the melt extrusion is preferably 160-240 ℃; the time for melt extrusion is preferably 1-6 min. The melt extrusion may be carried out using equipment well known to those skilled in the art, such as a twin screw extruder. Through melt extrusion, the antibacterial modifier is uniformly dispersed in the thermoplastic elastic matrix, and the formed antibacterial modified thermoplastic elastomer material has good antibacterial property and lasting antibacterial property; moreover, the antibacterial modifier provided by the invention is high-temperature resistant, and the antibacterial agent can not generate side reactions such as pyrolysis and the like in the melt extrusion process, so that the problem that the conventional antibacterial agent is difficult to melt and process is solved; moreover, the obtained antibacterial agent of the antibacterial modified thermoplastic elastomer has no toxic or side effect, and can be better used in the fields of medical instruments such as blood infusion instruments, interventional or implanted instruments and the like. In addition, the preparation method is simple and easy to implement, has no pollution to the environment, and is easy to realize large-scale continuous production.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
A polyhexamethylene biguanide hydrochloride aqueous solution (number average molecular weight of polyhexamethylene biguanide hydrochloride 533) at a concentration of 2.0% and a sodium stearate aqueous solution at a concentration of 2.0% were prepared, respectively, in accordance with the ratio of polyhexamethylene biguanide hydrochloride: and mixing the two solutions at room temperature according to the mass ratio of 1:1 to quickly form a water-insoluble precipitate, carrying out centrifugal separation, washing with water for three times, and drying to obtain the polyhexamethylene biguanide hydrochloride-sodium stearate compound antibacterial modifier.
10g of the antibacterial modifier and 990g of polyurethane TPU (model BASF 1180A, the melt index is 15g/10min, the test condition is 10kg and 190 ℃) are uniformly mixed in a high-stirring machine, then the mixture is melt-extruded in a double-screw extruder, the extrusion temperature is 200 ℃, the screw rotation speed is 130rpm, the material residence time is 1.5min, and the antibacterial modified polyurethane elastomer is obtained after melt-extrusion.
Example 2
Aqueous polyhexamethylene monoguanidine phosphate solutions (number average molecular weight of polyhexamethylene monoguanidine phosphate 241) at a concentration of 1.5% and aqueous potassium stearate solutions at a concentration of 1.5% were prepared, respectively, according to the molar ratio of polyhexamethylene monoguanidine phosphate: mixing the two solutions at room temperature to quickly form a water-insoluble precipitate, carrying out centrifugal separation, washing with water for three times, and drying to obtain the polyhexamethylene monoguanidine phosphate-potassium stearate compound antibacterial modifier.
Taking 15g of the antibacterial modifier and 985g of polyolefin elastomer (styrene-ethylene-butylene-styrene block copolymer SEBS, the melt index of which is 55g/10min, the test conditions are 5kg and 200 ℃), uniformly mixing in a high-stirring machine, then carrying out melt extrusion in a double-screw extruder, wherein the extrusion temperature is 180 ℃, the screw rotation speed is 100rpm, and the material residence time is 2.5min, and carrying out melt extrusion to obtain the antibacterial modified polyolefin elastomer.
Example 3
A 1.5% strength aqueous solution of polyaminopropyl biguanide hydrochloride (number average molecular weight of the polyaminopropyl biguanide hydrochloride is 474) and a 1.5% strength aqueous solution of sodium laurate were prepared, respectively, according to the following formula: and mixing the two solutions at room temperature according to the mass ratio of 1:1 to quickly form a water-insoluble precipitate, carrying out centrifugal separation, washing with water for three times, and drying to obtain the poly (aminopropyl biguanide hydrochloride) -sodium laurate compound antibacterial modifier.
10g of the antibacterial modifier and 990g of nylon elastomer (model PEBAX 2533, melt index of 10g/10min, test conditions of 10kg and 190 ℃) are uniformly mixed in a high-stirring machine, then the mixture is melt-extruded in a double-screw extruder, the extrusion temperature is 210 ℃, the screw rotation speed is 110rpm, the material residence time is 2.0min, and the antibacterial modified nylon elastomer is obtained after melt-extrusion.
Example 4
Respectively preparing 1.5% poly (1, 6-bis (p-chlorobiguanide) n-hexane digluconate aqueous solution (the number average molecular weight of the poly (1, 6-bis (p-chlorobiguanide) n-hexane digluconate is 1200) and 1.5% sodium myristate aqueous solution according to the weight ratio of the poly (1, 6-bis (p-chlorobiguanide) n-hexane digluconate: mixing the two solutions at room temperature according to the mass ratio of 1:1 to quickly form a water-insoluble precipitate, carrying out centrifugal separation, washing with water for three times, and drying to obtain the poly (1, 6-bis (p-chlorobiguanide) n-hexane digluconate-sodium myristate composite antibacterial modifier.
10g of the antibacterial modifier and 990g of nylon elastomer (model PEBAX 2533, melt index of 10g/10min, test conditions of 10kg and 190 ℃) are uniformly mixed in a high-stirring machine, then the mixture is melt-extruded in a double-screw extruder, the extrusion temperature is 210 ℃, the screw rotation speed is 110rpm, the material residence time is 2.0min, and the antibacterial modified nylon elastomer is obtained after melt-extrusion.
Example 5
The antibacterial modified thermoplastic elastomer materials of examples 1-4 were made into films with a thickness of 1mm in a flat vulcanizing machine, and the antibacterial property of the obtained films was tested according to standard astm e2149-01, and the bacteria for detection were escherichia coli and staphylococcus aureus, and the test results are shown in table 1.
TABLE 1 results of antibacterial property test of elastomer materials obtained in examples 1 to 4
| Fungus | Example 1 | Example 2 | Example 3 | Example 4 |
| Escherichia coli | 97.8％ | 97.5％ | 97.1％ | 95.8％ |
| Staphylococcus aureus | 98.6％ | 99.2％ | 97.9％ | 96.7％ |
The test results in table 1 show that the antibacterial properties of the antibacterial modified thermoplastic elastomer provided by the invention all reach more than 95%, and the antibacterial modified thermoplastic elastomer shows excellent antibacterial properties.
After the antibacterial modified thermoplastic elastomer films are soaked in water at 37 ℃ for one month, the antibacterial property of each film is tested according to the standard ASTM E2149-01, and the test results are shown in Table 2.
TABLE 2 results of the antibacterial durability test of the elastomer materials obtained in examples 1 to 4
| Fungus | Example 1 | Example 2 | Example 3 | Example 4 |
| Escherichia coli | 97.5％ | 96.5％ | 97.3％ | 95.2％ |
| Staphylococcus aureus | 97.7％ | 97.2％ | 97.1％ | 95.8％ |
The test results in table 2 show that the antibacterial performance of the elastic material provided by the invention can still be maintained above 95% after being soaked for one month, and the elastic material provided by the invention has excellent antibacterial durability.
Comparative example 1
An antibacterial modified thermoplastic elastomer material was prepared according to the preparation process of example 1, except that the antibacterial modifier was replaced with a nano zirconium phosphate silver-loaded antibacterial agent.
The resulting elastomeric material was tested for initial antimicrobial properties and after one month of water immersion according to the test methods of example 5, the test results are shown in table 3.
Table 3 results of antibacterial property test of elastomer material obtained in comparative example 1
| Fungus | Initial antibacterial property | Antibacterial property after one month |
| Escherichia coli | 97.8％ | 70.6％ |
| Staphylococcus aureus | 94.9％ | 65.4％ |
As can be seen from the test results in table 3, after one month of water immersion, the antibacterial property of comparative example 1 is greatly reduced, the antibacterial durability is extremely poor, and it is very unfavorable for practical application.
Comparative example 2
10g of polyhexamethylene biguanide hydrochloride (with the number average molecular weight of 241) and 990g of polyurethane TPU (BASF 1180A with the melt index of 15g/10min under the test conditions of 10kg and 190 ℃) are uniformly mixed in a high-stirring machine, and then are melt-extruded in a double-screw extruder at the extrusion temperature of 200 ℃, the screw rotation speed of 130rpm and the material residence time of 1.5min, and the antibacterial modified polyurethane elastomer is obtained after melt-extrusion.
The resulting elastomeric material was tested for initial antimicrobial properties and after one month of water immersion according to the test methods of example 5, the test results are shown in table 4.
Table 4 results of antibacterial property test of elastomer material obtained in comparative example 4
| Fungus | Initial antibacterial property | Antibacterial property after one month |
| Escherichia coli | 97.5％ | 67.6％ |
| Staphylococcus aureus | 97.7％ | 68.9％ |
As can be seen from the test results in Table 4, the antibacterial durability of the obtained material is obviously deteriorated only by introducing the polyguanylate to be combined with the thermoplastic elastomer, and the antibacterial effect of the elastomer material can be remarkably improved only by combining the polyguanylate and the fatty acid salt compound serving as the antibacterial agent with the thermoplastic elastomer.
Comparative examples 3 to 4
Comparative example 3: an antibacterial modified thermoplastic elastomer material was prepared by following the procedure of example 2 except that polyguanylate was replaced with guanidinium dodecyl acetate. As a result, the complex antibacterial modifier cannot be obtained by precipitation during the process of preparing the antibacterial modifier.
Comparative example 4: an antibacterial modified thermoplastic elastomer material was prepared by following the procedure of example 3 except that the polyaminopropyl biguanide hydrochloride was replaced with polyaminopropyl biguanide hydrochloride having a number average molecular weight of 100. As a result, the complex antibacterial modifier cannot be obtained by precipitation during the process of preparing the antibacterial modifier.
Therefore, the polyguanylate in the antibacterial modifier can not be replaced by monoguanylate or polyguanylate with lower molecular weight, and the polyguanylate-fatty acid salt compound antibacterial modifier can not be obtained, and only the polyguanylate provided by the invention can be combined with fatty acid salt to form the compound antibacterial modifier.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. An antibacterial modifier, which is characterized in that the antibacterial modifier is a polyguanylate-fatty acid salt compound formed by combining polyguanylate and fatty acid salt;
the antibacterial modifier is obtained by the following preparation method:
mixing an aqueous polyguanylate solution with an aqueous fatty acid salt solution to form a polyguanylate-fatty acid salt complex;
the mixing temperature is 0-50 ℃;
the polyguanidine hydrochloride is selected from one or more of polyguanidine hydrochloride, polyguanidine phosphate and polyguanidine gluconate;
the guanidine in the polyguanidine hydrochloride is selected from one or more of alkyl guanidine of C4-C22 and substituted alkyl guanidine of C4-C22;
the number average molecular weight of the polyguanylate is 150-3000;
the fatty acid salt is selected from one or more of C5-C31 fatty acid potassium and C5-C31 fatty acid sodium;
the mass ratio of the polyguanylate to the fatty acid salt is 1: 0.1-2;
the mass percentage concentration of the polyguanylate aqueous solution is 0.1-5%;
the mass percentage concentration of the fatty acid salt water solution is 0.1-5%.
2. The antibacterial modifier according to claim 1, wherein the fatty acid salt is one or more selected from the group consisting of potassium fatty acid salts of C12-C18 and sodium fatty acid salts of C12-C18.
3. The antibacterial modifier of claim 2, wherein the substituent in the substituted C4-C22 alkylguanidine is selected from amino, phenyl, and substituted phenyl.
4. The antimicrobial modifier of claim 2, wherein the polyguanylate is selected from one or more of polyhexamethylene biguanide hydrochloride, polyhexamethylene biguanide phosphate, polyaminopropyl biguanide hydrochloride, polyaminopropyl biguanide phosphate, polyaminopropyl monoguanidine hydrochloride, polyaminopropyl monoguanidine phosphate, poly 1, 6-bis (p-chlorobiguanide) n-hexane digluconate and poly 1, 6-bis (p-chlorobenzenemonoguanidine) n-hexane digluconate;
the fatty acid salt is selected from one or more of sodium stearate, potassium stearate, sodium palmitate, potassium palmitate, sodium myristate, potassium myristate, sodium laurate and potassium laurate.
5. A method for preparing the antibacterial modifier according to any one of claims 1 to 4, which comprises the following steps:
mixing the aqueous polyguanylate solution with the aqueous fatty acid salt solution to form a polyguanylate-fatty acid salt complex.
6. An antibacterial modified thermoplastic elastomer, which is characterized by comprising an antibacterial modifier and a thermoplastic elastomer;
the antibacterial modifier is the antibacterial modifier as claimed in any one of claims 1 to 4.
7. A method for preparing the antibacterial modified thermoplastic elastomer as claimed in claim 6, characterized by comprising:
and mixing the antibacterial modifier with the thermoplastic elastomer, and performing melt extrusion to obtain the antibacterial modified thermoplastic elastomer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810731914.3A CN108976768B (en) | 2018-07-05 | 2018-07-05 | Antibacterial modifier and preparation method thereof, antibacterial modified thermoplastic elastomer and preparation method thereof |
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| CN201810731914.3A CN108976768B (en) | 2018-07-05 | 2018-07-05 | Antibacterial modifier and preparation method thereof, antibacterial modified thermoplastic elastomer and preparation method thereof |
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| CN108976768B true CN108976768B (en) | 2020-07-28 |
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| CN111518356A (en) * | 2020-05-20 | 2020-08-11 | 中国科学院长春应用化学研究所 | Modified polypropylene and preparation method thereof |
| CN111534111A (en) * | 2020-05-20 | 2020-08-14 | 东莞市山普科技有限公司 | Antibacterial TPE (thermoplastic elastomer) super-soft material as well as preparation method and application thereof |
| CN112375231A (en) * | 2020-11-12 | 2021-02-19 | 齐鲁工业大学 | High-antibacterial-property modified nano lignin and preparation method and application thereof |
| CN112796161A (en) * | 2020-12-31 | 2021-05-14 | 南京林业大学 | Modified natural polymer and preparation method and application thereof |
| CN112876917B (en) * | 2021-03-08 | 2022-08-09 | 四川大学 | Antibacterial coating for inner wall of aviation fuel tank and preparation method thereof |
| CN114561034A (en) * | 2022-03-31 | 2022-05-31 | 中国科学院长春应用化学研究所 | Antimicrobial modified sulfonated styrene-based polymer compound and preparation method thereof |
| CN117264360A (en) * | 2023-09-15 | 2023-12-22 | 苏州创扬新材料科技股份有限公司 | Medical antibacterial thermoplastic elastomer and preparation method thereof |
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| CN101724284A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Anti-bacterial thermoplastic composite and preparation method thereof |
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| CN101724284A (en) * | 2008-10-31 | 2010-06-09 | 中国石油化工股份有限公司 | Anti-bacterial thermoplastic composite and preparation method thereof |
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