CN110835458B - Biodegradable material with antibacterial effect and high strength, and preparation and application thereof - Google Patents
Biodegradable material with antibacterial effect and high strength, and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses preparation and application of a biodegradable material with antibacterial effect and high strength. According to the invention, the mechanical property and the thermal stability of the polylactic acid are improved by adding the biological resin and blending the polylactic acid, and the antibacterial groups are grafted on the biological resin and uniformly distributed in the polylactic acid matrix, so that the polylactic acid biodegradable material is endowed with excellent antibacterial property, and the influence of the decomposition effect of microorganisms in the environment on the storage, the service life and the safety of the material is prevented. The invention can further improve the barrier property and the antibacterial property of the polylactic acid by functionally modifying the filler, ensure the safety of food or medicine in the packaging material and meet the high standard of the industry on the performance of the polylactic acid material. The method is simple, efficient and low in cost, and can be applied to the wide fields of material packaging and the like.
Description
Technical Field
The invention relates to the technical field of biodegradable materials, in particular to a biodegradable material with antibacterial effect and high strength, and preparation and application thereof.
Background
With the progress of society, people are more aware of the importance of environmental protection, and means for reducing white pollution and promoting environmental protection are continuously innovated along with the progress of raw material production and processing technology. The polylactic acid is a polymer which can be completely biodegraded, recycled and biocompatible, can be well applied to the field of packaging, and can greatly reduce white pollution caused by daily life. However, the application of polylactic acid in replacing the traditional plastic on a packaging film still has a plurality of problems, such as poor heat resistance, low toughness, poor water oxygen barrier property, easy hydrolysis, mildewing and bacteria generation during storage, no effective antibacterial protection for packaged articles and the like. At present, in the prior art, the mechanical property of polylactic acid is mainly solved by arranging a multilayer composite film, or the surface coating layer is adopted to reduce the corrosion of the environment to prolong the service life of the polylactic acid film or the antibacterial coating layer is used for protecting the content, but the multilayer compounding needs a special multilayer co-extrusion machine, the coating corrosion resistance needs large-scale coating process equipment, the material processing cost or the period cost is increased, and the application of the polylactic acid packaging film is restricted.
Disclosure of Invention
The invention aims to solve the technical problems of poor performance and low application degree of polylactic acid and provides a biodegradable material with antibacterial effect and high strength.
The invention also aims to solve the technical problem of a preparation method of the biodegradable material with antibacterial effect and high strength.
The purpose of the invention is realized by the following technical scheme:
the biodegradable material with the antibacterial effect and the high strength comprises, by weight, 60-90 parts of polylactic acid, 10-30 parts of biological resin, 0.5-3 parts of a grafting agent, 2-15 parts of a bacteriostatic agent, 0.1-0.5 part of a catalyst and 1-3 parts of a compatilizer. The above materials were prepared as follows:
s1, dissolving dried biological resin in a solvent, adding a bacteriostatic agent, a grafting auxiliary agent and a catalyst in a protective gas atmosphere, stirring and reacting completely, and drying to obtain a bacteriostatic agent-g-biological resin graft copolymer;
s2, carrying out melt polymerization reaction on the polylactic acid, the bacteriostatic agent-g-biological resin graft copolymer and the compatilizer through an extruder, and then granulating and dicing to obtain the biodegradable material with the bacteriostatic effect and high strength.
Further, the biological resin is one or more of polybutylene succinate, polypyrrole, benzoquinone polymer, polycaprolactone, polybutylene adipate-butylene terephthalate and polybutylene adipate-butylene glycol-urea. According to the invention, polylactic acid is selected and blended with the materials, so that advantages of various materials are complemented, and the mechanical property and the processing property of the polylactic acid are improved, thereby meeting the performance requirements of the packaging film.
Further, the solvent is one or more of ethyl acetate, N-methyl pyrrolidone or acetone
Further, the grafting agent is one or more of beta-glucan or yeast glucan, dopamine, multifunctional epoxy ester, multifunctional isocyanate and the like.
Further, the bacteriostatic agent comprises one or more of arecoline, quaternary phosphonium salt, chitosan, lactoferrin or sulfhydryl oxidase.
According to the invention, the polylactic acid mechanical property meets the requirement of an antibacterial film, the biological resin is further subjected to functional modification, and the blended resin additive is grafted with antibacterial groups, so that the blended resin additive has a certain antibacterial property, and the problems that the material and the packaging contents of the material are polluted by microorganisms such as mould and bacteria and the like and the service life of the polylactic acid material is reduced due to the decomposition of the microorganisms can be prevented.
Further, the catalyst is stannous octoate. The compatilizer is maleic anhydride grafted polylactic acid or maleic anhydride grafted polycaprolactone and is used for improving the compatibility of the polylactic acid and the biological resin. In the direct melting process of polylactic acid and biological resin, the compatibility of the polylactic acid and the biological resin is poor, so that the comprehensive mechanical property of the blend material is poor, and the blend can be compatibilized to a certain extent by adding a proper amount of compatilizer.
Further, the stirring reaction temperature of S1 is 25-50 ℃, and the time is 3-5 h; the drying mode is vacuum drying, the drying temperature is 45-60 ℃, and the drying temperature is 12-24 hours.
Further, the temperature of the extruder in S2 is 170-190 ℃, the rotating speed of the screw is 40-60 r/min, and the length-diameter ratio of the screw is 15-25: 1.
Furthermore, the biodegradable material with antibacterial effect and high strength can be further improved by adding a filler, wherein the filler is one or more of hydroxyapatite, zinc oxide, silicate, titanium oxide, talcum powder, halloysite nanotubes and graphene. The inorganic nano particles are added into the polymer, so that the strength and toughness of the polylactic acid biodegradable material can be improved, and the inorganic particles are uniformly distributed in the material, so that the permeation path of water and oxygen molecules can be prolonged, and the barrier property of the product can be improved.
The invention can also modify the antibacterial property of the filler, further improve the antibacterial property of the polylactic acid biodegradable material and prolong the service life. The preparation steps of the antibacterial functional filler comprise:
the filler and the silane bridging agent are put in ethanol water, the pH value is adjusted to be acidic, the mixture is stirred and modified, and the mixture is washed and dried; and then mixing the dried modified filler with a bacteriostatic aid and a boron trifluoride diethyl etherate solvent, stirring for reaction, centrifuging, cleaning and drying to obtain the antibacterial functional filler.
Furthermore, the silane bridging agent is one or more of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane or gamma-vinyl trimethoxy silane, isocyanate propyl triethoxy silane and the like. .
Furthermore, the bacteriostatic auxiliary agent is one or more of quaternary ammonium salt, quaternary phosphonium salt, chitosan, titanate and the like.
Further, the mass ratio of the filler to the silane bridging agent is 15-30: 1; the addition amount of the bacteriostatic auxiliary agent is 1-5% of the mass of the filler.
Further, adding boron trifluoride diethyl etherate with the concentration of 1-5%, and stirring and refluxing the modified filler and the bacteriostatic aid in the solvent at the temperature of 40-50 ℃ for reaction for 12-18 hours.
The prepared biodegradable material with antibacterial effect and high strength is used in the field of material packaging, and can be used for manufacturing shopping bags, kitchen ware, mulching films and the like.
Compared with the prior art, the beneficial effects are:
the invention takes the green and environment-friendly biodegradable material polylactic acid as a main body, and adds the toughening, heat-resisting and high-strength biological resin to blend with the polylactic acid to form advantage complementation, thereby improving the strength, toughness and heat-resisting property of the polylactic acid, leading the polylactic acid to meet the requirements of more fields on the material performance, expanding the application range of the polylactic acid and reducing the application of white pollution sources. The invention also carries out antibacterial functional modification on the biological resin, and the antibacterial groups are uniformly distributed in the composite material through the melt blending of the biological resin and the polylactic acid, thereby improving the antibacterial property of the biodegradable material, preventing the corrosion and decomposition of the material and the package contents by microorganisms such as mould, bacteria and the like, keeping the quality and freshness of the package contents, and reducing the decomposability of the biodegradable material to improve the service life of the biodegradable material.
The inorganic filler can be further modified, so that the mechanical property of the material can be enhanced, the barrier property can be improved by prolonging the molecular permeation path of water and oxygen, the antibacterial property can be further enhanced, the problem of service life reduction caused by environmental factors can be reduced, the safety of contents in the material is protected, particularly foods and medicines, and the degeneration, the deterioration or the overdue of the contents can be delayed or prevented. The matrix resin bacteriostasis and the functional filler bacteriostasis are dual bacteriostasis. And can inhibit bacteria and slow down the process of the raw bacteria and the mildew of the packaging material and the contents. But also can enhance the mechanical property of the polylactic acid and the barrier property to water vapor and oxygen.
The preparation process is simple, convenient, fast, efficient and low in cost, and granules with better performance can be obtained only by a common extrusion equipment blending mode, and the biodegradable packaging material is obtained by a film forming process. The invention has scientific collocation of raw materials and simple modification, greatly improves the performance of the polylactic acid and has wider application range. The components used in the invention can be degraded in a composting way, belong to completely biodegradable materials and are harmless to the environment.
Drawings
FIG. 1 is an electron microscope image of a biodegradable material prepared by the present invention;
FIG. 2 is a graph of the antimicrobial effect of a material that has not been antimicrobially modified;
FIG. 3 is a diagram showing the antibacterial effect of the material after the antibacterial modification.
Detailed Description
The following examples are further explained and illustrated, but the present invention is not limited in any way by the specific examples. Unless otherwise indicated, the methods and equipment used in the examples are conventional in the art and all materials used are conventional commercially available materials.
Example 1
The embodiment provides a preparation method of a biodegradable material with antibacterial effect and high strength, which comprises the following steps:
s1, dissolving dried biological resin in a solvent, filling protective gas, adding a bacteriostatic agent, a grafting aid and a catalyst, stirring at 45-60 ℃, reacting for 3-4 h, and drying at 45-60 ℃ for 12-24 h to obtain a bacteriostatic agent-g-biological resin graft copolymer;
s3, passing the polylactic acid, the bacteriostatic agent-g-biological resin graft copolymer and the compatilizer through an extruder, setting the extrusion temperature (from a feeding section to a die head) of the extruder to be 170,175,190,190,190,170 ℃, the rotation speed of a screw rod to be 40-60 r/min and the length-diameter ratio of the screw rod to be 15-25: 1 respectively, carrying out melt polymerization reaction, and then carrying out granulation and grain cutting to obtain the biodegradable material with the bacteriostatic effect and high strength.
Example 2
The embodiment provides a preparation method of a filler-reinforced biodegradable material with antibacterial effect and high strength, which comprises the following steps:
s1, dissolving dried biological resin in a solvent, filling protective gas, adding a bacteriostatic agent, a grafting aid and a catalyst, stirring at 45-60 ℃, reacting for 3-4 h, and drying at 45-60 ℃ for 12-24 h to obtain a bacteriostatic agent-g-biological resin graft copolymer;
s2, adding the filler and the silane bridging agent into an ethanol aqueous solution according to a ratio, adjusting the pH value to be weakly acidic, stirring for modification, cleaning and drying; then mixing the dried modified filler with the bacteriostatic aid and boron trifluoride diethyl etherate solvent, stirring for reaction, centrifuging, cleaning and drying to obtain the antibacterial functional filler
S3, passing the polylactic acid, the bacteriostatic agent-g-biological resin graft copolymer and the compatilizer through an extruder, setting the extrusion temperature (from a feeding section to a die head) of the extruder to be 170,175,190,190,190,170 ℃, the rotation speed of a screw rod to be 40-60 r/min and the length-diameter ratio of the screw rod to be 15-25: 1 respectively, carrying out melt polymerization reaction, and then carrying out granulation and grain cutting to obtain the biodegradable material with the bacteriostatic effect and high strength.
The silane bridging agent is one or more of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane vinyl trimethoxy silane, isocyanate propyl triethoxy silane and the like. .
The bacteriostatic auxiliary agent is one or more of quaternary ammonium salt, quaternary phosphonium salt, chitosan, titanate and the like.
The mass ratio of the filler to the silane bridging agent is 15-30: 1; the addition amount of the bacteriostatic auxiliary agent is 1-5% of the mass of the filler.
The concentration of the boron trifluoride diethyl etherate solvent is 1-5%, and the modified filler and the bacteriostatic aid are stirred and refluxed in the solvent at the temperature of 40-50 ℃ for reaction for 12-18 h.
Example 3
In this example, according to formula one, the biodegradable material with bacteriostatic effect and high strength is prepared from the raw materials according to the preparation method described in example 1. The formula I is as follows:
the formula I is as follows:
example 4
In this embodiment, according to the second formula, the biodegradable material having bacteriostatic effect and high strength is prepared from the raw materials according to the preparation method described in embodiment 1. The formula I is as follows:
and a second formula:
example 5
In this embodiment, according to formula three, the biodegradable material with bacteriostatic effect and high strength is prepared from the raw materials according to the preparation method described in embodiment 1. The formula I is as follows:
and the formula III:
example 6
In this embodiment, according to formula four, the biodegradable material with bacteriostatic effect and high strength is prepared from the raw materials according to the preparation method described in embodiment 1. The formula I is as follows:
the formula four:
example 7
In this embodiment, according to formula five, the biodegradable material with bacteriostatic effect and high strength is prepared from the raw materials according to the preparation method described in embodiment 1. The formula I is as follows:
and a fifth formula:
example 8
In this embodiment, according to the formula six, the biodegradable material having antibacterial effect and high strength is prepared from the raw materials according to the preparation method described in embodiment 1. The formula I is as follows:
and the formula six:
examples 9 to 14 are the raw materials described in examples 3 to 8, to which 3 parts of chitosan-grafted graphene modified filler, 2 parts of quaternary ammonium salt-grafted halloysite nanotube modified filler, 0.5 part of titanate-grafted talc powder modified filler, 5 parts of quaternary ammonium salt-grafted zinc oxide, 3 parts of quaternary phosphonium salt-grafted hydroxyapatite, and 2 parts of chitosan-grafted titanium oxide were added, respectively.
Comparative example 1
The comparative example is the same as the process steps of example 9, and is different from the comparative example in that antibacterial agent arecoline is not added to carry out antibacterial function modification on bio-resin polybutylene succinate.
Comparative example 2
The comparative example is the same as the example 9 in process steps, and is different in that the antibacterial function modification is not carried out on the bio-resin polybutylene succinate, but the antibacterial agent arecoline is directly added for mixing and extrusion.
Experimental example 1
In the experimental example, tensile property, impact property and thermal stability of examples 3 to 14 and comparative examples 1 to 2 and pure polylactic acid were tested with reference to GB/T10470-1992 test method for tensile property of plastics, GB/T1043.1-2008 test method for impact property of simple beam of plastics and thermal stability test, and the results are shown in Table 1:
TABLE 1
Experimental example 2
In the experimental example, according to QB/T2591-2003 standard, pure polylactic acid is used as a control group, and the antibacterial performance of the examples and the comparative examples is detected, wherein the antibacterial rate result is shown in Table 2:
TABLE 2
Experimental example 3
In the experimental example, the examples, the comparative examples and the pure polylactic acid are subjected to degradation experimental detection by referring to GB/T20197-2006, and the weight loss rate results are shown in Table 3:
TABLE 3
The data show that the biodegradable material with the antibacterial effect and the high strength has higher strength, can meet the mechanical property requirement and the thermal stability of the existing packaging material, has good antibacterial effect, enhances the barrier property to water vapor and oxygen, can prolong the service life of the material, and can ensure the safety of contents. The preparation method is simple, convenient, rapid and efficient, the matrix material can be completely degraded, and the pollution to the environment can not be caused.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. A biodegradable material with antibacterial effect and high strength is characterized by comprising, by weight, 60-90 parts of polylactic acid, 10-30 parts of biological resin, 0.5-3 parts of a grafting agent, 2-15 parts of a bacteriostatic agent, 0.1-0.5 part of a catalyst and 1-3 parts of a compatilizer;
the biological resin is one or more of polybutylene succinate, polypyrrole, benzoquinone polymer, polycaprolactone, butanediol adipate-butanediol terephthalate and poly adipic acid-butanediol-urea;
the grafting agent is one or more of glucan, dopamine, multifunctional epoxy resin, multifunctional isocyanate and the like;
the bacteriostatic agent comprises one or more of arecoline, quaternary phosphonium salt, quaternary ammonium salt, chitosan, lactoferrin or sulfhydryl oxidase;
the above materials were prepared as follows:
s1, dissolving dried biological resin in a solvent, adding a bacteriostatic agent, a grafting agent and a catalyst in a protective gas atmosphere, stirring and reacting completely, and drying to obtain a bacteriostatic agent-g-biological resin graft copolymer;
s2, carrying out melt polymerization reaction on polylactic acid, a bacteriostatic agent-g-biological resin graft copolymer and a compatilizer through an extruder, and then granulating and dicing to obtain a biodegradable material with bacteriostatic effect and high strength;
s1, stirring and reacting at the temperature of 45-60 ℃ for 3-4 h; the drying mode is vacuum drying, the drying temperature is 45-60 ℃, and the drying temperature is 12-24 hours.
2. The biodegradable material having bacteriostatic effect and high strength according to claim 1, wherein said catalyst is stannous octoate or stannous chloride; the compatilizer is maleic anhydride grafted polylactic acid or maleic anhydride grafted polycaprolactone.
3. The biodegradable material with antibacterial effect and high strength according to claim 1, wherein the temperature of the extruder S2 is 170-190 ℃, the rotation speed of a screw is 40-60 r/min, and the length-diameter ratio of the screw is 15-25: 1.
4. The biodegradable material with antibacterial effect and high strength according to claim 1, characterized by further comprising 0.5-5 parts of a filler; the filler is one or more of hydroxyapatite, zinc oxide, silicate, titanium oxide, talcum powder, halloysite nanotubes and graphene.
5. The biodegradable material with antibacterial effect and high strength according to claim 4, characterized in that the filler is an antibacterial functionalized filler, and the preparation steps thereof comprise:
the filler and the silane bridging agent are put in ethanol water, the pH value is adjusted to be acidic, the mixture is stirred and modified, and the mixture is washed and dried; and then mixing the dried modified filler with a bacteriostatic agent and a boron trifluoride diethyl etherate solvent, stirring for reaction, centrifuging, cleaning and drying to obtain the antibacterial functional filler.
6. The biodegradable material with antibacterial effect and high strength as claimed in any one of claims 1 to 5, wherein the biodegradable material with antibacterial effect and high strength is used for material packaging.
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| CN115160742A (en) * | 2022-07-12 | 2022-10-11 | 广东春夏新材料科技股份有限公司 | PBAT composite material and preparation method thereof |
| CN115536999B (en) * | 2022-11-02 | 2023-07-28 | 贵州省材料产业技术研究院 | High-barrier antibacterial biodegradable material and preparation method and application thereof |
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