CN116178732A - Antibacterial starch, food fresh-keeping packaging film and preparation method and application thereof - Google Patents

Antibacterial starch, food fresh-keeping packaging film and preparation method and application thereof Download PDF

Info

Publication number
CN116178732A
CN116178732A CN202310060448.1A CN202310060448A CN116178732A CN 116178732 A CN116178732 A CN 116178732A CN 202310060448 A CN202310060448 A CN 202310060448A CN 116178732 A CN116178732 A CN 116178732A
Authority
CN
China
Prior art keywords
starch
antibacterial
packaging film
mass ratio
pbat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310060448.1A
Other languages
Chinese (zh)
Inventor
李立
唐淑蓉
董庆丰
樊敏
康永锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Ocean University
Original Assignee
Shanghai Ocean University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Ocean University filed Critical Shanghai Ocean University
Priority to CN202310060448.1A priority Critical patent/CN116178732A/en
Publication of CN116178732A publication Critical patent/CN116178732A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses an antibacterial starch, a food fresh-keeping packaging film and a preparation method and application thereof, and belongs to the technical field of plastic packaging. The starch is modified by polyhexamethylene biguanidine hydrochloride to prepare the hydrophobic antibacterial starch. The glycerol in the food preservative packaging film plays a plasticizing role. The PLA/PBAT/antibacterial starch food preservative packaging film prepared by coextrusion casting enhances the moisture resistance and the oxygen resistance of the PLA/PBAT/starch food preservative packaging film, and the film has antibacterial property by adding the polyhexamethylene biguanide hydrochloride.

Description

Antibacterial starch, food fresh-keeping packaging film and preparation method and application thereof
Technical Field
The invention relates to an antibacterial starch, a food fresh-keeping packaging film and a preparation method and application thereof, and belongs to the technical field of plastic packaging.
Background
With the progress of society and the development of science and technology, plastic products have been widely paid attention to and studied by scientists, which makes the plastic products more useful for people's daily life. However, the frequent use of plastic products causes a series of problems such as exhaustion of energy, white pollution, etc., and white pollution caused by plastics has become a worldwide hazard. With the improvement of living standard, the requirements of people on living quality are higher and higher, so that people pay more attention to environmental protection, and the improvement and innovation of traditional plastics are caused. Since the last 70 th century, biotechnology has been as if a black horse intruded into people's line of sight, and at the same time, achieved a peace of mind in all areas. In order to solve the problem of plastic waste, in addition to recycling, the development of renewable and degradable plastics is the most fundamental approach.
Polylactic acid (PLA) has excellent physical and chemical properties, extremely high transparency, good biological and chemical degradation performance, controllable degradation time, no toxicity, no smell, acid and alkali resistance, germ resistance, ultraviolet resistance, easy processing and forming, easy degradation, no harm to environment, and the like, which are incomparable with the traditional plastics. Polybutylene terephthalate (PBAT) belongs to thermoplastic biodegradable plastics, has better ductility and elongation at break, also has better heat resistance and impact property, can be degraded into water and carbon dioxide after being abandoned, and has outstanding environmental protection effect. The PBAT has the advantages of high heat resistance, good film forming performance, good toughness, high hydrolysis resistance and the like. In addition, the composition has excellent biodegradability.
As a useful biodegradable polymer, the starch has the advantages of low cost, wide applicability, excellent reproducibility and the like.
The starch belongs to a pure natural pollution-free high polymer material, and is widely applied to thermoplastic starch, starch/aliphatic polyester blend materials and other completely biodegradable composite materials. However, natural starch has a polyhydroxy structure, has a large intermolecular force, has a microcrystalline structure, is difficult to melt and plasticize, has strong hydrophilicity and poor compatibility with most plastics, and has limited applications in production and living. After the starch is modified, the hydrophobicity is enhanced, and the interfacial compatibility of the starch and the nonpolar plastic can be improved, so that the starch and plastic blending composite material with better performance is produced.
The current research on packaging films mainly aims at improving mechanical properties, and previous research on improving mechanical properties of films by mixing starch, PLA and PBAT has been reported by the subject group (Zhao, M., Z.Zhang, H.Cai, L.Wang, C.Hu, D.Li, Y.Chen, Y.Kang and L.Li (2022), "Controlled moisture permeability of thermoplastic starch/polylactic acid/poly butylene adipate-co-terephthalate film for the autolysis of straw mushroom Volvariella volvacea.," Food Chem 373 (Pt A): 131409.), "but also important for antibacterial properties for packaging with Food. The subject group also studied the addition of natural bacteriostatic materials to films, (Zhao, m., Z.Zhang, H.Cai, L.Wang, C.Hu, D.Li, Y.Chen, Y.Kang and l.li (2022), "Controlled moisture permeability of thermoplastic starch/polylactic acid/poly butylene adipate-co-terephthalate film for the autolysis of straw mushroom Volvariella volvacea.," Food Chem 373 (Pt a): 131409 ]) to prepare antimicrobial packages by adding essential oils. Although the addition of essential oils achieves bacteriostasis to a certain extent, the essential oils are volatile and migrate into the food, not only affecting the flavor of the food, but also diminishing the antimicrobial properties over time. The development of the antibacterial starch, the food fresh-keeping packaging film and the preparation method and the application thereof have very practical significance.
Disclosure of Invention
The invention aims to solve the technical problems of providing an antibacterial starch, a food fresh-keeping packaging film, and a preparation method and application thereof, and aims to prolong the food fresh-keeping time.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
the preparation method of the antibacterial starch comprises the following steps: mixing starch and maleic anhydride according to the mass ratio of 10:0.5-1.5, and grafting to obtain esterified starch; under the action of isophorone diisocyanate, the esterified starch is grafted with an antibacterial agent to obtain antibacterial starch, wherein the mass ratio of the esterified starch to the antibacterial agent is 1:0.15-0.25; the mass ratio of isophorone diisocyanate to the antibacterial agent is 2-3:1.
preferably, the mass ratio of the starch to the maleic anhydride is 10:1, and the mass ratio of the esterified starch to the antibacterial agent is 1:0.2. The mass ratio of isophorone diisocyanate to the antibacterial agent is 2.5:1.
Preferably, the reaction conditions are that the dried starch and maleic anhydride are mixed uniformly according to the proportion, ball-milled and reacted for 1.5 to 2.5 hours at the temperature of 75 to 85 ℃, washed and dried to obtain esterified starch;
the esterified starch and dimethyl sulfoxide are mixed according to the mass ratio of 1:9-12, and react for 1-1.5 h at 75-85 ℃ to obtain a product 1;
under the catalysis of dibutyl tin dilaurate, isophorone diisocyanate and an antibacterial agent are reacted for 1 to 1.5 hours at the temperature of 55 to 65 ℃ according to the proportion, and the product 2 is obtained by washing and filtering;
according to esterified starch with antimicrobial agent 1: and (3) mixing the product 1 and the product 2 in a mass ratio of 0.15-0.25, reacting for 3-3.5 h at 55-65 ℃, washing and drying to obtain the antibacterial starch.
Preferably, the antibacterial agent is polyhexamethylene biguanide hydrochloride or polyhexamethylene monoguanidine hydrochloride.
The preparation method of the antibacterial starch comprises the following steps of drying starch at 80 ℃, uniformly mixing the dried starch with maleic anhydride according to a mass ratio of 10:1, ball milling for 10min, reacting for 2h at 80 ℃, washing with acetone, and drying at 45 ℃ to obtain esterified starch;
mixing esterified starch and dimethyl sulfoxide according to a mass ratio of 1:10, and reacting at 80 ℃ for 1h to obtain a product 1;
under the catalysis of dibutyl tin dilaurate, isophorone diisocyanate and polyhexamethylene biguanide hydrochloride are reacted for 1h at 60 ℃ according to the mass ratio of 5:2, and then xylene is used for filtering 3 times to obtain a product 2;
according to esterified starch with antimicrobial agent 1: and (3) mixing the product 1 and the product 2 according to the mass ratio of 0.2, reacting for 3 hours at 60 ℃, washing with ethanol, and drying at 45 ℃ to obtain the antibacterial starch.
An antibacterial starch is prepared by the preparation method.
The antibacterial starch can be applied to preparing food fresh-keeping packages.
A biguanide grafted antibacterial starch-based food preservative packaging film, comprising the following substrates:
PLA, PBAT and plasticized starch prepared from the antibacterial starch; wherein the mass ratio of the plasticized starch to the PBAT to the PLA is 2-2.5:3.8-4.2:1.
Preferably, the mass ratio of the plasticized starch, the PBAT and the PLA is 2.4:4:1.
The preparation method of the food preservative packaging film comprises the following steps:
(1) Uniformly mixing and plasticizing antibacterial starch and glycerin according to a mass ratio of 10:2-4 to obtain plasticized starch;
(2) And (3) drying the plasticized starch, PBAT and PLA, sequentially adding an antioxidant and a chain extender, uniformly mixing, granulating to obtain antibacterial master batches, and casting to obtain the food preservative packaging film.
Preferably, in step (1), the mass ratio of the antibacterial starch to the glycerol is 10:3;
preferably, in step (2), the antioxidant comprises 1 to 1.5%, preferably 1% of the total mass of the plasticized starch, PBAT, PLA, antioxidant, chain extender; the chain extender accounts for 1 to 1.5 percent, preferably 1 percent of the total mass of the plasticized starch, the PBAT, the PLA, the antioxidant and the chain extender. The granulating condition is that the rotating speed is 260-280 rpm/min, the temperature is 145-175 ℃, the casting condition is that the temperature processing parameters of each zone of the single screw casting machine are 145-175 ℃, and the rotating speed of the single screw is 75-85 r/min.
Further, in the step (2), the antioxidant is antioxidant 245, the chain extender is chain extender ADR4380, the content is 1% of the total mass of the mixture, the granulating condition is that the rotating speed is 270rpm/min, the temperature is 145 ℃, 155 ℃, 165 ℃, 175 ℃, 170 ℃, 165 ℃ and 160 ℃, and the casting condition is that the temperature processing parameters of each zone of the single screw casting machine are 145 ℃, 155 ℃, 165 ℃, 175 ℃, 170 ℃, 165 ℃ and 160 ℃ and the single screw rotating speed is 80r/min.
Advantageous effects
(1) The base materials PLA, PBAT and the antibacterial starch used in the invention are all biodegradable materials, so that the composite preservative film prepared from the base materials has good biodegradability;
(2) According to the invention, as the hydrophilic hydroxyl of the starch is replaced by the hydrophobic functional group, the hydrophobicity of the film is enhanced;
(3) The invention has high moisture resistance, oxygen resistance and bacteriostasis, and the moisture resistance can prevent the water loss in food and the water in air from entering; the oxygen barrier can prevent oxygen from entering, and avoid oxidation of food nutrient components and growth and reproduction of bacteria, thereby prolonging the shelf life of the food; the bacteriostasis is achieved by electrostatic action of guanidine cation and bacterial cell membrane anion surface, so that cell membrane damage directly leads to loss of cell components, and finally cell death is caused, thereby inhibiting food spoilage.
Drawings
FIG. 1 is a chart showing the comparison of Fourier transform infrared spectra of raw starch (A), esterified starch (B) and antibacterial starch (C) in example 1;
FIG. 2 is a scanning electron microscope comparison chart of the raw starch (A) and the antibacterial starch (B) in example 1;
FIG. 3 is a thermal weight comparison chart of raw starch and antimicrobial starch in example 1;
FIG. 4 is a graph showing comparison of primary starch and antibacterial starch in example 1, wherein the left graph shows comparison of primary starch and antibacterial starch against E.coli respectively, and the right graph shows comparison of primary starch and antibacterial starch against Staphylococcus aureus respectively;
FIG. 5 is a graph showing the contact angle between the common film (A) and the food preservative packaging film (B) in example 2;
FIG. 6 is a scanning electron microscope comparison chart of the common film and the food preservative packaging film in the embodiment 2;
fig. 7 is a comparison of the antibacterial graph of the common film and the food preservative packaging film in example 2, wherein a is the antibacterial graph of the common film against staphylococcus aureus, B is the antibacterial graph of the food preservative packaging film against staphylococcus aureus, C is the antibacterial graph of the common film against escherichia coli, and a is the antibacterial graph of the food preservative packaging film against escherichia coli;
fig. 8 is a photograph of the shelf life of fresh abalone in example 3;
figure 9 is a graph of malondialdehyde content during refrigeration of fresh abalone in example 3;
figure 10 is a graph of the relative moisture content of fresh abalone during the refrigeration period of example 3.
Detailed Description
The invention will be further described with reference to the following embodiments in order to make the technical means, the creation features, the achievement of the objects and the effects of the invention easy to understand.
Example 1 preparation of antibacterial starch
(1) The preparation process of the esterified starch comprises the following steps: drying starch at 80 ℃, uniformly mixing the starch and maleic anhydride according to the mass ratio of 10:1, ball-milling for 10min in a ball mill, reacting for 2h in an oven at 80 ℃, washing with acetone, and drying the obtained sample in the oven to obtain esterified starch;
(2) The preparation process of the antibacterial starch comprises the following steps: mixing esterified starch and dimethyl sulfoxide according to a mass ratio of 1:10, and reacting for 1h at 80 ℃ to obtain a product 1;
under the catalysis of dibutyltin dilaurate, isophorone diisocyanate and polyhexamethylene biguanide hydrochloride react for 1h at 60 ℃ according to a mass ratio of 5:2, the obtained substance is filtered by xylene for 3 times to obtain a product 2, the product 1 and the product 2 (esterified starch: polyhexamethylene biguanide hydrochloride with a mass ratio of 5:1) react for 3h at 60 ℃, the obtained product is washed by ethanol, and the obtained product is dried in a baking oven at 45 ℃ to obtain the antibacterial starch.
The antibacterial starch was characterized by FTIR, SEM, TG, antibacterial test.
Esterified starch at 1721cm was obtained by FTIR testing (as shown in FIG. 1) -1 Characteristic peaks of ester groups appear at the positions, and the antibacterial starch is 1555cm -1 Characteristic peaks of guanidino groups appear. The grafting was confirmed to be successful.
After the SEM test of the antibacterial starch (shown in figure 2) shows that the grafted polyhexamethylene biguanide hydrochloride, the structure of the antibacterial starch is destroyed, the morphology is changed, and the antibacterial starch becomes irregular and has a rough surface.
After the TG test of the antibacterial starch (as shown in fig. 3), the grafted polyhexamethylene biguanide hydrochloride has been obtained, the antibacterial starch has enhanced thermal stability, and starts to degrade after 350 ℃, and does not decompose in a high-temperature extrusion device.
The antibacterial property of the antibacterial starch is tested by an oxford cup method (shown in figure 4), and the starch grafted polyhexamethylene biguanide hydrochloride is shown to be the antibacterial starch, so that the antibacterial starch has an obvious antibacterial circle, and the obvious antibacterial property on escherichia coli and staphylococcus aureus is shown.
Example 2 preparation of food preservative packaging film from antibacterial starch and PLA and PBAT
(1) The antibacterial starch and the glycerol are uniformly mixed according to the mass ratio of 10:3, and are placed in a self-sealing bag for plasticizing, so that the plasticized starch is obtained.
(2) The plasticized starch, PBAT and PLA are put into a baking oven according to the mass ratio of 2.4:4:1, antioxidant 245 (accounting for 1% of the total mass of the mixture) and chain extender ADR4380 (accounting for 1% of the total mass of the mixture) are added, and after being uniformly mixed, the mixture is granulated by a granulator to obtain antibacterial master batches, the rotating speed of a double-screw casting machine is 270rpm/min, the inner part of the double-screw casting machine is divided into seven temperature areas, and the temperatures are 145, 155, 165, 175, 170, 165 and 160 ℃ respectively.
(3) And (3) feeding and casting the antibacterial master batch through a single-screw casting machine to prepare the food preservative packaging film. The temperature processing parameters of each zone of the single-screw casting machine are 145, 155, 165, 175, 170, 165 and 160 ℃, and the rotating speed of the single screw is set to be 80r/min.
Comparative example 1 preparation of food preservative packaging film from starch, PLA and PBAT
This comparative example is substantially the same as example 2 except that a common film having a base material of starch/PLA/PBAT in a mass ratio of 2.4:4:1 is used, and polyhexamethylene biguanide hydrochloride is not added to the common film.
Example 2 was compared to comparative example 1 and characterized by the moisture permeability, oxygen permeability, contact angle, SEM, antimicrobial tests of the films.
TABLE 1 moisture and oxygen permeability of films
Figure BDA0004061153310000081
As can be seen from Table 1, the water vapor permeability of the ordinary film made of PLA/PBAT/starch (comparative example 1) was from 707.9 g/(m) as compared with the food preservative packaging film made of PLA/PBAT/antibacterial starch (example 2) 2 D) drop to 550.56 g/(m) 2 D) oxygen transmission from 770.33cm 3 /m 2 Day 0.1MPa drop to 495.44cm 3 /m 2 Day 0.1MPa, so that the humidity resistance and the oxygen resistance of the food preservative packaging film are stronger than those of the common film.
As can be seen from the contact angle graph (CA) of the film (shown in fig. 5), the contact angle of the food preservative packaging film (example 2) is larger than that of the common film, indicating the enhanced hydrophobicity.
As can be seen from the scanning electron microscope image of the film (as shown in FIG. 6), the surface of the common film is smooth, but the surface has a plurality of cracks; the surface of the food fresh-keeping packaging film becomes rough, and a plurality of starch particles are inlaid on the surface.
According to the film bacteriostasis graph (shown in fig. 7), the bacteriostasis measurement is carried out by a shake flask method, so that the food fresh-keeping packaging film has the inhibition on escherichia coli and staphylococcus aureus, and is stronger than the common film in bacteriostasis on escherichia coli and staphylococcus aureus, and in addition, the bacteriostasis on staphylococcus aureus of the food fresh-keeping packaging film is stronger than that of escherichia coli.
Example 3 abalone preservation
(1) And sealing the food preservative packaging film prepared in the embodiment 2 by a heat sealing machine to obtain a preservative bag.
(2) Abalone fresh-keeping experiment.
Purchasing living abalone, removing shell and viscera, retaining abalone meat, washing with sterile physiological saline, and wiping the water on the surface of the abalone meat with kitchen paper. Abalone meat is randomly divided into 3 groups, namely a naked group (a), a PLA/PBAT/starch group (b) and a PLA/PBAT/antibacterial starch group (c), and the abalone meat is refrigerated in a refrigerator at the temperature of 4+/-1 ℃.
The exposed group (a) is that the abalone meat is not wrapped by a film and is exposed outside;
PLA/PBAT/starch group (b) refers to abalone meat group wrapped by fresh-keeping bag made of common film, PLA/PBAT/antibacterial starch (c) refers to abalone meat group wrapped by fresh-keeping bag made of food fresh-keeping packaging film.
The fresh-keeping effect and the shelf life of the food fresh-keeping packaging film are characterized by measuring the content of malondialdehyde in the fresh abalone refrigerating period and the total colony count in the fresh abalone refrigerating period.
By measuring the malondialdehyde content of fresh abalone in the refrigerating period (shown in figure 9), the TBARS index shows that the TBARS value gradually becomes larger along with the storage time, and the PLA/PBAT/antibacterial starch group (c) has the minimum TBARS value, so that the food preservative packaging film has obvious preservative effect.
By measuring the total number of colonies during the refrigeration of fresh abalone (as shown in fig. 10), the total number of colonies gradually rises with the lapse of storage time, and the PLA/PBAT/antimicrobial starch group (c) rises slowest, which indicates that the food preservative packaging film can effectively prolong the shelf life of abalone.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be appreciated by persons skilled in the art that the present invention is not limited to the embodiments described above, but is capable of numerous variations and modifications without departing from the spirit and scope of the invention as hereinafter claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (8)

1. The preparation method of the antibacterial starch is characterized by comprising the following steps of: mixing starch and maleic anhydride according to the mass ratio of 10:0.5-1.5, and grafting to obtain esterified starch; the esterified starch is grafted with an antibacterial agent under the action of isophorone diisocyanate to obtain antibacterial starch;
the mass ratio of the esterified starch to the antibacterial agent is 1:0.15-0.25; the mass ratio of isophorone diisocyanate to the antibacterial agent is 2-3:1.
2. the preparation method of the antibacterial starch according to claim 1, wherein the reaction conditions are that the dried starch and maleic anhydride are mixed uniformly according to a proportion, ball-milled and reacted for 1.5 to 2.5 hours at 75 to 85 ℃, washed and dried to obtain esterified starch;
the esterified starch and dimethyl sulfoxide are mixed according to the mass ratio of 1:9-12, and react for 1-1.5 h at 75-85 ℃ to obtain a product 1;
under the catalysis of dibutyl tin dilaurate, isophorone diisocyanate and an antibacterial agent are reacted for 1 to 1.5 hours at the temperature of 55 to 65 ℃ according to the proportion, and the product 2 is obtained by washing and filtering;
according to esterified starch with antimicrobial agent 1: and (3) mixing the product 1 and the product 2 in a mass ratio of 0.15-0.25, reacting for 3-3.5 h at 55-65 ℃, washing and drying to obtain the antibacterial starch.
3. The method for preparing an antibacterial starch according to claim 1 or 2, wherein the antibacterial agent is polyhexamethylene biguanide hydrochloride or polyhexamethylene monoguanidine hydrochloride.
4. An antibacterial starch prepared by the preparation method of any one of claims 1 to 3.
5. Use of the antibacterial starch according to claim 4 for preparing fresh-keeping packages for food.
6. The biguanide grafted antibacterial starch-based food preservative packaging film is characterized by comprising the following base materials in parts by mass:
a plasticized starch made from PLA, PBAT and the antimicrobial starch of claim 4; wherein the mass ratio of the plasticized starch to the PBAT to the PLA is 2-2.5:3.8-4.2:1.
7. The method for preparing the food preservative packaging film according to claim 6, which is characterized by comprising the following steps:
(1) Uniformly mixing and plasticizing antibacterial starch and glycerin according to a mass ratio of 10:2-4 to obtain plasticized starch;
(2) And (3) drying the plasticized starch, PBAT and PLA, sequentially adding an antioxidant and a chain extender, uniformly mixing, granulating to obtain antibacterial master batches, and casting to obtain the food preservative packaging film.
8. The method for producing a fresh-keeping packaging film for food according to claim 7, wherein in the step (2), the antioxidant accounts for 1 to 1.5% of the total mass of the plasticized starch, the PBAT, the PLA, the antioxidant and the chain extender, the chain extender accounts for 1 to 1.5% of the total mass of the plasticized starch, the PBAT, the PLA, the antioxidant and the chain extender, the granulating condition is that the rotating speed is 260 to 280rpm/min, the temperature is 145 to 175 ℃, the casting condition is that the temperature processing parameters of each zone of the single screw casting machine are 145 to 175 ℃, and the single screw rotating speed is 75 to 85r/min.
CN202310060448.1A 2023-01-19 2023-01-19 Antibacterial starch, food fresh-keeping packaging film and preparation method and application thereof Pending CN116178732A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310060448.1A CN116178732A (en) 2023-01-19 2023-01-19 Antibacterial starch, food fresh-keeping packaging film and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310060448.1A CN116178732A (en) 2023-01-19 2023-01-19 Antibacterial starch, food fresh-keeping packaging film and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116178732A true CN116178732A (en) 2023-05-30

Family

ID=86435932

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310060448.1A Pending CN116178732A (en) 2023-01-19 2023-01-19 Antibacterial starch, food fresh-keeping packaging film and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116178732A (en)

Similar Documents

Publication Publication Date Title
EP0474705B1 (en) Starch derived shaped articles
US5883199A (en) Polyactic acid-based blends
Martínez-Camacho et al. Extruded films of blended chitosan, low density polyethylene and ethylene acrylic acid
Júnior et al. Kefiran-based films: Fundamental concepts, formulation strategies and properties
Imam et al. Biodegradation of starch-poly (β-hydroxybutyrate-co-valerate) composites in municipal activated sludge
EP3064542B1 (en) Biodegradable thermoplastic polymer compostion, method for its manufacture and use thereof
WO2020088214A1 (en) Pha-modified tps/pbat biodegradable resin and preparation method therefor
CN112251005A (en) Natural antibacterial and mildew-resistant refrigerator fresh-keeping PLA film and processing technology thereof
CN111334016A (en) Degradable self-synergistic antibacterial bio-based polyester alloy material and preparation method and application thereof
Zena et al. Essential characteristics improvement of metallic nanoparticles loaded carbohydrate polymeric films-A review
CN103788603A (en) Polylactic acid bidirectional stretching matte thin film and preparation method thereof
CN114806113A (en) Heat-resistant antibacterial PLA full-biodegradable straw and preparation method thereof
CN114410078A (en) Slow-release degradable antibacterial preservative film and preparation method thereof
CN109988400A (en) A kind of environment-friendly type degradable packaging composite film and preparation method thereof
CN112175361B (en) High-barrier stretch-resistant antibacterial film type degradable material and preparation method thereof
CN116178732A (en) Antibacterial starch, food fresh-keeping packaging film and preparation method and application thereof
Machado et al. Melt extrusion of environmentally friendly poly (L-lactic acid)/sodium metabisulfite films for antimicrobial packaging applications
CN114410077B (en) Nano composite active packaging preservative film based on esterification modification and preparation method and application thereof
CN115584043A (en) High-barrier biodegradable film and preparation method and application thereof
CN107474501B (en) A kind of degradable food fresh keeping membrane and preparation method thereof
CN114106419A (en) Biodegradable sheet and preparation method thereof
KR102354919B1 (en) Mothod of manufacturing Antibacterial packaging film using modified zeolite and Antibacterial packaging film manufactured by the method
CN115678221B (en) Full-biodegradable bone strip material and preparation method thereof
CN114539697B (en) PVA film modified by one-step reaction extrusion method and preparation method and application thereof
CN116082744B (en) Antibacterial biodegradable preservative film and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination