CN113003596A - Light calcium carbonate in-situ filled biomacromolecule film and application thereof in packaging of oily food and medicines - Google Patents
Light calcium carbonate in-situ filled biomacromolecule film and application thereof in packaging of oily food and medicines Download PDFInfo
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Abstract
The invention belongs to the technical field of films, and relates to a light calcium carbonate in-situ filled biomacromolecule film and application thereof in packaging oily food and medicines. The method comprises the following steps: adding Ca into the mixed solution of N-hydroxypropyl-3-trimethyl chitosan HTCC and carboxymethyl cellulose CMC2+Then adding CO3 2‑Preparing light calcium carbonate in situ; and adding a plasticizer to form a film to obtain the biological macromolecular film. The chitosan/cellulose macromolecular membrane filled with the light calcium carbonate has strong antibacterial property and mechanical property, low water and oil permeability, zero cytotoxicity and proper biodegradation period.
Description
Technical Field
The invention relates to the technical field of films, and relates to a preparation method of light calcium carbonate and a biological macromolecular film as additives and application of the light calcium carbonate and the biological macromolecular film in oily food and medicine packaging.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the increasing awareness of environmental protection and government restrictions on the use of petroleum-based film materials in daily life, the development of degradable films for food and drug packaging has received urgent attention.
Cellulose is the largest biological macromolecule in nature and is produced in approximately 10 yields per year11-1012Ton, the cost is also low, is the first choice material of preparation degradable membrane. A single cellulose membrane has the disadvantages of poor thermal stability, brittleness, no antibacterial property, and the like. Carboxymethyl cellulose (CMC) is one of the most common water-soluble derivatives of cellulose and has the characteristic of uniform film formation.
The chitosan is a biological macromolecule with the content second to that of cellulose in nature, has the advantages of good biocompatibility, degradability, natural sterilization and bacteriostasis and the like, and is widely applied to the fields of food, cosmetics and medicines. N-hydroxypropyl-3-trimethyl chitosan (HTCC) is a common cationic chitosan derivative, and has the advantages of good adhesion to mucosa, promotion of cell growth, sterilization and bacteriostasis, good water solubility, no influence of solution pH on water solubility and the like. When the chitosan is used as an additive, a large amount of hydrogen bond interaction and electrostatic interaction effectively enhance the mechanical strength of the cellulose membrane and endow the cellulose membrane with antibacterial property.
In order to meet the market demand and reduce the production cost of commodities, inorganic micro-nano materials such as calcium carbonate, titanium dioxide, montmorillonite and the like are usually added into the biological macromolecular membrane. The retrieval finds that the existing reported calcium carbonate/chitosan composite membrane is unmodified chitosan in the preparation process. Unmodified chitosan can only be dissolved in an acidic solution, so that solutions such as acetic acid, hydrochloric acid and the like are needed when the solution is prepared, which promotes the dissolution of the chitosan, but has negative effects on the solubility of CMC and the property of the solution; the bactericidal and bacteriostatic activity of the common chitosan is derived from the added acid (H)+) and-NH2Combine to form-NH3 +So that the chitosan is difficult to be compounded with the carboxymethyl cellulose into a film with excellent mechanical property and sterilization and bacteriostasis.
Calcium carbonate in a calcium carbonate/chitosan or calcium carbonate/carboxymethyl cellulose composite membrane reported at present is mostly micro-nano particles obtained by grinding natural calcium carbonate, when the calcium carbonate is used as an additive in the membrane, the calcium carbonate is subjected to the processes of preparation, drying, filling and membrane forming, the process is complicated, the energy consumption is high, the particle size of the calcium carbonate is large, the particle size distribution is wide, the calcium carbonate is not well compatible with chitosan or cellulose, and the calcium carbonate is not uniformly dispersed in a membrane forming solution, so that the texture of the membrane is not uniform, and the property of the membrane is not stable. And the few composite membranes using the light calcium carbonate as an additive have the defects of complicated process and high energy consumption after the light calcium carbonate is subjected to the processes of preparation, drying, filling and film forming, so that the application of the light calcium carbonate as an auxiliary agent in film forming is limited.
Disclosure of Invention
In order to overcome the problems and reduce the use of petroleum-based membrane materials in daily life, the invention provides a light calcium carbonate in-situ filled biomacromolecule membrane and application thereof in packaging oily food and medicines. At present, the macromolecular membrane is difficult to have good mechanical property, sterilization and bacteriostasis, whiteness and hydrophilicity, low oil-water permeability and zero cytotoxicity simultaneously, and the chitosan/cellulose macromolecular membrane filled with the light calcium carbonate in situ prepared by the invention has strong antibacterial property and mechanical property, low water and oil permeability, zero cytotoxicity and local biodegradation period.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method for preparing light calcium carbonate as an in-situ additive by regulating and controlling biopolymer solution with opposite charges, comprising:
adding Ca into mixed solution of N-hydroxypropyl-3-trimethyl chitosan (HTCC) with cations and carboxymethyl cellulose (CMC) with anions2+Then adding CO3 2-And preparing the light calcium carbonate. The crystal form and the appearance of the calcium carbonate are adjusted by adjusting the mass ratio of the HTCC to the CMC and the crystallization temperature of the calcium carbonate.
In a second aspect of the invention, a method for preparing an HTCC/CMC composite membrane by in-situ filling of precipitated calcium carbonate is provided.
The method comprises the following steps:
adding plasticizer into the system for preparing light calcium carbonate, and forming film to obtain raw calcium carbonateA macromolecular membrane. The invention adopts light calcium carbonate in-situ filling, and Ca is firstly added into a mixed solution of modified chitosan HTCC and carboxymethyl cellulose CMC2 +Then adding CO3 2Controlling the crystallization of calcium carbonate in the mixed HTCC/CMC solution, and directly adding HTCC/CMC/CaCO to the film-forming solution without separating and drying the calcium carbonate from the solution3The system is used for preparing the membrane, the operation steps are simple, the production period is short, and the energy consumption is low.
In the third aspect of the present invention, the biopolymer membrane prepared according to the above-described method has excellent properties.
The chitosan adopted by the invention is a cationic derivative of chitosan, and has constant quaternary ammonium salt ions (cations) in the molecules, and the solubility of the chitosan in water is not influenced by the pH value of the solution. The other biological macromolecule is carboxymethyl chitosan with negative charge. The cationic chitosan derivative HTCC and CMC have a large number of hydrogen bond actions and strong electrostatic actions, and the compatibility between two biological macromolecules and light calcium carbonate, so that the chitosan/cellulose macromolecular membrane filled with the light calcium carbonate has strong antibacterial property and mechanical property, low water and oil permeability, zero cytotoxicity and proper biodegradation period.
In a fourth aspect of the invention, the application of the biomacromolecule film in oily food packaging is provided.
The chitosan/cellulose macromolecular membrane filled with the light calcium carbonate prepared by the invention has strong antibacterial property and mechanical property, good biocompatibility, low water and oil permeability, zero cytotoxicity and proper biodegradation period, so that the chitosan/cellulose macromolecular membrane is expected to be widely applied to packaging of oily food and medicines.
The invention has the beneficial effects that:
(1) in the invention, HTCC and CMC form a stable spatial network structure through electrostatic force and hydrogen bonding, and excessive carboxylic acid ions (HTCC is less than CMC) in the mixture can react with Ca2+Bonding by strong electrostatic action to make Ca2+Fused into a space network structure to achieve the effect of efficiently regulating and controlling calcium carbonate。
(2) In the crystallization process of calcium carbonate, HTCC is adsorbed on the surface of calcium carbonate through cations, hydroxyl and amino; CMC is adsorbed on the surface of calcium carbonate microcrystal through carboxyl and hydroxyl. During the aging process of the calcium carbonate crystals, part of the HTCC and the CMC are wrapped in the interior of the calcium carbonate crystals, and part of the HTCC and the CMC are adsorbed on the surfaces of the calcium carbonate crystals. The HTCC and CMC on the surface of the crystal are homologous with the HTCC and CMC in the film-forming solution, so the filling of calcium carbonate is facilitated; the strong electrostatic and hydrogen bond interaction between HTCC and CMC molecules on the surface of calcium carbonate and HTCC and CMC molecules in the film forming solution enhances the mechanical properties of the film.
(3) The light calcium carbonate/natural macromolecular membrane prepared by the method has a flat surface, a compact interface and no obvious pores, and the interface presents small protrusions of calcium carbonate particles. The breaking strength of the light calcium carbonate/natural macromolecular membrane is 10-37MPa, and the breaking elongation is 8-35%.
(4) The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance of 0.6-1.3cm for Staphylococcus aureus and 0.5-1.4cm for colibacillus.
(5) The light calcium carbonate/natural polymer film has water vapor transmission rate of 50-78 gm.m-2·d-1(relative humidity 90%, measured at 37 ℃).
(6) The light calcium carbonate/natural polymer film has a permeability of 0.3-1.1 g/(m) to peanut oil-2·d-1)(37℃)。
(7) The whiteness of the light calcium carbonate/natural polymer film is 85-93%. The contact angle between the light calcium carbonate/natural polymer film and the water drop is 30-48 degrees.
(8) The light calcium carbonate/natural polymer membrane has the growth promoting capacity of 102-120 percent to the endothelial cells of the umbilical vein of human.
(9) The preparation method is simple, convenient to operate, high in practicability and easy to popularize.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
A preparation method of a light calcium carbonate in-situ filled biomacromolecule membrane comprises the following steps:
adding Ca into a mixed solution of N-hydroxypropyl-3-trimethyl chitosan (HTCC) and carboxymethyl cellulose (CMC)2+Then adding CO3 2-Preparing light calcium carbonate in situ; and adding a plasticizer to form a film to obtain the biological macromolecular film.
In some embodiments, [ Ca ] when preparing precipitated calcium carbonate2+]Andis 5-20mmol/L, [ Ca ]2+]/1/1, the aging time is 2-6h, the electromagnetic stirring speed is 300-1200rpm, and the temperature is 25-60 ℃.
In some embodiments, the film-forming solution has a CMC concentration of 1-3% by weight, mHTCC/mCMCThe dosage m of the polyvinyl alcohol is 1/10-5/10PVA/(mCMC+mHTCC) 20-30 percent of light calcium carbonate, and the dosage m of the light calcium carbonateCaCO3/(mCMC+mHTCC) 0.17-0.68 percent.
The present invention is further described with reference to specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting.
In the following examples, the mechanical properties of the films are tested, with reference to the international standard ISO 1184-1983;
the antibacterial property test refers to ' the light industry standard of the people's republic of China (QB/T2591-2003) ';
the water vapor transmission rate is referred to the national standard GB/T21529-;
the peanut oil transmittance is referred to the national standard GB/T24999-;
in the cell growth experiment, blank samples are used as reference standards.
Example 1:
1. preparation of biological macromolecule mixed solution
Mother solutions with the concentration of N-hydroxypropyl-3-trimethyl chitosan (HTCC) and carboxymethyl cellulose (CMC) of 4 percent are respectively prepared and are dissolved in a water bath at the temperature of 60 ℃ by electromagnetic stirring. The mother liquor can be used after standing at room temperature for 12 hours.
2. Preparation of calcium chloride and sodium carbonate mother liquor
Accurately weighing 1.11g of calcium chloride solid at room temperature, dissolving, fixing the volume in a volumetric flask of 200mL, and filtering by using qualitative filter paper to obtain calcium chloride mother liquor with the concentration of 50 mmol/L. The same method is used for preparing sodium carbonate mother liquor with the same concentration. The mixture was left to stand at room temperature for 12 hours and then used.
3. Regulated preparation of light calcium carbonate
In the experiment for regulating and controlling the preparation of the light calcium carbonate, the concentration of the carboxymethyl cellulose is 2 percent and mHTCC/mCMC1/10. Weighing 20g of CMC mother liquor and 18g of deionized water, sequentially adding into a small beaker with the capacity of 100ml, stirring for 2h at constant temperature in a water bath at 60 ℃, slowly dropwise adding 2g of HTCC mother liquor, and continuously stirring for 2h at constant temperature to ensure that the HTCC and the CMC are fully interacted.
Under the condition of electromagnetic stirring at the stirring speed of 300rpm, slowly dropwise adding 2.25mL of calcium chloride solution (the dropwise adding speed is 0.1mL/min) into 20mL of the HTCC/CMC mixed solution, and stirring for 30min to obtain [ Ca ]2+]Is HTCC/CMC/Ca of 5mmol/L2+And (3) solution. To HTCC/CMC/Ca2+2.25mL of sodium carbonate solution is added into the solution drop by drop at the speed of 0.05mL/min, and the stirring is continued for 2h at the temperature of 60 ℃ to obtain the light calcium carbonate regulated and controlled by the HTCC/CMC mixed solution.
4. Light calcium carbonate in-situ filled biological macromolecular membrane
The system of "3" above was cooled to room temperature (20 ℃) and then polyvinyl alcohol (PVA), a plasticizer, was added in an amount of 30% of the total mass of CMC and HTCC. Mixing HTCC/CMC/CaCO3Pouring the PVA film forming solution into a polytetrafluoroethylene mold while the PVA film forming solution is hot, transferring the polytetrafluoroethylene mold to a blast drying oven at the temperature of 30 ℃, and preparing the light calcium carbonate in-situ filled biological macromolecular film.
5.HTCC/CMC/CaCO3Properties of PVA film
The thermal decomposition temperature of the light calcium carbonate/natural macromolecular membrane is 276.3 ℃.
The breaking strength of the light calcium carbonate/natural macromolecular membrane is 27MPa, and the breaking elongation is 16%.
The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance, the diameter of the bacteriostasis circle to staphylococcus aureus is 1.0cm, and the diameter of the bacteriostasis circle to escherichia coli is 0.8 cm.
The water vapor transmission rate of the light calcium carbonate/natural polymer film is 55 gm.m-2·d-1(relative humidity 90%, 37 ℃).
The light calcium carbonate/natural polymer film has a permeability of 0.5 g/(m)-2·d-1)(37℃)。
The whiteness of the light calcium carbonate/natural polymer film is 89%.
The contact angle between the light calcium carbonate/natural polymer film and the water drop is 38 degrees.
The light calcium carbonate/natural polymer membrane has 112 percent of growth promoting capacity on human umbilical vein endothelial cells.
The light calcium carbonate/natural polymer film degraded to 0.65 times of the average molecular weight of the original HTCC/CMC mixture at 30 days, degraded to 0.35 times of the average molecular weight of the original HTCC/CMC mixture at 60 days, and completely degraded (40 ℃, 90% humidity) at 108 days.
Example 2
1. The difference from example 1 is that: the concentration of the carboxymethyl cellulose was 1% by mass.
2.HTCC/CMC/CaCO3Of PVA filmProperties of
The thermal decomposition temperature of the light calcium carbonate/natural macromolecular membrane is 276.7 ℃.
The breaking strength of the light calcium carbonate/natural macromolecular membrane is 20MPa, and the breaking elongation is 12%.
The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance of 0.9cm for Staphylococcus aureus and 0.86cm for colibacillus.
The water vapor transmission rate of the light calcium carbonate/natural polymer film is 70 gm.m-2·d-1(relative humidity 90%, 37 ℃).
The light calcium carbonate/natural polymer film has a permeability of 0.95 g/(m)-2·d-1)(37℃)。
The whiteness of the light calcium carbonate/natural polymer film is 93 percent.
The contact angle between the light calcium carbonate/natural polymer film and the water drop is 30 degrees.
The light calcium carbonate/natural polymer membrane has 102 percent of growth promoting capacity on human umbilical vein endothelial cells.
The light calcium carbonate/natural polymer film degraded to 0.60 times of the average molecular weight of the original HTCC/CMC mixture at 30 days, degraded to 0.31 times of the average molecular weight of the original HTCC/CMC mixture at 60 days, and completely degraded (40 ℃, 90% humidity) at 100 days.
Example 3
1. The difference from example 1 is that: the concentration of the carboxymethyl cellulose was 3 mass%.
2.HTCC/CMC/CaCO3Properties of PVA film
The thermal decomposition temperature of the light calcium carbonate/natural macromolecular membrane is 279.5 ℃.
The breaking strength of the light calcium carbonate/natural macromolecular membrane is 37MPa, and the breaking elongation is 14%.
The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance, the diameter of the bacteriostasis circle to staphylococcus aureus is 1.0cm, and the diameter of the bacteriostasis circle to escherichia coli is 1.1 cm.
Steam of light calcium carbonate/natural polymer filmThe transmittance was 52gm m-2·d-1(relative humidity 90%, 37 ℃).
The light calcium carbonate/natural polymer film has a permeability of 0.45 g/(m)-2·d-1)(37℃)。
The whiteness of the light calcium carbonate/natural polymer film is 85 percent.
The contact angle between the light calcium carbonate/natural polymer film and the water drop is 41 degrees.
The light calcium carbonate/natural polymer membrane has 120 percent of growth promoting capacity on human umbilical vein endothelial cells.
The light calcium carbonate/natural polymer film degraded to 0.66 times of the average molecular weight of the original HTCC/CMC mixture at 30 days, 0.36 times of the average molecular weight of the original HTCC/CMC mixture at 60 days, and completely degraded (40 ℃, 90% humidity) at 115 days.
Example 4
1. The difference from example 1 is that: m isHTCC/mCMcThe ratio is 3/10.
2.HTCC/CMC/CaCO3Properties of PVA film
The thermal decomposition temperature of the light calcium carbonate/natural macromolecular membrane is 274.3 ℃.
The breaking strength of the light calcium carbonate/natural macromolecular membrane is 30MPa, and the breaking elongation is 12%.
The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance, the diameter of the bacteriostasis circle to staphylococcus aureus is 1.3cm, and the diameter of the bacteriostasis circle to escherichia coli is 1.4 cm.
The water vapor transmission rate of the light calcium carbonate/natural polymer film is 65 gm.m-2·d-1(relative humidity 90%, 37 ℃).
The light calcium carbonate/natural polymer film has a permeability of 0.86 g/(m)-2·d-1)(37℃)。
The whiteness of the light calcium carbonate/natural polymer film is 87%.
The contact angle between the light calcium carbonate/natural polymer film and the water drop is 45 degrees.
The light calcium carbonate/natural polymer membrane has 118 percent of growth promoting capacity on human umbilical vein endothelial cells.
The light calcium carbonate/natural polymer film degraded to 0.68 times of the average molecular weight of the original HTCC/CMC mixture at 30 days, 0.37 times of the average molecular weight of the original HTCC/CMC mixture at 60 days, and completely degraded (40 ℃, 90% humidity) at 120 days.
Example 5
1. The difference from example 1 is that: m isHTCC/mCMCThe ratio is 5/10.
2.HTCC/CMC/CaCO3Properties of PVA film
The thermal decomposition temperature of the light calcium carbonate/natural macromolecular membrane is 275.2 ℃.
The breaking strength of the light calcium carbonate/natural macromolecular membrane is 33MPa, and the breaking elongation is 8%.
The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance, the diameter of the bacteriostasis circle to staphylococcus aureus is 1.3cm, and the diameter of the bacteriostasis circle to escherichia coli is 1.4 cm.
The water vapor transmission rate of the light calcium carbonate/natural polymer film is 50 gm.m-2·d-1(relative humidity 90%, 37 ℃).
The light calcium carbonate/natural polymer film has a permeability of 0.3 g/(m)-2·d-1)(37℃)。
The whiteness of the light calcium carbonate/natural polymer film is 85 percent.
The contact angle between the light calcium carbonate/natural polymer film and the water drop is 48 degrees.
The light calcium carbonate/natural polymer membrane has 120 percent of growth promoting capacity on human umbilical vein endothelial cells.
The light calcium carbonate/natural polymer film degraded to 0.67 times of the average molecular weight of the original HTCC/CMC mixture at 30 days, 0.36 times of the average molecular weight of the original HTCC/CMC mixture at 60 days, and completely degraded (40 ℃, 90% humidity) at 121 days.
Example 6
1. The difference from example 1 is that: [ Ca ]2+]=[CO3 2-]=10mmol/L。
2.HTCC/CMC/CaCO3Properties of PVA film
The thermal decomposition temperature of the light calcium carbonate/natural macromolecular membrane is 276.1 ℃.
The breaking strength of the light calcium carbonate/natural macromolecular membrane is 33MPa, and the breaking elongation is 13%.
The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance of 0.9cm for Staphylococcus aureus and 0.9cm for colibacillus.
The water vapor transmission rate of the light calcium carbonate/natural polymer film is 69 gm.m-2·d-1(relative humidity 90%, 37 ℃).
The light calcium carbonate/natural polymer film has a permeability of 0.71 g/(m)-2·d-1)(37℃)。
The whiteness of the light calcium carbonate/natural polymer film is 90 percent.
The contact angle between the light calcium carbonate/natural polymer film and the water drop is 42 degrees.
The light calcium carbonate/natural polymer film has 115 percent of growth promoting capacity on human umbilical vein endothelial cells.
The light calcium carbonate/natural polymer film degraded to 0.65 times of the average molecular weight of the original HTCC/CMC mixture at 30 days, degraded to 0.34 times of the average molecular weight of the original HTCC/CMC mixture at 60 days, and completely degraded (40 ℃, 90% humidity) at 108 days.
Example 7
1. The difference from example 1 is that: [ Ca ]2+]=[CO3 2-]=20mmol/L。
2.HTCC/CMC/CaCO3Properties of PVA film
The thermal decomposition temperature of the light calcium carbonate/natural macromolecular membrane is 274.6 ℃.
The breaking strength of the light calcium carbonate/natural macromolecular membrane is 10MPa, and the breaking elongation is 18%.
The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance, the diameter of a bacteriostasis ring for staphylococcus aureus is 0.6cm, and the diameter of a bacteriostasis ring for escherichia coli is 0.65 cm.
The water vapor transmission rate of the light calcium carbonate/natural polymer film is 78 gm.m-2·d-1(relative humidity 90%, 37 ℃).
The light calcium carbonate/natural polymer film has a permeability of 1.1 g/(m)-2·d-1)(37℃)。
The whiteness of the light calcium carbonate/natural polymer film is 92 percent.
The contact angle between the light calcium carbonate/natural polymer film and the water drop is 43 degrees.
The light calcium carbonate/natural polymer membrane has 105 percent of growth promoting capacity on human umbilical vein endothelial cells.
The light calcium carbonate/natural polymer film degraded to 0.64 times of the average molecular weight of the original HTCC/CMC mixture at 30 days, degraded to 0.35 times of the average molecular weight of the original HTCC/CMC mixture at 60 days, and completely degraded (40 ℃, 90% humidity) at 110 days.
Example 8
1. The difference from example 1 is that: in step 3, under the condition of electromagnetic stirring at a stirring speed of 300rpm, slowly dropwise adding 2.25mL of calcium chloride solution (the dropwise adding speed is 0.1mL/min) into 20mL of the HTCC/CMC mixed solution, and stirring for 30min to obtain [ Ca ]2+]Is HTCC/CMC/Ca of 5mmol/L2+And (3) solution. To HTCC/CMC/Ca2+2.25mL of sodium carbonate solution is added dropwise into the solution at the speed of 0.05mL/min, and stirring is continued for 2h at the temperature of 60 ℃ to obtain a crude product of calcium carbonate.
2.HTCC/CMC/CaCO3Properties of PVA film
The thermal decomposition temperature of the light calcium carbonate/natural macromolecular membrane is 277.5 ℃.
The breaking strength of the light calcium carbonate/natural macromolecular membrane is 35MPa, and the breaking elongation is 35%.
The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance, the diameter of a bacteriostasis ring for staphylococcus aureus is 0.95cm, and the diameter of a bacteriostasis ring for escherichia coli is 1.05 cm.
The water vapor transmission rate of the light calcium carbonate/natural polymer film is 55 gm.m-2·d-1(relative humidity 90%, 37 ℃).
The light calcium carbonate/natural polymer film has a permeability of 0.35 g/(m)-2·d-1)(37℃)。
The whiteness of the light calcium carbonate/natural polymer film is 0.90 percent.
The contact angle between the light calcium carbonate/natural polymer film and the water drop is 35 degrees.
The light calcium carbonate/natural polymer film has 115 percent of growth promoting capacity on human umbilical vein endothelial cells.
The light calcium carbonate/natural polymer film degraded to 0.65 times of the average molecular weight of the original HTCC/CMC mixture at 30 days, degraded to 0.35 times of the average molecular weight of the original HTCC/CMC mixture at 60 days, and completely degraded (40 ℃, 90% humidity) at 108 days.
Example 9
1. The difference from example 1 is that: in step 3, under electromagnetic stirring at 1200rpm, slowly dropwise adding 2.25mL of calcium chloride solution (dropwise adding speed of 0.1mL/min) into 20mL of the HTCC/CMC mixed solution, and stirring for 30min to obtain [ Ca ]2+]Is HTCC/CMC/Ca of 5mmol/L2+And (3) solution. To HTCC/CMC/Ca2+2.25mL of sodium carbonate solution is added dropwise into the solution at the speed of 0.05mL/min, and stirring is continued for 6h at 25 ℃ to obtain a crude product of calcium carbonate.
2.HTCC/CMC/CaCO3Properties of PVA film
The thermal decomposition temperature of the light calcium carbonate/natural macromolecular membrane is 275.9 ℃.
The breaking strength of the light calcium carbonate/natural macromolecular membrane is 10MPa, and the breaking elongation is 18%.
The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance, the diameter of a bacteriostasis ring for staphylococcus aureus is 0.6cm, and the diameter of a bacteriostasis ring for escherichia coli is 0.65 cm.
The water vapor transmission rate of the light calcium carbonate/natural polymer film is 78 gm.m-2·d-1(relative humidity 90%, 37 ℃).
The light calcium carbonate/natural polymer film has a permeability of 1.1 g/(m)-2·d-1)(37℃)。
The whiteness of the light calcium carbonate/natural polymer film is 92 percent.
The contact angle between the light calcium carbonate/natural polymer film and the water drop is 43 degrees.
The light calcium carbonate/natural polymer membrane has 105 percent of growth promoting capacity on human umbilical vein endothelial cells.
The light calcium carbonate/natural polymer film degraded to 0.64 times of the average molecular weight of the original HTCC/CMC mixture at 30 days, 0.35 times of the average molecular weight of the original HTCC/CMC mixture at 60 days, and completely degraded (40 ℃, 90% humidity) at 119 days.
Example 10
1. The difference from example 1 is that: in step 3, under the condition of electromagnetic stirring at 800rpm, slowly dripping 2.25mL of calcium chloride solution (dripping speed is 0.1mL/min) into 20mL of the HTCC/CMC mixed solution, and stirring for 30min to obtain [ Ca ]2+]Is HTCC/CMC/Ca of 5mmol/L2+And (3) solution. To HTCC/CMC/Ca2+2.25mL of sodium carbonate solution was added dropwise to the solution at a rate of 0.05mL/min, and stirring was continued at 40 ℃ for 4.5h to obtain a crude product, calcium carbonate.
2.HTCC/CMC/CaCO3Properties of PVA film
The thermal decomposition temperature of the light calcium carbonate/natural macromolecular membrane is 276.0 ℃.
The breaking strength of the light calcium carbonate/natural macromolecular membrane is 20MPa, and the breaking elongation is 15%.
The light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance of 0.85cm for Staphylococcus aureus and 0.88cm for colibacillus.
The water vapor transmission rate of the light calcium carbonate/natural polymer film is 71 gm.m-2·d-1(relative humidity 90%, 37 ℃).
The light calcium carbonate/natural polymer film has a permeability of 0.45 g/(m)-2·d-1)(37℃)。
The whiteness of the light calcium carbonate/natural polymer film is 91 percent.
The contact angle between the light calcium carbonate/natural polymer film and the water drop is 40 degrees.
The light calcium carbonate/natural polymer membrane has 114 percent of growth promoting capacity on human umbilical vein endothelial cells.
The light calcium carbonate/natural polymer film degraded to 0.66 times of the average molecular weight of the original HTCC/CMC mixture at 30 days, 0.36 times of the average molecular weight of the original HTCC/CMC mixture at 60 days, and completely degraded (40 ℃, 90% humidity) at 125 days.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A method for preparing light calcium carbonate as a filler in situ is characterized by comprising the following steps:
adding Ca into the mixed solution of N-hydroxypropyl-3-trimethyl chitosan HTCC and carboxymethyl cellulose CMC2+Wait for Ca2+Adding CO after fully reacting with carboxylic acid and ions in CMC3 2-And preparing the light calcium carbonate at the reaction temperature under mechanical stirring.
2. Precipitated calcium carbonate produced by the process of claim 1, wherein the crystalline form of the precipitated calcium carbonate comprises a calcite, aragonite, and aragonite mixture; the appearance comprises micron-sized spherical particles formed by aggregating hexahedron-shaped spherical small nano particles layer by layer and irregularly-shaped micro-nano calcium carbonate particles; the side length of the hexahedron is 0.8-6 μm, the particle size of the nano particles is 10-60nm, and the particle size of the micro spherical particles formed by aggregating the nano particles is 0.5-5 μm; the specific gravity of the light calcium carbonate is 1.6-1.68g/cm3Specific surface area of 8-12m2(ii)/g; the whiteness of the light calcium carbonate is 93.8-96.1%.
3. The preparation method of the light calcium carbonate in-situ filled biomacromolecule membrane is characterized by comprising the following steps:
adding Ca into the mixed solution of N-hydroxypropyl-3-trimethyl chitosan HTCC and carboxymethyl cellulose CMC2+Then adding CO3 2-Preparing light calcium carbonate; and adding a plasticizer to form a film to obtain the biological macromolecular film.
4. The method for preparing the light calcium carbonate in-situ filled biomacromolecule membrane as claimed in claim 1, wherein the in-situ preparation comprises the following specific steps: adding Ca into the mixed solution of N-hydroxypropyl-3-trimethyl chitosan HTCC and carboxymethyl cellulose CMC dropwise2+The solution is evenly mixed to obtain HTCC/CMC/Ca2+A solution; then to HTCC/CMC/Ca2+Dropwise adding CO-containing solution3 2-The solution is aged at 25-60 ℃ under electromagnetic stirring to obtain the light calcium carbonate.
5. The method for preparing light calcium carbonate in-situ-filled biomacromolecule membrane as claimed in claim 1, wherein Ca2+And CO3 2-The concentration of (A) is 5-20mmol/L, Ca2+/CO3 2-Is 1/1.
6. The method for preparing in-situ light calcium carbonate-filled biomacromolecule membrane as claimed in claim 1, wherein the aging time is 2-6h, and the stirring speed is 300-1200 rpm.
7. The method for preparing the light calcium carbonate in-situ filled biomacromolecule membrane as claimed in claim 1, wherein the concentration of the carboxymethyl cellulose CMC is 1-3% by mass percent;
at the same time, mHTCC/mCMCThe ratio is 1/10-5/10.
8. The method for preparing the light calcium carbonate in-situ filling biomacromolecule film as claimed in claim 1, wherein the plasticizer is polyvinyl alcohol PVA, and the adding amount of the plasticizer is 30-40% of the total mass of CMC and HTCC.
9. The biological macromolecular membrane prepared by the method of any one of claims 3 to 8, characterized in that preferably, the light calcium carbonate/natural macromolecular membrane has a flat surface, small protrusions of calcium carbonate particles are presented on the interface, the interface is compact, and no obvious pores are left;
the light calcium carbonate/natural macromolecular membrane simultaneously has the following properties: the breaking strength is more than 10MPa, and the breaking elongation is more than 8 percent;
the light calcium carbonate/natural polymer film has the sterilization and bacteriostasis performance, the diameter of a bacteriostasis ring on staphylococcus aureus is larger than 0.6cm, and the diameter of a bacteriostasis ring on escherichia coli is larger than 0.5 cm;
the water vapor transmission rate of the light calcium carbonate/natural polymer film is less than 78 gm.m-2·d-1Relative humidity of 90%, measured at 37 ℃;
the light calcium carbonate/natural polymer film has a permeability of less than 1.1 g/(m)-2·d-1),37℃;
The whiteness of the light calcium carbonate/natural polymer film is more than 85 percent; the contact angle between the light calcium carbonate/natural polymer film and the water drop is less than 48 degrees;
the growth promoting capacity of the light calcium carbonate/natural polymer membrane on human umbilical vein endothelial cells is more than 102 percent.
10. Use of the biomacromolecule membrane of claim 9 in the packaging of oily food and pharmaceuticals.
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CN108190935A (en) * | 2018-04-04 | 2018-06-22 | 广西民族大学 | A kind of preparation method of strip of sheet calcium carbonate superfine particle |
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