CN113003596B - 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 PDF

Info

Publication number
CN113003596B
CN113003596B CN202110205363.9A CN202110205363A CN113003596B CN 113003596 B CN113003596 B CN 113003596B CN 202110205363 A CN202110205363 A CN 202110205363A CN 113003596 B CN113003596 B CN 113003596B
Authority
CN
China
Prior art keywords
calcium carbonate
light calcium
membrane
cmc
htcc
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.)
Active
Application number
CN202110205363.9A
Other languages
Chinese (zh)
Other versions
CN113003596A (en
Inventor
杨效登
李燕
王领
李天铎
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.)
Qilu University of Technology
Original Assignee
Qilu University of Technology
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 Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN202110205363.9A priority Critical patent/CN113003596B/en
Publication of CN113003596A publication Critical patent/CN113003596A/en
Application granted granted Critical
Publication of CN113003596B publication Critical patent/CN113003596B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • 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
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials For Medical Uses (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention belongs to the technical field of membranes, and relates to a light calcium carbonate in-situ filled biomacromolecule membrane and application thereofThe application 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 CMC 2+ Then adding CO 3 2‑ Preparing light calcium carbonate in situ; and adding a plasticizer to form a film, thus obtaining 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

Light calcium carbonate in-situ filled biomacromolecule film and application thereof in packaging of oily food and medicines
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 year 11 -10 12 Ton, 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, cell growth promotion, 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-NH 2 Combine to form-NH 3 + 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 a mixed solution of N-hydroxypropyl-3-trimethyl chitosan (HTCC) with cations and carboxymethyl cellulose (CMC) with anions 2+ Then adding CO 3 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:
and adding a plasticizer into the system for preparing the light calcium carbonate to form a film, thus obtaining the biological macromolecular film. 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 CMC 2 + Adding CO 3 2 Controlling 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 solution 3 The 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) the HTCC and CMC of the present invention form a stable spatial network structure by electrostatic force and hydrogen bonding, and excessive carboxylic acid heel ions (HTCC is used in an amount less than CMC) in the mixture can react with Ca 2+ Bonding by strong electrostatic action to make Ca 2+ 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. 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 bonding interaction between the HTCC and CMC molecules on the surface of the calcium carbonate and the 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 should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. 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 CO 3 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 carbonate 2+ ]And
Figure BDA0002950266590000051
is 5-20mmol/L, [ Ca ] 2+ ]/
Figure BDA0002950266590000052
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, m HTCC /m CMC The dosage m of the polyvinyl alcohol is 1/10-5/10 PVA /(m CMC +m HTCC ) 20-30 percent of light calcium carbonate, and the dosage m of the light calcium carbonate CaCO3 /(m CMC +m HTCC ) 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 as the national standard GB/T24999-2010 of the people's republic of China;
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 is 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 m HTCC /m CMC 1/10. 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/L 2+ And (3) solution. To HTCC/CMC/Ca 2+ 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/CaCO 3 Pouring 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/CaCO 3 Properties 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 (relatively Wet)Degree 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/CaCO 3 Properties of PVA film
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/CaCO 3 Properties 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 that the diameter of an inhibition zone for staphylococcus aureus is 1.0cm, and the diameter of an inhibition zone for escherichia coli is 1.1 cm.
The water vapor transmission rate of the light calcium carbonate/natural polymer film is 52 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 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 is HTCC /m CMc The ratio is 3/10.
2.HTCC/CMC/CaCO 3 Properties 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 is HTCC /m CMC The ratio is 5/10.
2.HTCC/CMC/CaCO 3 Properties 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 50gm·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+ ]＝[CO 3 2- ]＝10mmol/L。
2.HTCC/CMC/CaCO 3 Properties 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 bactericidal and bacteriostatic activity, the diameter of a bacteriostatic circle for staphylococcus aureus is 0.9cm, and the diameter of a bacteriostatic circle for escherichia coli is 0.9 cm.
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 a 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+ ]＝[CO 3 2- ]＝20mmol/L。
2.HTCC/CMC/CaCO 3 Properties 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, 20mL of the HTCC/CMC was mixed with the above-mentioned mixture under electromagnetic stirring at a stirring speed of 300rpmSlowly dripping 2.25mL calcium chloride solution (dripping speed is 0.1mL/min) into the mixed solution, and stirring for 30min to obtain [ Ca ] 2+ ]Is HTCC/CMC/Ca of 5mmol/L 2+ And (3) solution. To HTCC/CMC/Ca 2+ 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/CaCO 3 Properties 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) to peanut oil -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/L 2+ And (3) solution. To HTCC/CMC/Ca 2+ 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/CaCO 3 Properties 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 electromagnetic stirring speed of 800rpm, slowly dripping 2.25mL of calcium chloride solution (dripping 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/L 2+ And (3) solution. To HTCC/CMC/Ca 2+ 2.25mL of sodium carbonate solution is added dropwise into the solution at the speed of 0.05mL/min, and stirring is continued for 4.5h at 40 ℃ to obtain a crude product of calcium carbonate.
2.HTCC/CMC/CaCO 3 Properties 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 (9)

1. The preparation method of the light calcium carbonate in-situ filled biomacromolecule membrane is characterized by comprising the following steps:
preparing light calcium carbonate, adding a plasticizer, and forming a film to obtain a biological macromolecular film;
the preparation method of the light calcium carbonate comprises the following steps: adding Ca into the mixed solution of N-hydroxypropyl-3-trimethyl chitosan HTCC and carboxymethyl cellulose CMC 2+ Wait for Ca 2+ After fully reacting with carboxylate ions in CMC, adding CO 3 2- And preparing the light calcium carbonate at the reaction temperature under mechanical stirring.
2. The method for preparing the light calcium carbonate in-situ filled biomacromolecule membrane as claimed in claim 1, wherein the crystal form of the light calcium carbonate obtained by the light calcium carbonate preparation method comprises 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/cm 3 Specific surface area of 8-12m 2 (ii)/g; the whiteness of the light calcium carbonate is 93.8-96.1%.
3. 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 dropwise 2+ The solution is evenly mixed to obtain HTCC/CMC/Ca 2+ A solution; then to HTCC/CMC/Ca 2+ Dropwise adding CO-containing solution 3 2- The solution is aged at 25-60 ℃ under electromagnetic stirring to obtain the light calcium carbonate.
4. The method for preparing light calcium carbonate in-situ-filled biomacromolecule membrane as claimed in claim 1, wherein Ca 2+ And CO 3 2- The concentration of (A) is 5-20mmol/L, Ca 2+ /CO 3 2- Is 1/1.
5. 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.
6. 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, m HTCC /m CMC The ratio is 1/10-5/10.
7. 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.
8. The biological macromolecular membrane prepared by the method of any one of claims 1 to 7, characterized in that the surface of the biological macromolecular membrane is flat, the interface presents calcium carbonate particle small protrusions, the interface is compact and has no obvious pores;
the biological macromolecular membrane simultaneously has the following properties: the breaking strength is more than 10MPa, and the breaking elongation is more than 8 percent;
the biological macromolecular membrane has the bactericidal and bacteriostatic properties, the diameter of a bacteriostatic circle for staphylococcus aureus is more than 0.6cm, and the diameter of a bacteriostatic circle for escherichia coli is more than 0.5 cm;
the water vapor transmission rate of the biological macromolecular membrane is less than 78 g.m -2 ·d -1 Relative humidity of 90%, measured at 37 ℃;
the permeability of the biological macromolecular membrane to the peanut oil is less than 1.1g(m -2 ·d -1 )，37℃；
The whiteness of the biological macromolecular membrane is more than 85 percent; the contact angle between the biomacromolecule film and the water drop is less than 48 degrees;
the growth promoting capacity of the biological macromolecular membrane to human umbilical vein endothelial cells is more than 102 percent.
9. Use of the biomacromolecule membrane of claim 8 in the packaging of oily food and pharmaceuticals.
CN202110205363.9A 2021-02-24 2021-02-24 Light calcium carbonate in-situ filled biomacromolecule film and application thereof in packaging of oily food and medicines Active CN113003596B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110205363.9A CN113003596B (en) 2021-02-24 2021-02-24 Light calcium carbonate in-situ filled biomacromolecule film and application thereof in packaging of oily food and medicines

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110205363.9A CN113003596B (en) 2021-02-24 2021-02-24 Light calcium carbonate in-situ filled biomacromolecule film and application thereof in packaging of oily food and medicines

Publications (2)

Publication Number Publication Date
CN113003596A CN113003596A (en) 2021-06-22
CN113003596B true CN113003596B (en) 2022-09-20

Family

ID=76385605

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110205363.9A Active CN113003596B (en) 2021-02-24 2021-02-24 Light calcium carbonate in-situ filled biomacromolecule film and application thereof in packaging of oily food and medicines

Country Status (1)

Country Link
CN (1) CN113003596B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113698640B (en) * 2021-09-15 2023-06-20 湖南科技学院 Preparation method of nano calcium carbonate/bio-based film

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2001270168B9 (en) * 2000-11-22 2004-11-18 Clopay Plastic Products Company, Inc. Air and moisture vapor breathable biodegradable films and method of manufacture
CN108190935B (en) * 2018-04-04 2020-05-08 广西民族大学 Preparation method of strip-shaped and sheet-shaped calcium carbonate ultrafine particles

Also Published As

Publication number Publication date
CN113003596A (en) 2021-06-22

Similar Documents

Publication Publication Date Title
Xu et al. Multifunctional chiral nematic cellulose nanocrystals/glycerol structural colored nanocomposites for intelligent responsive films, photonic inks and iridescent coatings
CN107722733B (en) Antibacterial antifogging spray and preparation method and application thereof
JP2000169133A (en) Combined sol of silica-magnesium fluoride hydrate and its production
Kotachi et al. Morphological evaluation and film formation with iso-oriented calcite crystals using binary poly (acrylic acid)
CN113003596B (en) Light calcium carbonate in-situ filled biomacromolecule film and application thereof in packaging of oily food and medicines
CN112225894B (en) Hybrid nano particle, preparation method and anti-ultraviolet application
CN113045787A (en) Preparation method of nano cellulose liquid crystal paper with optical limiting characteristic
US20210108001A1 (en) Nanocrystalline cellulose, its preparation and uses of such nanocrystalline cellulose
CN106757785B (en) Preparation method of silver-loaded chitosan/polyvinyl alcohol micron belt
CN107057611A (en) A kind of preparation method of polyacrylic hydrogels binder
Wei et al. Cellulose Nanocrystal-based Liquid Crystal Structures and the Unique Optical Characteristics of Cellulose Nanocrystal Films.
CN105040509A (en) Nano chitosan base quaternary alkyl ammonium starch ether compound antibacterial paper, preparation and application thereof
CN104891548A (en) Method for preparing spherical calcite-type calcium carbonate
Sharma et al. Superabsorbent composites (SACs) based on xanthan gum-g-poly (itaconic acid)/kaolinite
CN112920438A (en) Preparation method of sarcosine-induced reinforced bacterial nano-cellulose chiral liquid crystal film
Muthami et al. Hairy cellulose nanocrystals: from synthesis to advanced applications in the water–energy–health–food nexus
JP2714559B2 (en) Spherical calcium carbonate and its production method
CN112370437A (en) Amoxicillin capsule and preparation method thereof
CN109971010B (en) Starch composite film material and preparation method thereof
CN112778556A (en) Preparation method of D-xylitol-induced reinforced nanocellulose chiral liquid crystal film
CN104893206A (en) Water-resistant high-temperature-resistant fully-degradable plastic film and preparation method thereof
WO1985003648A1 (en) Capsules and process for their preparation
CN106987016B (en) High-freshness-retaining nano Zr/TiO2Preparation method of bimetal modified PE coating film
CN104893203A (en) Antibacterial and anti-insect fully-degradable plastic film and manufacturing method thereof
CN114097774B (en) Preparation method of mesoporous silica nano double-layer microsphere controlled release agent

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
GR01 Patent grant
GR01 Patent grant