CN113897040A - Preparation method of degradable food packaging material with high mechanical strength - Google Patents
Preparation method of degradable food packaging material with high mechanical strength Download PDFInfo
- Publication number
- CN113897040A CN113897040A CN202111199432.6A CN202111199432A CN113897040A CN 113897040 A CN113897040 A CN 113897040A CN 202111199432 A CN202111199432 A CN 202111199432A CN 113897040 A CN113897040 A CN 113897040A
- Authority
- CN
- China
- Prior art keywords
- packaging material
- food packaging
- parts
- mechanical strength
- lubricant
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—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
- 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
- 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
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- 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
- C08J2429/00—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
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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)
- Compositions Of Macromolecular Compounds (AREA)
- Wrappers (AREA)
Abstract
The invention discloses a preparation method of a high-mechanical-strength degradable food packaging material, which is prepared from the following materials in parts by mass: 55-65 parts of polylactic acid, 45-55 parts of polyvinyl alcohol, 15-25 parts of maleic anhydride grafted compatilizer and 3-6 parts of nano titanium dioxide, wherein the nano titanium dioxide is in an anatase crystal form, 20-30 parts of composite filler and 5-8 parts of lubricant, the composite filler is one or more of sodium carboxymethyl cellulose, chitosan and calcium stearate, the maleic anhydride grafted compatilizer is polylactic acid-g-polyvinyl alcohol grafted copolymer, and the lubricant is one or more of acetylated monoglyceride fatty acid ester, polyethylene wax and polyamide wax. The main components of the degradable food packaging material with high mechanical strength of the invention, namely polylactic acid and polyvinyl alcohol, can be degraded in the environment, and the prepared graft copolymer also has good degradability, thereby solving the problem that the existing food packaging material is difficult to degrade.
Description
The application is a divisional application, the application number of the original application is 2019106150626, the application date is number 07 and 09 in 2019, and the patent names of the invention are as follows: a method for preparing degradable food packaging material.
Technical Field
The invention relates to the technical field of food packaging materials, in particular to a preparation method of a degradable food packaging material with high mechanical strength.
Background
With the development of society, in daily life, many non-instant products need to be preserved by using packaging materials, and various food-grade plastics such as polyvinylidene chloride, PP, ultra-high molecular weight polyethylene, PET and the like can be used. However, the existing food packaging materials are not easy to degrade when placed in the environment after use, and the environmental problems such as white pollution and the like caused by the existing food packaging materials are a great hidden danger threatening the living environment of human beings.
And the existing degradable food packaging material has low mechanical strength, is easy to damage, and is not beneficial to the quality safety of food in the processes of carrying, storing and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a degradable food packaging material with high mechanical strength, which solves the problems that the existing food packaging material is difficult to biodegrade and has low mechanical strength.
In order to solve the above problems, the present invention provides the following technical solutions:
a high-mechanical-strength degradable food packaging material is prepared from the following materials in parts by mass: 55-65 parts of polylactic acid, 45-55 parts of polyvinyl alcohol, 15-25 parts of maleic anhydride grafted compatilizer and 3-6 parts of nano titanium dioxide, wherein the nano titanium dioxide is in an anatase crystal form, 20-30 parts of composite filler and 5-8 parts of lubricant, the composite filler is one or more of sodium carboxymethyl cellulose, chitosan and calcium stearate, the maleic anhydride grafted compatilizer is polylactic acid-g-polyvinyl alcohol grafted copolymer, and the lubricant is one or more of acetylated monoglyceride fatty acid ester, polyethylene wax and polyamide wax.
Preferably, 63 parts of polylactic acid, 55 parts of polyvinyl alcohol, 22 parts of maleic anhydride grafted compatilizer, 6 parts of nano titanium dioxide, 30 parts of composite filler and 6 parts of lubricant, and the degradable food packaging material prepared according to the proportion has stronger mechanical property on the basis of considering degradability.
Preferably, the polylactic acid is 65 parts, the polyvinyl alcohol is 55 parts, the maleic anhydride grafting compatilizer is 25 parts, the nano titanium dioxide is 6 parts, the composite filler is 30 parts, and the lubricant is 8 parts, so that the degradable food packaging material prepared according to the proportion has the best mechanical property on the basis of considering the degradability.
Preferably, the lubricant is a mixture of acetylated monoglyceride and polyamide wax, the mass ratio of the acetylated monoglyceride to the polyamide wax is 1: 2-3, and the lubricant with the mass ratio has good compatibility with degradable food packaging materials.
Preferably, the lubricant is a mixture of polyethylene wax and polyamide wax, the mass ratio of the polyethylene wax to the polyamide wax is 2: 2-3, and the lubricant with the mass ratio has a good effect of enhancing the mechanical properties of the degradable food packaging material.
Preferably, the lubricant is a mixture of acetylated monoglyceride and polyethylene wax, the mass ratio of the acetylated monoglyceride to the polyethylene wax is 1: 1-2, and the lubricant with the mass ratio is the best in compatibility of the degradable food packaging material and enhancement effect on mechanical properties.
Preferably, the mass ratio of the sodium carboxymethylcellulose to the chitosan to the calcium stearate is 2: 2-3: 2-5, and the degradable food packaging material of the composite filler with the mass ratio has the best degradation performance.
A method for preparing the food packaging material comprises the following specific steps:
(1) weighing polylactic acid, polyvinyl alcohol, maleic anhydride grafted compatilizer, lubricant, composite filler and nano titanium dioxide according to the mass parts, adding the weighed materials into a batching container, uniformly stirring at the temperature of 80-125 ℃, wherein the stirring speed is 300-500r/min, and then cooling to the temperature below 80 ℃ to obtain a primarily mixed material I;
(2) adding the material I into a double-screw extruder, and carrying out melting, extrusion bracing, cooling and grain cutting to obtain a granular material II for manufacturing the food packaging material;
(3) and adding the prepared granules II into a tabletting machine to be pressed into a film or a plate, and degrading the food packaging material with high mechanical strength.
The temperature in the double-screw extruder is 120-190 ℃.
Compared with the prior art, the invention has the following advantages:
the main components of the degradable food packaging material with high mechanical strength can be degraded in the environment, and the prepared graft copolymer also has good microbial degradability, so that the problem that the existing food packaging material is difficult to degrade is solved; meanwhile, the anatase crystal form nano titanium dioxide in the food packaging material is a photocatalyst, and can catalyze the decomposition of organic matters such as polylactic acid and polyvinyl alcohol to further degrade under the radiation of ultraviolet light in the environment, so that the degradable performance of the degradable food packaging material is further enhanced. The compatibility of polylactic acid and polyvinyl alcohol is improved through graft polymerization of the maleic anhydride graft compatilizer, the molecular weight of the polylactic acid and the polyvinyl alcohol is changed, hydrogen bonds between the polyvinyl alcohol and polylactic acid molecules are strengthened, the mechanical property between the polylactic acid and the polyvinyl alcohol graft polymer is enhanced, the brittle and breakable property of the polylactic acid is improved, and the mechanical property of a common polylactic acid material is improved. The composite filler can reduce the use of polymerization raw materials on the premise of having a use function, and saves the cost. The calcium stearate and the lubricant in the composite material can further enhance the compatibility between the polylactic acid and the polyvinyl alcohol, and intermolecular hydrogen bonds formed by the calcium stearate and the lubricant and the graft copolymer of the polylactic acid and the polyvinyl alcohol also enhance the mechanical properties of the food packaging material.
The method for preparing the food packaging material can prepare the clean degradable food packaging material with high mechanical strength. The food packaging material contains the nano titanium dioxide with the anatase crystal form, so that the surface of the packaging material has certain antibacterial activity, microorganisms on the surface can be killed, the microorganisms are prevented from entering the interior of food packaged by the packaging material, and the packaging material has clean capability. The main components of the packaging material are degradable organic matters, the packaging material can be degraded in a natural environment by using the two degradable organic matters, and the nano titanium dioxide in the packaging material in the environment is a photocatalyst, so that the decomposition of the degradable material can be further promoted under the irradiation of ultraviolet light, and the problem that the existing food packaging material is difficult to degrade is solved; the maleic anhydride grafting compatilizer is used for copolymerizing two incompatible material systems together, so that the mechanical property of the material is enhanced, and the problem of low mechanical strength of the existing food packaging material is solved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
Example 1: the embodiment provides a food packaging material, which is prepared according to the method for preparing the food packaging material, and the method comprises the following specific steps:
(1) weighing 55 parts of polylactic acid, 45 parts of polyvinyl alcohol, 15 parts of maleic anhydride grafted compatilizer, 5 parts of lubricant, 20 parts of composite filler and 3 parts of nano titanium dioxide according to the mass parts, adding the weighed materials into a batching container, uniformly stirring the materials at 80-90 ℃, wherein the stirring speed is 300r/min in the preparation process of the material I, and then cooling the materials to be below 80 ℃ to obtain a primarily mixed material I;
(2) and adding the material I into a double-screw extruder, and melting, extruding, bracing, cooling and granulating at the temperature of 120-125 ℃ in the double-screw extruder to obtain granules II for manufacturing the food packaging material.
(3) And adding the prepared granules II into a tabletting machine to be pressed into a film or a plate, and degrading the food packaging material with high mechanical strength.
Example 2: the embodiment provides a food packaging material, which is prepared according to the method for preparing the food packaging material, and the method comprises the following specific steps:
(1) weighing 58 parts of polylactic acid, 50 parts of polyvinyl alcohol, 18 parts of maleic anhydride grafted compatilizer, 6 parts of lubricant, 24 parts of composite filler and 4 parts of nano titanium dioxide according to the mass parts, and adding the materials into a batching container, wherein the composite filler is sodium carboxymethylcellulose and chitosan and the mass ratio of the composite filler to the chitosan is 1:1, and the lubricant is acetylated monoglyceride and polyethylene wax and the mass ratio of the acetylated monoglyceride and the polyethylene wax is 1: 2; uniformly stirring at 80-100 ℃, wherein the stirring speed is 350r/min in the preparation process of the material I, and then cooling to below 80 ℃ to obtain a primarily mixed material I;
(2) and adding the material I into a double-screw extruder, melting, extruding into strips, cooling and granulating, wherein the temperature in the double-screw extruder is 130-135 ℃, and obtaining granules II for manufacturing the food packaging material.
(3) And adding the prepared granules II into a tabletting machine to be pressed into a film or a plate, and degrading the food packaging material with high mechanical strength.
Example 3: the embodiment provides a food packaging material, which is prepared according to the method for preparing the food packaging material, and the method comprises the following specific steps:
(1) weighing 60 parts of polylactic acid, 52 parts of polyvinyl alcohol, 20 parts of maleic anhydride grafted compatilizer, 6 parts of lubricant, 25 parts of composite filler and 4 parts of nano titanium dioxide according to the mass parts, and adding the materials into a batching container, wherein the composite filler is sodium carboxymethylcellulose, chitosan and calcium stearate, the mass ratio of the composite filler to the composite filler is 2:2:2, and the lubricant is acetylated monoglyceride and polyethylene wax, and the mass ratio of the lubricant to the polyethylene wax is 1: 3; uniformly stirring at 90-115 ℃, wherein the stirring speed is 380r/min in the preparation process of the material I, and then cooling to below 80 ℃ to obtain a primarily mixed material I;
(2) and adding the material I into a double-screw extruder, and melting, extruding, bracing, cooling and granulating at the temperature of 135-140 ℃ in the double-screw extruder to obtain granules II for manufacturing the food packaging material.
(3) And adding the prepared granules II into a tabletting machine to be pressed into a film or a plate, and degrading the food packaging material with high mechanical strength.
Example 4: the embodiment provides a food packaging material, which is prepared according to the method for preparing the food packaging material, and the method comprises the following specific steps:
(1) weighing 63 parts of polylactic acid, 55 parts of polyvinyl alcohol, 22 parts of maleic anhydride grafted compatilizer, 6 parts of lubricant, 30 parts of composite filler and 6 parts of nano titanium dioxide according to the mass parts, and adding the materials into a batching container, wherein the composite filler is sodium carboxymethylcellulose, chitosan and calcium stearate, the mass ratio of the composite filler to the chitosan to the calcium stearate is 2:2.5:3, and the lubricant is a mixture of polyethylene wax and polyamide wax, and the mass ratio of the lubricant to the polyamide wax is 1: 1; uniformly stirring at 110-120 ℃, wherein the stirring speed is 400r/min in the preparation process of the material I, and then cooling to below 80 ℃ to obtain a primarily mixed material I;
(2) and adding the material I into a double-screw extruder, and melting, extruding, bracing, cooling and granulating at the temperature of 140-150 ℃ in the double-screw extruder to obtain granules II for manufacturing the food packaging material.
(3) And adding the prepared granules II into a tabletting machine to be pressed into a film or a plate, and degrading the food packaging material with high mechanical strength.
Example 5: the embodiment provides a food packaging material, which is prepared according to the method for preparing the food packaging material, and the method comprises the following specific steps:
(1) weighing 65 parts of polylactic acid, 55 parts of polyvinyl alcohol, 25 parts of maleic anhydride grafted compatilizer, 8 parts of lubricant, 30 parts of composite filler and 6 parts of nano titanium dioxide according to the mass parts, and adding the materials into a batching container, wherein the composite filler is sodium carboxymethylcellulose, chitosan and calcium stearate, the mass ratio of the composite filler to the composite filler is 2:3:5, the lubricant is a mixture of polyethylene wax and polyamide wax, and the mass ratio of the lubricant to the polyamide wax is 2: 2.5; uniformly stirring at 115-125 ℃, wherein the stirring speed is 450r/min in the preparation process of the material I, and then cooling to below 80 ℃ to obtain a primarily mixed material I;
(2) and adding the material I into a double-screw extruder, and melting, extruding, bracing, cooling and granulating at the temperature of 150-160 ℃ in the double-screw extruder to obtain granules II for manufacturing the food packaging material.
(3) And adding the prepared granules II into a tabletting machine to be pressed into a film or a plate, and degrading the food packaging material with high mechanical strength.
Example 6: the embodiment provides a food packaging material, which is prepared according to the method for preparing the food packaging material, and the method comprises the following specific steps:
(1) weighing 55 parts of polylactic acid, 55 parts of polyvinyl alcohol, 15 parts of maleic anhydride grafted compatilizer, 6 parts of lubricant, 25 parts of composite filler and 6 parts of nano titanium dioxide according to the mass parts, and adding the materials into a batching container, wherein the composite filler is chitosan and calcium stearate, the mass ratio of the composite filler to the calcium stearate is 1:1, and the lubricant is a mixture of polyethylene wax and polyamide wax, and the mass ratio of the lubricant to the polyamide wax is 2: 3; uniformly stirring at 120-125 ℃, wherein the stirring speed is 500r/min in the preparation process of the material I, and then cooling to below 80 ℃ to obtain a primarily mixed material I;
(2) and adding the material I into a double-screw extruder, and melting, extruding, bracing, cooling and granulating at the temperature of 170-190 ℃ in the double-screw extruder to obtain granules II for manufacturing the food packaging material.
(3) And adding the prepared granules II into a tabletting machine to be pressed into a film or a plate, and degrading the food packaging material with high mechanical strength.
Comparative example 1: the embodiment provides a degradable antibacterial food packaging material, which is prepared according to the published Chinese invention patent CN 201811286335.9;
comparative example 2: the embodiment provides a food packaging material and a preparation method thereof, which are prepared according to the published Chinese invention patent CN 201610711294.8;
table 1: component contents of food packaging materials prepared in examples 1 to 6
Table 2: the contents of the respective components of the degradable antibacterial food packaging material prepared in comparative example 1 and the food packaging material prepared in comparative example 2
The high mechanical strength degradable food packaging materials prepared in examples 1-6 of the present invention were compared with the degradable antibacterial food packaging material of comparative example 1 and the food packaging material of comparative example 2 in terms of mechanical properties and degradation properties, respectively. The mechanical properties were tested according to the GB13022-91 standard. The degradation performance test adopts a soil burying method, the degradable food packaging material with high mechanical strength prepared in examples 1-6 of the invention, the degradable antibacterial food packaging material in comparative example 1 and the food packaging material in comparative example 2 are respectively manufactured into plates with the length, width and thickness of 10cm, 10cm and 1cm, then 10 plates of each material are respectively selected as a sample, the sample is placed in a drying box, the temperature is kept at 105 ℃, the heating and drying are carried out until the mass is constant, the mass is weighed, and the initial mass M is obtained0. Taking out the soil after burying for a fixed time, washing the corresponding sample twice by using deionized water and ethanol, drying, weighing the mass to obtain the degraded mass M1And calculating the degradation mass delta M and the degradation rate W of the sample. The calculation formula is as follows:
ΔM＝M0-M1 (1)
W＝ΔM/M0×100％ (2)
wherein, the soil physicochemical indexes of the embedded sample are as follows: 28 g/kg of organic matter-10.144 g.kg of available nitrogen-1Is effectivePhosphorus 0.137 g.kg-1Effective potassium 0.194 g.kg-1And ph 6.83.
Table 3: performance test results of the products of examples 1-6 and comparative examples 1 and 2
Note: in Table 3, the degradability is expressed as the mass M after degradation of a sample obtained after a fixed time (unit: hour/h)1Initial mass M of the sample0The smaller the percentage is, the more the sample is degraded, the better the degradability of the food packaging material is; otherwise, the worse.
As can be seen from tables 1 to 3, the degradable food packaging materials in the six embodiments prepared by using the method for preparing a degradable food packaging material of the present invention have the advantages that as the content of the maleic anhydride grafted compatibilizer increases, the mechanical properties of the degradable food packaging material are enhanced, and the tensile strength, the flexural modulus and the impact strength of the degradable food packaging material are gradually enhanced, and accordingly, the degradable property of the packaging material with a low content of the maleic anhydride grafted compatibilizer is good because the molecular polymerization amount is low, and the packaging material is completely degraded after 1000 hours, which is shown in the degradable food packaging materials of examples 1 and 6 in table 3; with the increase of the content of the maleic anhydride grafted compatilizer, the molecular weight of the polymer is increased, and the degradable performance of the prepared degradable food packaging material is gradually reduced, see the composition table and the degradable performance of the degradable food packaging material of examples 2-5 in tables 1 and 3, the degradable food packaging material prepared in examples 1-6 is better than the degradable performance of comparative examples 1 and 2, the mass percentage of the degradable packaging material after the degradable food packaging material prepared in examples 1-6 is degraded for 1000h is smaller than that of the packaging material of comparative examples 1 and 2, and the mechanical performance of the degradable food packaging material prepared in examples 1-6 is stronger than that of comparative examples 1 and 2.
The degradable food packaging material provided by the embodiment of the invention has the main components of polylactic acid and polyvinyl alcohol, and can be degraded in the environment, the prepared graft copolymer also has good degradable performance, and meanwhile, the anatase crystal form nano titanium dioxide in the food packaging material is a photocatalyst, and can catalyze the decomposition and further degradation of organic matters such as polylactic acid and polyvinyl alcohol under the radiation of ultraviolet light in the environment, so that the problem that the existing food packaging material is difficult to degrade is solved. The compatibility of the polylactic acid and the polyvinyl alcohol is improved through the graft polymerization of the maleic anhydride graft compatilizer, the adhesive force between the polylactic acid and the polyvinyl alcohol is enhanced, meanwhile, the hydrogen bond between the polyvinyl alcohol and the polylactic acid molecules is enhanced, the polymerized molecular weight of the polylactic acid and the polyvinyl alcohol is changed, and the characteristic that the polylactic acid is brittle and easy to break is improved. The composite filler can reduce the use of polymerization raw materials on the premise of meeting the use function, saves the cost, and can degrade the sodium carboxymethyl cellulose and the chitosan in natural environment without polluting the environment; calcium stearate is also readily degraded by microorganisms that prefer fatty organic substances. The compatibility between the polylactic acid and the polyvinyl alcohol can be further enhanced by the calcium stearate and the lubricant in the composite filler; wherein the molecular weight of the polyvinyl alcohol is 20000-180000, the molecular weight of the polylactic acid is 200000-500000, and the molecular weight of the polymer with a larger range can be prepared into degradable food packaging materials suitable for different performance requirements. And hydrogen bonds are formed between molecules such as acetylated monoglyceride, polyethylene wax and polyamide wax in the lubricant and the polylactic acid and polyvinyl alcohol graft polymerization molecules to further enhance the mechanical property of the food packaging material.
The main components of the invention, polylactic acid and polyvinyl alcohol, can be degraded in the environment, and solves the problem that the existing food packaging material is difficult to degrade. The compatibility of polylactic acid and polyvinyl alcohol is improved through the graft polymerization of the maleic anhydride graft compatilizer, the molecular weight of the polylactic acid and the molecular weight of ethanol polymerization are changed, the mechanical property between the polylactic acid and the polyvinyl alcohol is enhanced, and the hydrogen bond between the polyvinyl alcohol and the polylactic acid molecules is enhanced, so that the characteristic that the polylactic acid is brittle and easy to break is improved. The composite filler can reduce the use of polymerization raw materials on the premise of having a use function, and saves the cost. The compatibility between the polylactic acid and the polyvinyl alcohol can be further enhanced by the calcium stearate and the lubricant in the composite material.
The method for preparing the food packaging material can prepare the clean degradable food packaging material with high mechanical strength. The food packaging material contains the anatase crystal form nano titanium dioxide, so that the surface of the packaging material has certain antibacterial activity, microorganisms on the surface are killed, the microorganisms are prevented from entering the interior of food packaged by the packaging material, and the packaging material has clean capability. The problem that the existing food packaging material is difficult to degrade is solved by using two degradable organic matters, and the problem that the mechanical strength of the existing food packaging material is low is solved by the mechanical property of the two degradable organic matter graft polymerization reinforced materials.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the high-mechanical-strength degradable food packaging material is characterized in that the high-mechanical-strength degradable food packaging material is prepared from the following materials in parts by mass: 55-65 parts of polylactic acid, 45-55 parts of polyvinyl alcohol, 15-25 parts of maleic anhydride grafted compatilizer, 3-6 parts of nano titanium dioxide, 20-30 parts of composite filler and 5-8 parts of lubricant;
the preparation method of the degradable food packaging material with high mechanical strength comprises the following specific steps:
(1) weighing polylactic acid, polyvinyl alcohol, maleic anhydride grafted compatilizer, lubricant, composite filler and nano titanium dioxide according to the mass parts, adding the weighed materials into a batching container, uniformly stirring at the temperature of 80-125 ℃, wherein the stirring speed is 300-500r/min, and then cooling to the temperature below 80 ℃ to obtain a primarily mixed material I;
(2) adding the material I into a double-screw extruder, and carrying out melting, extrusion bracing, cooling and grain cutting to obtain a granular material II for manufacturing the food packaging material;
(3) and adding the prepared granules II into a tabletting machine to be pressed into a film or a plate, thus obtaining the finished product.
2. The method for preparing the high mechanical strength degradable food packaging material of claim 1, wherein the method comprises the following steps: the temperature in the double-screw extruder is 120-190 ℃.
3. The method for preparing the high mechanical strength degradable food packaging material of claim 1, wherein the method comprises the following steps: the lubricant is one or more of acetylated monoglyceride, polyethylene wax and polyamide wax.
4. The method for preparing the high mechanical strength degradable food packaging material of claim 3, wherein the method comprises the following steps: the lubricant is a mixture of acetylated monoglyceride and polyamide wax, and the mass ratio of the acetylated monoglyceride to the polyamide wax is 1: 2-3.
5. The method for preparing the high mechanical strength degradable food packaging material of claim 3, wherein the method comprises the following steps: the lubricant is a mixture of polyethylene wax and polyamide wax, and the mass ratio of the lubricant to the polyamide wax is 2: 2-3.
6. The method for preparing the high mechanical strength degradable food packaging material of claim 3, wherein the method comprises the following steps: the lubricant is a mixture of acetylated monoglyceride and polyethylene wax, and the mass ratio of the acetylated monoglyceride to the polyethylene wax is 1: 1-2.
7. The method for preparing the high mechanical strength degradable food packaging material of claim 1, wherein the method comprises the following steps: the nano titanium dioxide is in an anatase crystal form.
8. The method for preparing the high mechanical strength degradable food packaging material of claim 1, wherein the method comprises the following steps: the composite filler is one or more of sodium carboxymethylcellulose, chitosan and calcium stearate.
9. The method for preparing the high mechanical strength degradable food packaging material of claim 8, wherein the method comprises the following steps: the mass ratio of the sodium carboxymethylcellulose to the chitosan to the calcium stearate is 2: 2-3: 2-5.
10. The method for preparing the high mechanical strength degradable food packaging material of claim 1, wherein the method comprises the following steps: the maleic anhydride grafted compatilizer is polylactic acid-g-polyvinyl alcohol grafted copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111199432.6A CN113897040A (en) | 2019-07-09 | 2019-07-09 | Preparation method of degradable food packaging material with high mechanical strength |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111199432.6A CN113897040A (en) | 2019-07-09 | 2019-07-09 | Preparation method of degradable food packaging material with high mechanical strength |
| CN201910615062.6A CN110423441B (en) | 2019-07-09 | 2019-07-09 | Degradable food packaging material and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910615062.6A Division CN110423441B (en) | 2019-07-09 | 2019-07-09 | Degradable food packaging material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113897040A true CN113897040A (en) | 2022-01-07 |
Family
ID=68409080
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910615062.6A Active CN110423441B (en) | 2019-07-09 | 2019-07-09 | Degradable food packaging material and preparation method thereof |
| CN202111199432.6A Pending CN113897040A (en) | 2019-07-09 | 2019-07-09 | Preparation method of degradable food packaging material with high mechanical strength |
| CN202111199434.5A Active CN113817303B (en) | 2019-07-09 | 2019-07-09 | Degradable food packaging material with high mechanical strength |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910615062.6A Active CN110423441B (en) | 2019-07-09 | 2019-07-09 | Degradable food packaging material and preparation method thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111199434.5A Active CN113817303B (en) | 2019-07-09 | 2019-07-09 | Degradable food packaging material with high mechanical strength |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN110423441B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456562A (en) * | 2022-02-22 | 2022-05-10 | 深圳潘道医学检验实验室 | Degradable virus sampling tube and preparation method thereof |
| CN115746523A (en) * | 2022-11-16 | 2023-03-07 | 深圳市鼎力盛科技有限公司 | Novel material air column bag with strong degradation capability and preparation method thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112048102A (en) * | 2020-09-14 | 2020-12-08 | 谢强 | Environment-friendly food packaging plastic and preparation method thereof |
| CN112080118B (en) * | 2020-09-29 | 2022-09-09 | 中星中大印刷（深圳）有限公司 | Degradable polylactic acid plastic |
| CN114573962B (en) * | 2022-04-01 | 2023-11-14 | 安徽海铭塑业有限公司 | Degradable food packaging material |
| CN115322525B (en) * | 2022-10-11 | 2022-12-20 | 南通佰凯吉包装科技有限公司 | Multilayer composite transparent packaging bag and production process thereof |
| CN115938518B (en) * | 2022-12-26 | 2024-03-19 | 苏州市恒福包装制品有限公司 | Preparation process optimization method and system of degradable food packaging material |
| CN116082744B (en) * | 2023-03-15 | 2023-09-19 | 河北立亚包装科技有限公司 | Antibacterial biodegradable preservative film and preparation method thereof |
| CN117126517B (en) * | 2023-08-24 | 2024-03-12 | 广东岭南大健康生态科技集团有限公司 | Environment-controllable degradable mulching film and application thereof in weeding |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215411A (en) * | 2008-01-21 | 2008-07-09 | 南京大学 | Light degradation antibiotic polylactic acid material and preparation method thereof |
| WO2012026653A1 (en) * | 2010-08-24 | 2012-03-01 | Republic Of Korea (Management : Rural Development Administration) | Biodegradable, photodegradable bio film containing rice hull and rice bran, and manufacturing method thereof |
| CN103319865A (en) * | 2013-06-08 | 2013-09-25 | 上海博疆新材料科技有限公司 | Polylactic acid alloy membrane and application thereof |
| CN103502356A (en) * | 2011-03-31 | 2014-01-08 | 英美烟草(投资)有限公司 | Blends of a polylactic acid and a water soluble polymer |
| CN104530668A (en) * | 2014-12-17 | 2015-04-22 | 广州飞胜高分子材料有限公司 | 3D printing material having self-cleaning antibacterial function as well as preparation method and application of 3D printing material |
| CN106883578A (en) * | 2017-03-28 | 2017-06-23 | 天津科技大学 | A kind of antibacterial degradable fresh-keeping foodstuff packaging material and its preparation |
| CN109853083A (en) * | 2018-12-28 | 2019-06-07 | 青岛科凯达橡塑有限公司 | A kind of water solubility biodegradable fiber and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429266C (en) * | 2005-11-16 | 2008-10-29 | 朱家牧 | Synthetic paper made of environmental protection plastic and its preparation method |
| US9388581B2 (en) * | 2012-09-21 | 2016-07-12 | Lg Hausys, Ltd. | Biodegradable panels |
| CN109456582A (en) * | 2018-10-31 | 2019-03-12 | 安徽双平包装有限公司 | A kind of degradable antibacterial food bag material |
-
2019
- 2019-07-09 CN CN201910615062.6A patent/CN110423441B/en active Active
- 2019-07-09 CN CN202111199432.6A patent/CN113897040A/en active Pending
- 2019-07-09 CN CN202111199434.5A patent/CN113817303B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215411A (en) * | 2008-01-21 | 2008-07-09 | 南京大学 | Light degradation antibiotic polylactic acid material and preparation method thereof |
| WO2012026653A1 (en) * | 2010-08-24 | 2012-03-01 | Republic Of Korea (Management : Rural Development Administration) | Biodegradable, photodegradable bio film containing rice hull and rice bran, and manufacturing method thereof |
| CN103502356A (en) * | 2011-03-31 | 2014-01-08 | 英美烟草(投资)有限公司 | Blends of a polylactic acid and a water soluble polymer |
| CN103319865A (en) * | 2013-06-08 | 2013-09-25 | 上海博疆新材料科技有限公司 | Polylactic acid alloy membrane and application thereof |
| CN104530668A (en) * | 2014-12-17 | 2015-04-22 | 广州飞胜高分子材料有限公司 | 3D printing material having self-cleaning antibacterial function as well as preparation method and application of 3D printing material |
| CN106883578A (en) * | 2017-03-28 | 2017-06-23 | 天津科技大学 | A kind of antibacterial degradable fresh-keeping foodstuff packaging material and its preparation |
| CN109853083A (en) * | 2018-12-28 | 2019-06-07 | 青岛科凯达橡塑有限公司 | A kind of water solubility biodegradable fiber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 范燕平: "聚乙烯醇对聚乳酸的改性研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》, no. 01, pages 38 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456562A (en) * | 2022-02-22 | 2022-05-10 | 深圳潘道医学检验实验室 | Degradable virus sampling tube and preparation method thereof |
| CN114456562B (en) * | 2022-02-22 | 2024-05-17 | 深圳潘道医学检验实验室 | Degradable virus sampling tube and preparation method thereof |
| CN115746523A (en) * | 2022-11-16 | 2023-03-07 | 深圳市鼎力盛科技有限公司 | Novel material air column bag with strong degradation capability and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110423441A (en) | 2019-11-08 |
| CN113817303B (en) | 2023-12-12 |
| CN110423441B (en) | 2021-11-30 |
| CN113817303A (en) | 2021-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110423441B (en) | Degradable food packaging material and preparation method thereof | |
| CN110791069B (en) | Full-degradable high-barrier composite material for flexible package | |
| US5910520A (en) | Melt processable biodegradable compositions and articles made therefrom | |
| CN113861635A (en) | Starch modified PBAT/PLA biodegradable plastic film and preparation method thereof | |
| US10526490B2 (en) | Melt processed polymer composition derived from leaf sheaths of trees of the genus Arecaceae | |
| CN104059341B (en) | A kind of nanometer silver polyester biological degradation preservative film and Synthesis and applications thereof | |
| CN1950448A (en) | Biodegradable poly(lactic acid) polymer composition and films, coatings and products comprising biodegradable poly(lactic acid) polymer compositions | |
| CN111409346A (en) | Degradable film and preparation method thereof | |
| CN102432942A (en) | Non-starch biodegradable plastic film | |
| CN111205611B (en) | Biodegradable preservative film and preparation method thereof | |
| CN109867819A (en) | Polylactic acid-starch-PVA composite degradable packaging film and preparation method thereof | |
| CN101497731B (en) | Environment degrading thermoplastic glucomanan film and preparation thereof | |
| CN104945870A (en) | All-biodegradable modified polylactic acid film-blowing resin and preparation method thereof | |
| Zhang et al. | Development of biodegradable polyamide 4/polyvinyl alcohol/poly (lactic acid) multilayer films with tunable water barrier property and superior oxygen barrier property | |
| CN109988400A (en) | A kind of environment-friendly type degradable packaging composite film and preparation method thereof | |
| Rech et al. | Recyclable Extrudable Biopolymer Composites from Alginate and Lignocellulosic Biomass Waste | |
| JPH11124485A (en) | Composite resin composition | |
| CN114836012B (en) | Completely biodegradable garbage bag film material and preparation method of garbage bag film | |
| CN114907680A (en) | Recyclable water-soluble degradable foam material and preparation method thereof | |
| JP2009221336A (en) | Resin composition, and molded article and film comprising the resin composition | |
| Malucelli | High barrier composite materials based on renewable sources for food packaging applications | |
| CN111057274A (en) | High-filling starch-based thermoplastic composite material and preparation method thereof | |
| CN114163788B (en) | Preparation method of high-strength high-barrier biodegradable film | |
| CN102649861A (en) | Modified polyvinyl alcohol composition and preparation method thereof | |
| JP2752880B2 (en) | Polyester seat |
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 |