CN113072787A - PVA biodegradable film - Google Patents
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- CN113072787A CN113072787A CN202110365546.7A CN202110365546A CN113072787A CN 113072787 A CN113072787 A CN 113072787A CN 202110365546 A CN202110365546 A CN 202110365546A CN 113072787 A CN113072787 A CN 113072787A
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- 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
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- 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
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- 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
- C08J2401/02—Cellulose; Modified cellulose
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- 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
- C08K3/16—Halogen-containing compounds
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
Abstract
The invention discloses a PVA biodegradable film, and particularly relates to the technical field of food processing, and the PVA biodegradable film comprises the following components in parts by weight: 60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent, 0.3-0.6 part of antioxidant, 60-100 parts of deionized water, 60-100 parts of butyl acrylate, 100-120 parts of cellulose aqueous solution, 10-20 parts of glycerol and 1-5 parts of sodium chloride. According to the invention, after maltose obtained by decomposing starch is compounded with polyvinyl alcohol, the modified PVA film has good plasticity and good biodegradability, and the modified PVA biodegradable film with good chemical properties and excellent degradation properties can be prepared by optimizing the proportion of raw materials and optimizing process conditions, so that the economic added value of the PVA biodegradable film is improved.
Description
Technical Field
The invention relates to the technical field of polyvinyl alcohol processing, in particular to a PVA biodegradable film.
Background
The plastic is a plastic (flexible) material formed by processing and molding or a rigid material formed by curing and crosslinking by using a high molecular weight synthetic resin as a main component and adding appropriate additives such as a plasticizer, a stabilizer, an antioxidant, a flame retardant, a colorant and the like. Particularly in the field of packaging, plastics are a widely used packaging material, but with increasing environmental problems, energy depletion and food safety threats, people aim at biodegradable materials. The polyvinyl alcohol (PVA) has the performance and the characteristics of the traditional plastic, can be split and degraded in water with different water temperatures or under natural conditions, is finally biodegraded into carbon dioxide and water, returns to the natural environment in a form, and is a biodegradable environment-friendly material.
The PVA water-soluble film is mostly produced and prepared by a solution casting method, the processing cost is extremely high, the productivity is low, and the biodegradability and the mechanical property of the PVA film sold in the market are poor.
Disclosure of Invention
In order to overcome the above defects in the prior art, embodiments of the present invention provide a PVA biodegradable film, wherein after maltose obtained by starch decomposition is compounded with polyvinyl alcohol, the modified PVA biodegradable film has good plasticity and good biodegradability, and the modified PVA biodegradable film having good chemical properties and excellent degradation properties can be prepared by optimizing the ratio of raw materials and optimizing process conditions, which is beneficial to improving the economic added value of the PVA biodegradable film.
In order to achieve the purpose, the invention provides the following technical scheme: 60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent, 0.3-0.6 part of antioxidant, 60-100 parts of deionized water, 60-100 parts of butyl acrylate, 100 parts of cellulose aqueous solution, 10-20 parts of glycerol and 1-5 parts of sodium chloride.
In a preferred embodiment, the following ingredients and parts by weight thereof are included: 70-90 parts of polyvinyl alcohol, 25-35 parts of starch, 0.2-0.4 part of coupling agent, 0.4-0.5 part of antioxidant, 70-90 parts of deionized water, 70-90 parts of butyl acrylate, 115 parts of cellulose aqueous solution 105-containing liquid, 12-18 parts of glycerol and 2-4 parts of sodium chloride.
In a preferred embodiment, the following ingredients and parts by weight thereof are included: 80 parts of polyvinyl alcohol, 30 parts of starch, 0.3 part of coupling agent, 0.5 part of antioxidant, 80 parts of deionized water, 80 parts of butyl acrylate, 110 parts of cellulose aqueous solution, 15 parts of glycerol and 3 parts of sodium chloride.
In a preferred embodiment, the coupling agent is selected from one of a silane coupling agent and a titanate coupling agent, and the antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
A processing technology of a PVA biodegradable film comprises the following specific preparation steps:
step 1, preparing raw materials, namely 60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent, 0.3-0.6 part of antioxidant, 60-100 parts of deionized water, 60-100 parts of butyl acrylate, 100 parts of cellulose aqueous solution, 10-20 parts of glycerol and 1-5 parts of sodium chloride;
step 2, pretreatment, namely adding 60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent and 0.3-0.6 part of antioxidant into a stirring kettle, continuously injecting 60-100 parts of deionized water into the stirring kettle, keeping the temperature unchanged, and stirring for 2-3 hours in a counterclockwise manner to obtain an original PVA solution;
step 3, preparing a modified PVA mixed solution A, injecting half of the original PVA solution prepared in the step 2 into a reaction kettle, continuously adding 10-20 parts of glycerol into the reaction kettle, keeping the temperature and stirring for 30-60min to obtain a suspension solution, continuously adding 60-100 parts of butyl acrylate into the suspension solution, heating and keeping the temperature for 4 hours, adding 1-5 parts of sodium chloride, stirring, cooling and standing to obtain the modified PVA mixed solution A;
step 4, preparing a modified PVA mixed solution B, injecting the other half of the original PVA solution prepared in the step 2 into a magnetic stirrer, continuously adding 120 parts of cellulose aqueous solution into the magnetic stirrer, controlling the temperature in the magnetic stirrer to be 25-35 ℃, controlling the rotating speed to be 650-750 r/min, and stirring for 3-5 hours to obtain the modified PVA mixed solution B;
step 5, preparing a first layer of film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on a flat film plate to scrape the film until the thickness of the film is 0.3mm-0.6mm, and standing at room temperature for 48-72 hours to obtain the first layer of film;
step 6, preparing a double-layer film, namely uniformly spraying the modified PVA mixed solution B prepared in the step 4 on the first layer of film for film scraping until the thickness of the second layer of film is 0.2-0.4 mm, and standing at room temperature for 48-72 hours to obtain the double-layer film;
step 7, preparing a three-layer composite film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on the double-layer film for film scraping until the thickness of the third layer film is 0.3-0.6 mm, and standing at room temperature for 48-72 hours to obtain the three-layer composite film;
and step 8, cleaning and drying: and (4) washing the three-layer composite film prepared in the step (7) by using a hydrochloric acid solution heated to 40-50 ℃, then washing by using clear water, and putting the washed three-layer composite film into a steam drying box for drying under pressure to obtain the formed PVA biological film.
In a preferred embodiment, the temperature in the stirred tank is controlled to be 80-85 ℃ by heating in a water bath in the step 2.
In a preferred embodiment, in the step 3, the temperature of the reaction kettle after the butyl acrylate is added is raised to 60 ℃, and the rotation speed is controlled to be 800-1000 r/min.
The invention has the technical effects and advantages that:
in the invention, the glycerol and the butyl acrylate are properly added through a reasonable process in the raw material modification production process, the mixture ratio of the glycerol and the butyl acrylate is proper, the hydrophilic hydroxyl of the glycerol and the hydrophilic bond of the butyl acrylate react with the unsaturated bond of the polyvinyl alcohol, the barrier property of water molecules is greatly enhanced, simultaneously, when the raw material modification production is carried out, the modified PVA film has good plasticity and good biodegradability after maltose obtained by decomposing starch is compounded with the polyvinyl alcohol, the modified PVA biodegradable film with good mechanical property and excellent degradation property can be prepared by optimizing the mixture ratio of the raw materials, the economic added value of the PVA biodegradable film is favorably improved, the PVA biodegradable film prepared by the invention has 100 percent environmental degradability and is completely converted into water, carbon dioxide and organic matters, no harm to environment or soil, simple process, low equipment requirement and high cost performance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent, 0.3-0.6 part of antioxidant, 60-100 parts of deionized water, 60-100 parts of butyl acrylate, 100 parts of cellulose aqueous solution, 10-20 parts of glycerol and 1-5 parts of sodium chloride.
Specifically, in this embodiment, the following steps are specifically performed: 60 parts of polyvinyl alcohol, 20 parts of starch, 0.1 part of coupling agent, 0.3 part of antioxidant, 60 parts of deionized water, 60 parts of butyl acrylate, 100 parts of cellulose aqueous solution, 10 parts of glycerol and 1 part of sodium chloride;
further, in the above components, the coupling agent is a silane coupling agent;
on the basis, the processing technology of the PVA biodegradable film comprises the following specific preparation steps:
step 1, preparing raw materials, namely 60 parts of polyvinyl alcohol, 20 parts of starch, 0.1 part of coupling agent, 0.3 part of antioxidant, 60 parts of deionized water, 60 parts of butyl acrylate, 100 parts of cellulose aqueous solution, 10 parts of glycerol and 1 part of sodium chloride;
step 2, pretreatment, namely adding 60 parts of polyvinyl alcohol, 20 parts of starch, 0.1 part of coupling agent and 0.3 part of antioxidant into a stirring kettle, continuously injecting 60 parts of deionized water into the stirring kettle, controlling the internal temperature of the stirring kettle to be 80 ℃ by using a water bath heating mode, and stirring for 2 hours in a counterclockwise mode to obtain an original PVA solution;
step 3, preparing a modified PVA mixed solution A, injecting half of the original PVA solution prepared in the step 2 into a reaction kettle, continuously adding 10 parts of glycerol into the reaction kettle, keeping the temperature and stirring for 30min to obtain a suspension solution, continuously adding 60 parts of butyl acrylate into the suspension solution, heating to 60 ℃, controlling the rotating speed to be 800r/min, keeping the temperature for 4 hours, adding 1 part of sodium chloride, stirring, cooling and standing to obtain the modified PVA mixed solution A;
step 4, preparing a modified PVA mixed solution B, injecting the other half of the original PVA solution prepared in the step 2 into a magnetic stirrer, continuously adding 100 parts of cellulose aqueous solution into the magnetic stirrer, controlling the temperature in the magnetic stirrer to be 25 ℃, controlling the rotating speed to be 650r/minn, and stirring for 3 hours to obtain the modified PVA mixed solution B;
step 5, preparing a first layer of film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on a flat film plate to scrape the film until the thickness of the film is 0.3mm, and standing for 48 hours at room temperature to obtain the first layer of film;
step 6, preparing a double-layer film, namely uniformly spraying the modified PVA mixed solution B prepared in the step 4 on the first layer film for film scraping until the thickness of the second layer film is 0.2mm, and standing for 48 hours at room temperature to obtain the double-layer film;
step 7, preparing a three-layer composite film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on the double-layer film for film scraping until the thickness of the third layer film is 0.3mm, and standing at room temperature for 48 hours to obtain the three-layer composite film;
and step 8, cleaning and drying: and (4) washing the three-layer composite film prepared in the step (7) by using a hydrochloric acid solution heated to 40 ℃, then washing by using clear water, and putting the film into a steam drying box for drying under pressure to obtain the formed PVA biological film.
Example 2:
60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent, 0.3-0.6 part of antioxidant, 60-100 parts of deionized water, 60-100 parts of butyl acrylate, 100 parts of cellulose aqueous solution, 10-20 parts of glycerol and 1-5 parts of sodium chloride.
Specifically, in this embodiment, the following steps are specifically performed: a PVA biodegradable film comprises the following components and parts by weight, 70 parts of polyvinyl alcohol, 25 parts of starch, 0.2 part of coupling agent, 0.4 part of antioxidant, 70 parts of deionized water, 70 parts of butyl acrylate, 105 parts of cellulose aqueous solution, 12 parts of glycerol and 2 parts of sodium chloride;
further, in the above components, the coupling agent is a titanate coupling agent, and the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester;
on the basis, the processing technology of the PVA biodegradable film comprises the following specific preparation steps:
step 1, preparing raw materials, namely 70 parts of polyvinyl alcohol, 25 parts of starch, 0.2 part of coupling agent, 0.4 part of antioxidant, 70 parts of deionized water, 70 parts of butyl acrylate, 105 parts of cellulose aqueous solution, 12 parts of glycerol and 2 parts of sodium chloride;
step 2, pretreatment, namely adding 70 parts of polyvinyl alcohol, 25 parts of starch, 0.2 part of coupling agent and 0.4 part of antioxidant into a stirring kettle, continuously injecting 70 parts of deionized water into the stirring kettle, controlling the internal temperature of the stirring kettle to be 82 ℃ by using a water bath heating mode, and stirring for 2 hours in a counterclockwise mode to obtain an original PVA solution;
step 3, preparing a modified PVA mixed solution A, injecting half of the original PVA solution prepared in the step 2 into a reaction kettle, continuously adding 12 parts of glycerol into the reaction kettle, keeping the temperature and stirring for 35min to obtain a suspension solution, continuously adding 70 parts of butyl acrylate into the suspension solution, heating to 60 ℃, controlling the rotation speed to 850r/min, keeping the temperature for 4 hours, adding 2 parts of sodium chloride, stirring, cooling and standing to obtain the modified PVA mixed solution A;
step 4, preparing a modified PVA mixed solution B, injecting the other half of the original PVA solution prepared in the step 2 into a magnetic stirrer, continuously adding 105 parts of cellulose aqueous solution into the magnetic stirrer, controlling the temperature in the magnetic stirrer to be 27 ℃, controlling the rotating speed to be 680r/min, and stirring for 4 hours to obtain the modified PVA mixed solution B;
step 5, preparing a first layer of film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on a flat film plate to scrape the film until the thickness of the film is 0.4mm, and standing at room temperature for 60 hours to obtain the first layer of film;
step 6, preparing a double-layer film, namely uniformly spraying the modified PVA mixed solution B prepared in the step 4 on the first layer film for film scraping until the thickness of the second layer film is 0.3mm, and standing at room temperature for 60 hours to obtain the double-layer film;
step 7, preparing a three-layer composite film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on the double-layer film for film scraping until the thickness of the third layer film is 0.4mm, and standing at room temperature for 60 hours to obtain the three-layer composite film;
and step 8, cleaning and drying: and (4) washing the three-layer composite film prepared in the step (7) by using a hydrochloric acid solution heated to 42 ℃, then washing by using clear water, and putting the film into a steam drying box for pressurization and drying to obtain the formed PVA biological film.
Example 3:
60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent, 0.3-0.6 part of antioxidant, 60-100 parts of deionized water, 60-100 parts of butyl acrylate, 100 parts of cellulose aqueous solution, 10-20 parts of glycerol and 1-5 parts of sodium chloride.
Specifically, in this embodiment, the following steps are specifically performed: a PVA biodegradable film comprises the following components and parts by weight, 80 parts of polyvinyl alcohol, 30 parts of starch, 0.3 part of coupling agent, 0.4 part of antioxidant, 80 parts of deionized water, 80 parts of butyl acrylate, 110 parts of cellulose aqueous solution, 15 parts of glycerol and 3 parts of sodium chloride;
further, in the above components, the coupling agent is selected from silane coupling agents, and the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
on the basis, the processing technology of the PVA biodegradable film comprises the following specific preparation steps:
step 1, preparing raw materials, namely 80 parts of polyvinyl alcohol, 30 parts of starch, 0.3 part of coupling agent, 0.4 part of antioxidant, 80 parts of deionized water, 80 parts of butyl acrylate, 110 parts of cellulose aqueous solution, 15 parts of glycerol and 3 parts of sodium chloride;
step 2, pretreatment, namely adding 80 parts of polyvinyl alcohol, 30 parts of starch, 0.3 part of coupling agent and 0.4 part of antioxidant into a stirring kettle, continuously injecting 80 parts of deionized water into the stirring kettle, controlling the internal temperature of the stirring kettle to be 83 ℃ by using a water bath heating mode, and stirring for 3 hours in a counterclockwise mode to obtain an original PVA solution;
step 3, preparing a modified PVA mixed solution A, injecting half of the original PVA solution prepared in the step 2 into a reaction kettle, continuously adding 15 parts of glycerol into the reaction kettle, keeping the temperature and stirring for 40min to obtain a suspension solution, continuously adding 80 parts of butyl acrylate into the suspension solution, heating to 60 ℃, controlling the rotating speed to be 900r/min, keeping the temperature for 4 hours, adding 3 parts of sodium chloride, stirring, cooling and standing to obtain the modified PVA mixed solution A;
step 4, preparing a modified PVA mixed solution B, injecting the other half of the original PVA solution prepared in the step 2 into a magnetic stirrer, continuously adding 110 parts of cellulose aqueous solution into the magnetic stirrer, controlling the temperature in the magnetic stirrer to be 30 ℃, controlling the rotating speed to be 700r/min, and stirring for 4 hours to obtain the modified PVA mixed solution B;
step 5, preparing a first layer of film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on a flat film plate to scrape the film until the thickness of the film is 0.4mm, and standing at room temperature for 64 hours to obtain the first layer of film;
step 6, preparing a double-layer film, namely uniformly spraying the modified PVA mixed solution B prepared in the step 4 on the first layer film for film scraping until the thickness of the second layer film is 0.3mm, and standing at room temperature for 64h to obtain the double-layer film;
step 7, preparing a three-layer composite film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on the double-layer film for film scraping until the thickness of the third layer film is 0.4mm, and standing at room temperature for 64 hours to obtain the three-layer composite film;
and step 8, cleaning and drying: and (4) washing the three-layer composite film prepared in the step (7) by using a hydrochloric acid solution heated to 45 ℃, then washing by using clear water, and putting the film into a steam drying box for drying under pressure to obtain the formed PVA biological film.
Example 4:
60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent, 0.3-0.6 part of antioxidant, 60-100 parts of deionized water, 60-100 parts of butyl acrylate, 100 parts of cellulose aqueous solution, 10-20 parts of glycerol and 1-5 parts of sodium chloride.
Specifically, in this embodiment, the following steps are specifically performed: a PVA biodegradable film comprises the following components and parts by weight, 90 parts of polyvinyl alcohol, 35 parts of starch, 0.4 part of coupling agent, 0.5 part of antioxidant, 90 parts of deionized water, 90 parts of butyl acrylate, 115 parts of cellulose aqueous solution, 18 parts of glycerol and 4 parts of sodium chloride;
further, in the above components, the coupling agent is one of titanate coupling agents, and the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ];
on the basis, the processing technology of the PVA biodegradable film comprises the following specific preparation steps:
step 1, preparing raw materials, namely 90 parts of polyvinyl alcohol, 35 parts of starch, 0.4 part of coupling agent, 0.5 part of antioxidant, 90 parts of deionized water, 90 parts of butyl acrylate, 115 parts of cellulose aqueous solution, 18 parts of glycerol and 4 parts of sodium chloride;
step 2, pretreatment, namely adding 90 parts of polyvinyl alcohol, 35 parts of starch, 0.4 part of coupling agent and 0.5 part of antioxidant into a stirring kettle, continuously injecting 90 parts of deionized water into the stirring kettle, controlling the internal temperature of the stirring kettle to be 83 ℃ by using a water bath heating mode, and stirring for 3 hours in a counterclockwise mode to obtain an original PVA solution;
step 3, preparing a modified PVA mixed solution A, injecting half of the original PVA solution prepared in the step 2 into a reaction kettle, continuously adding 18 parts of glycerol into the reaction kettle, keeping the temperature and stirring for 50min to obtain a suspension solution, continuously adding 90 parts of butyl acrylate into the suspension solution, heating to 60 ℃, controlling the rotation speed to 950r/min, keeping the temperature for 4 hours, adding 4 parts of sodium chloride, stirring, cooling and standing to obtain the modified PVA mixed solution A;
step 4, preparing a modified PVA mixed solution B, injecting the other half of the original PVA solution prepared in the step 2 into a magnetic stirrer, continuously adding 115 parts of cellulose aqueous solution into the magnetic stirrer, controlling the temperature in the magnetic stirrer to be 32 ℃, controlling the rotating speed to be 720r/min, and stirring for 4 hours to obtain the modified PVA mixed solution B;
step 5, preparing a first layer of film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on a flat film plate to scrape the film until the thickness of the film is 0.5mm, and standing at room temperature for 68 hours to obtain the first layer of film;
step 6, preparing a double-layer film, namely uniformly spraying the modified PVA mixed solution B prepared in the step 4 on the first layer of film for film scraping until the thickness of the second layer of film is 0.3mm, and standing at room temperature for 68 hours to obtain the double-layer film;
step 7, preparing a three-layer composite film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on the double-layer film for film scraping until the thickness of the third layer film is 0.5mm, and standing at room temperature for 68 hours to obtain the three-layer composite film;
and step 8, cleaning and drying: and (4) washing the three-layer composite film prepared in the step (7) by using a hydrochloric acid solution heated to 48 ℃, then washing by using clear water, and putting the film into a steam drying box for pressurization and drying to obtain the formed PVA biological film.
Example 5:
60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent, 0.3-0.6 part of antioxidant, 60-100 parts of deionized water, 60-100 parts of butyl acrylate, 100 parts of cellulose aqueous solution, 10-20 parts of glycerol and 1-5 parts of sodium chloride.
Specifically, in this embodiment, the following steps are specifically performed: a PVA biodegradable film comprises the following components and parts by weight, 100 parts of polyvinyl alcohol, 40 parts of starch, 0.5 part of coupling agent, 0.6 part of antioxidant, 100 parts of deionized water, 100 parts of butyl acrylate, 120 parts of cellulose aqueous solution, 20 parts of glycerol and 5 parts of sodium chloride;
further, in the above components, the coupling agent is a titanate coupling agent, and the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester;
on the basis, the processing technology of the PVA biodegradable film comprises the following specific preparation steps:
step 1, preparing raw materials, namely 60-100 parts of polyvinyl alcohol, 40 parts of starch, 0.5 part of coupling agent, 0.6 part of antioxidant, 100 parts of deionized water, 100 parts of butyl acrylate, 120 parts of cellulose aqueous solution, 20 parts of glycerol and 5 parts of sodium chloride;
step 2, pretreatment, namely adding 100 parts of polyvinyl alcohol, 40 parts of starch, 0.5 part of coupling agent and 0.6 part of antioxidant into a stirring kettle, continuously injecting 100 parts of deionized water into the stirring kettle, controlling the internal temperature of the stirring kettle to be 85 ℃ by using a water bath heating mode, and stirring for 3 hours in a counterclockwise mode to obtain an original PVA solution;
step 3, preparing a modified PVA mixed solution A, injecting half of the original PVA solution prepared in the step 2 into a reaction kettle, continuously adding 20 parts of glycerol into the reaction kettle, keeping the temperature and stirring for 60min to obtain a suspension solution, continuously adding 100 parts of butyl acrylate into the suspension solution, heating to 60 ℃, controlling the rotation speed to be 1000r/min, keeping the temperature for 4 hours, adding 5 parts of sodium chloride, stirring, cooling and standing to obtain the modified PVA mixed solution A;
step 4, preparing a modified PVA mixed solution B, injecting the other half of the original PVA solution prepared in the step 2 into a magnetic stirrer, continuously adding 120 parts of cellulose aqueous solution into the magnetic stirrer, controlling the temperature in the magnetic stirrer to be 35 ℃, controlling the rotating speed to be 750r/min, and stirring for 5 hours to obtain the modified PVA mixed solution B;
step 5, preparing a first layer of film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on a flat film plate to scrape the film until the thickness of the film is 0.6mm, and standing at room temperature for 72 hours to obtain the first layer of film;
step 6, preparing a double-layer film, namely uniformly spraying the modified PVA mixed solution B prepared in the step 4 on the first layer film for film scraping until the thickness of the second layer film is 0.4mm, and standing at room temperature for 72 hours to obtain the double-layer film;
step 7, preparing a three-layer composite film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on the double-layer film for film scraping until the thickness of the third layer film is 0.6mm, and standing at room temperature for 72 hours to obtain the three-layer composite film;
and step 8, cleaning and drying: and (4) washing the three-layer composite film prepared in the step (7) by using a hydrochloric acid solution heated to 50 ℃, then washing by using clear water, and putting the film into a steam drying box for pressurization and drying to obtain the formed PVA biological film.
Comparative example 1:
the following components are added in sequence according to the parts by weight: 80 parts of polyvinyl alcohol, 0.4 part of antioxidant, 80 parts of deionized water, 80 parts of butyl acrylate, 110 parts of cellulose aqueous solution, 15 parts of glycerol and 3 parts of sodium chloride.
Comparative example 2:
the following components are added in sequence according to the parts by weight: 80 parts of polyvinyl alcohol, 30 parts of starch, 0.3 part of coupling agent, 0.4 part of antioxidant, 80 parts of deionized water, 110 parts of cellulose aqueous solution and 3 parts of sodium chloride.
Five PVA biodegradable films can be obtained through the five groups of embodiments, and the results of testing the five PVA biodegradable films respectively show that the biodegradability of the PVA biodegradable films in the five groups of embodiments has different changes, wherein the PVA biodegradable film in the embodiment 3 has the best biodegradability and the lowest water vapor permeability, and in the testing process, the obtained parameters are as follows:
from the data, the PVA biodegradable film prepared in the embodiment 3 of the invention has obvious and excellent effect, strongest biodegradability, lowest water vapor permeability and strong wear resistance in the testing process, the invention properly adds the glycerol and the butyl acrylate through a reasonable process in the raw material modification production process, the mixture ratio of the glycerol and the butyl acrylate is proper, the hydrophilic hydroxyl of the glycerol and the hydrophilic bond of the butyl acrylate react with the unsaturated bond of the polyvinyl alcohol, the barrier property of water molecules is greatly enhanced, simultaneously, when the raw materials are modified and produced, the modified PVA film has good plasticity and good biodegradability after the maltose obtained by decomposing starch is compounded with the polyvinyl alcohol, the modified PVA biodegradable film with good mechanical property and excellent degradability can be prepared by optimizing the mixture ratio of the raw materials and optimizing the process conditions, the PVA biodegradable film prepared by the method has 100% environmental degradability, is completely converted into water, carbon dioxide and organic matters, is not harmful to the environment or soil, and has the advantages of simple process, low equipment requirement and high cost performance.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (7)
1. A PVA biodegradable film is characterized by comprising the following components in parts by weight: 60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent, 0.3-0.6 part of antioxidant, 60-100 parts of deionized water, 60-100 parts of butyl acrylate, 100-120 parts of cellulose aqueous solution, 10-20 parts of glycerol and 1-5 parts of sodium chloride.
2. The PVA biodegradable film according to claim 1, comprising the following components in parts by weight: 70-90 parts of polyvinyl alcohol, 25-35 parts of starch, 0.2-0.4 part of coupling agent, 0.4-0.5 part of antioxidant, 70-90 parts of deionized water, 70-90 parts of butyl acrylate, 115 parts of cellulose aqueous solution 105-containing liquid, 12-18 parts of glycerol and 2-4 parts of sodium chloride.
3. The PVA biodegradable film according to claim 1, comprising the following components in parts by weight: 80 parts of polyvinyl alcohol, 30 parts of starch, 0.3 part of coupling agent, 0.5 part of antioxidant, 80 parts of deionized water, 80 parts of butyl acrylate, 110 parts of cellulose aqueous solution, 15 parts of glycerol and 3 parts of sodium chloride.
4. The PVA biodegradable film according to claim 1, wherein the coupling agent is one selected from a silane coupling agent and a titanate coupling agent, and the antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
5. The PVA biodegradable film according to any one of claims 1 to 4, further comprising a PVA biodegradable film processing technology, specifically comprising the following steps:
step 1, preparing raw materials, namely 60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent, 0.3-0.6 part of antioxidant, 60-100 parts of deionized water, 60-100 parts of butyl acrylate, 100 parts of cellulose aqueous solution, 10-20 parts of glycerol and 1-5 parts of sodium chloride;
step 2, pretreatment, namely adding 60-100 parts of polyvinyl alcohol, 20-40 parts of starch, 0.1-0.5 part of coupling agent and 0.3-0.6 part of antioxidant into a stirring kettle, continuously injecting 60-100 parts of deionized water into the stirring kettle, keeping the temperature unchanged, and stirring for 2-3 hours in a counterclockwise manner to obtain an original PVA solution;
step 3, preparing a modified PVA mixed solution A, injecting half of the original PVA solution prepared in the step 2 into a reaction kettle, continuously adding 10-20 parts of glycerol into the reaction kettle, keeping the temperature and stirring for 30-60min to obtain a suspension solution, continuously adding 60-100 parts of butyl acrylate into the suspension solution, heating and keeping the temperature for 4 hours, adding 1-5 parts of sodium chloride, stirring, cooling and standing to obtain the modified PVA mixed solution A;
step 4, preparing a modified PVA mixed solution B, injecting the other half of the original PVA solution prepared in the step 2 into a magnetic stirrer, continuously adding 120 parts of cellulose aqueous solution into the magnetic stirrer, controlling the temperature in the magnetic stirrer to be 25-35 ℃, controlling the rotating speed to be 650-750 r/min, and stirring for 3-5 hours to obtain the modified PVA mixed solution B;
step 5, preparing a first layer of film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on a flat film plate to scrape the film until the thickness of the film is 0.3mm-0.6mm, and standing at room temperature for 48-72 hours to obtain the first layer of film;
step 6, preparing a double-layer film, namely uniformly spraying the modified PVA mixed solution B prepared in the step 4 on the first layer of film for film scraping until the thickness of the second layer of film is 0.2-0.4 mm, and standing at room temperature for 48-72 hours to obtain the double-layer film;
step 7, preparing a three-layer composite film, uniformly spraying the modified PVA mixed solution A prepared in the step 3 on the double-layer film for film scraping until the thickness of the third layer film is 0.3-0.6 mm, and standing at room temperature for 48-72 hours to obtain the three-layer composite film;
and step 8, cleaning and drying: and (4) washing the three-layer composite film prepared in the step (7) by using a hydrochloric acid solution heated to 40-50 ℃, then washing by using clear water, and putting the washed three-layer composite film into a steam drying box for drying under pressure to obtain the formed PVA biological film.
6. The processing technology of PVA biodegradable film according to claim 5, characterized in that: in the step 2, the internal temperature of the stirring kettle is controlled to be 80-85 ℃ by a water bath heating mode.
7. The processing technology of PVA biodegradable film according to claim 5, characterized in that: in the step 3, the temperature of the reaction kettle added with the butyl acrylate is raised to 60 ℃, and the rotating speed is controlled to be 800-1000 r/min.
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