CN114437481A - Polyvinyl alcohol composition, polyvinyl alcohol film and preparation method thereof - Google Patents

Polyvinyl alcohol composition, polyvinyl alcohol film and preparation method thereof Download PDF

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CN114437481A
CN114437481A CN202011189213.5A CN202011189213A CN114437481A CN 114437481 A CN114437481 A CN 114437481A CN 202011189213 A CN202011189213 A CN 202011189213A CN 114437481 A CN114437481 A CN 114437481A
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polyvinyl alcohol
weight
component
composition
plasticizer
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CN114437481B (en
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徐萌
白弈青
高达利
张师军
徐凯
权慧
董穆
吕芸
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2427/00—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 a halogen; Derivatives of such polymers
    • C08J2427/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
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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
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    • 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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    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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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
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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
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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
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    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids

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Abstract

The invention relates to the field of polyvinyl alcohol films, and discloses a polyvinyl alcohol composition, a polyvinyl alcohol film and a preparation method thereof. The polyvinyl alcohol composition comprises polyvinyl alcohol, a plasticizer, water and a lubricant; wherein the plasticizer comprises a component A, a component B and a component C; wherein the component A is one or more of glycerol, polyethylene glycol and pentaerythritol; the component B is one or more of magnesium chloride, magnesium nitrate, copper sulfate and sodium acetate; the component C is one or more of potassium iodide, zinc nitrate, lithium iodide, cobalt nitrate and cobalt sulfate. The polyvinyl alcohol film provided by the invention has the advantages of high mechanical property, less plasticizer precipitation amount, good optical property and strong stability, and the preparation method is simple, the production rate is high, and the polyvinyl alcohol film is suitable for industrial popularization.

Description

Polyvinyl alcohol composition, polyvinyl alcohol film and preparation method thereof
Technical Field
The invention relates to the field of polyvinyl alcohol films, in particular to a polyvinyl alcohol composition, a polyvinyl alcohol film and a preparation method thereof.
Background
Polyvinyl alcohol (PVA) film is a few of industrially produced non-petroleum-based polymer materials which can be prepared from natural gas, has excellent acid and alkali resistance and organic solvent resistance, has excellent barrier property and good biocompatibility, can be degraded by 75% in 46 days under the action of bacteria and enzyme, belongs to a biodegradable polymer material, has unique advantages in the fields of textile, food, medicine, construction, wood processing, paper making, printing, agriculture, steel, polymer chemical industry and the like, and has wide application.
At present, the polyvinyl alcohol film is difficult to be processed by hot molding, and is mainly produced by adopting a solution casting method. In the production process of the polyvinyl alcohol film, various additives, particularly a plasticizer, need to be added. However, the addition amount of the plasticizer is generally large, so that the plasticizer is easy to remain in the preparation process of the polyvinyl alcohol film, and the processing efficiency is low; and in the use process of the polyvinyl alcohol film, the plasticizer can be slowly separated out, so that the haze of the polyvinyl alcohol film is increased, the light transmittance is reduced, and the service life is shortened. If the amount of the plasticizer is directly reduced, the processability of the polyvinyl alcohol film is deteriorated, and the quality of the polyvinyl alcohol film is reduced.
Therefore, it is desired to provide a polyvinyl alcohol film having good processability, a small amount of plasticizer precipitation and stable optical properties, and a method for producing the same.
Disclosure of Invention
The invention aims to solve the problems of unstable optical performance and poor processability of a polyvinyl alcohol film in the prior art, and provides a polyvinyl alcohol composition, a polyvinyl alcohol film and a preparation method thereof.
In order to achieve the above objects, an aspect of the present invention provides a polyvinyl alcohol composition comprising polyvinyl alcohol, a plasticizer, water, and a lubricant; wherein the plasticizer accounts for 4 to 10 percent of the weight of the composition; the water accounts for 10 to 20 percent of the weight of the composition; the lubricant accounts for 0.5 to 2 percent of the weight of the composition, and the polyvinyl alcohol accounts for 68 to 85.5 percent of the weight of the composition;
wherein the plasticizer comprises 50-80 parts by weight of component A, 10-30 parts by weight of component B and 10-20 parts by weight of component C; the component A is one or more of glycerol, polyethylene glycol and pentaerythritol; the component B is one or more of magnesium chloride, magnesium nitrate, copper sulfate and sodium acetate; the component C is one or more of potassium iodide, zinc nitrate, lithium iodide, cobalt nitrate and cobalt sulfate.
In a second aspect, the present invention provides a method for preparing a polyvinyl alcohol film, which comprises melt-extruding and casting a mixture of polyvinyl alcohol, a plasticizer, water, a lubricant, and optionally an antioxidant to form a film, thereby obtaining the polyvinyl alcohol film.
The third aspect of the invention provides a polyvinyl alcohol film, wherein after the polyvinyl alcohol film is subjected to high-temperature and high-humidity treatment, the precipitation rate of a plasticizer is less than 0.5%;
wherein the light transmittance of the polyvinyl alcohol film is more than 92%, the haze is not more than 3%, and the water content is not more than 13%;
preferably, the thickness of the polyvinyl alcohol film is 40-80 μm, and the polyvinyl alcohol film can bear the stretching speed of more than 300%/s when being subjected to unidirectional stretching in an air atmosphere.
Through the technical scheme, the invention has the following beneficial technical effects:
1) according to the polyvinyl alcohol composition provided by the invention, through the synergistic effect of the components, the mechanical property and the optical property of the polyvinyl alcohol film can be maintained and even further improved on the premise of reducing the dosage of the plasticizer, the problems of plasticizer residue in the preparation process of the polyvinyl alcohol film and plasticizer precipitation in the use process of the polyvinyl alcohol film are solved, and the plasticizer precipitation rate of the polyvinyl alcohol film is less than 0.5%, so that the stability of the optical property of the polyvinyl alcohol film is improved, and the service life of the polyvinyl alcohol film is prolonged;
2) the polyvinyl alcohol film provided by the invention has the advantage of good optical performance, the light transmittance of the polyvinyl alcohol film is more than 92%, and the haze is not more than 3%; the polyvinyl alcohol film provided by the invention also has the advantage of stable optical performance, and the change of light transmittance and haze is small after high-temperature and high-humidity treatment, wherein the light transmittance of the polyvinyl alcohol film is not less than 90%, and the haze of the polyvinyl alcohol film is not more than 5%;
3) the preparation method of the polyvinyl alcohol film solves the problems of complicated steps and poor product quality existing in the preparation of the polyvinyl alcohol film by a solution casting method, the obtained polyvinyl alcohol film has the water content of not more than 13 percent, can be directly stretched, omits a drying step, simplifies the operation process, has good mechanical property of the product, can bear the stretching speed of more than 300 percent/s, improves the production rate of the film, and is suitable for industrial popularization.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides in a first aspect a polyvinyl alcohol composition comprising polyvinyl alcohol, a plasticizer, water and a lubricant; wherein, the weight percentage of the plasticizer in the composition is 4-10%, the weight percentage of the water in the composition is 10-20%, the weight percentage of the lubricant in the composition is 0.5-2%, and the weight percentage of the polyvinyl alcohol in the composition is 68-85.5%;
wherein the plasticizer comprises 50-80 parts by weight of component A, 10-30 parts by weight of component B and 10-20 parts by weight of component C; wherein the component A is one or more of glycerol, polyethylene glycol and pentaerythritol; the component B is one or more of magnesium chloride, magnesium nitrate, copper sulfate and sodium acetate; the component C is one or more of potassium iodide, zinc nitrate, lithium iodide, cobalt nitrate and cobalt sulfate.
In the invention, the inventor finds that the addition of the component B can improve the processing stability of the polyvinyl alcohol film, and the addition of the component C can improve the light transmittance and the subsequent optical property stability of the polyvinyl alcohol film. At present, in the production process of polyvinyl alcohol, the addition amount of a plasticizer is generally more than 15%, and in the invention, the component A, the component B and the component C with specific contents, the polyvinyl alcohol with specific contents, water and a lubricant are combined together to realize interaction and synergistic interaction, so that on one hand, the use amount of the plasticizer can be reduced, the use amount of the plasticizer is lower than 10%, the problems of residue and precipitation of the plasticizer are solved, the service life of the polyvinyl alcohol film is prolonged, and on the other hand, the optical performance and the mechanical performance of the polyvinyl alcohol film can be maintained and even further improved, and the modification effect is realized.
In a preferred embodiment, the plasticizer is present in an amount of 5 to 8% by weight of the composition, the water is present in an amount of 12 to 18% by weight of the composition, the lubricant is present in an amount of 1 to 1.8% by weight of the composition, and the polyvinyl alcohol is present in an amount of 72.2 to 82% by weight of the composition.
The inventor researches and discovers that when the using amounts of the polyvinyl alcohol, the plasticizer, the water and the lubricant are limited to the ranges, the prepared polyvinyl alcohol film has better optical performance, higher mechanical property and stronger stability.
In a preferred embodiment, the degree of alcoholysis of the polyvinyl alcohol is 97-99 mol%, the degree of polymerization is 2000-400-micron, and the particle size is 320-400 μm.
In a preferred embodiment, the plasticizer comprises 60 to 75 parts by weight of component a, 15 to 25 parts by weight of component B, 10 to 15 parts by weight of component C.
In a preferred embodiment, in the plasticizer, the component A is one of a mixture of polyethylene glycol and glycerol and a mixture of polyethylene glycol and pentaerythritol; wherein, in the mixture of polyethylene glycol and glycerol, the weight ratio of polyethylene glycol to glycerol is 1:1-6, preferably 1: 2-5; in the mixture of polyethylene glycol and pentaerythritol, the weight ratio of polyethylene glycol to pentaerythritol is 1:1 to 6, preferably 1:2 to 5.
In a preferred embodiment, the polyethylene glycol in component A has an average molecular weight of 400-.
The polyethylene glycol has better plasticizing effect under the molecular weight, and is not easy to separate out in the using and placing processes of the polyvinyl alcohol film.
In a preferred embodiment, component B is one of magnesium chloride and magnesium nitrate; the component C is one of potassium iodide, zinc nitrate and cobalt sulfate.
In a preferred embodiment, the lubricant is selected from one or two of a polyethylene glycol-based lubricant, a fluoropolymer-based lubricant, and a silicone-based lubricant, and is preferably a polyethylene glycol-based lubricant.
In the present invention, the polyethylene glycol lubricant refers to polyethylene glycol with a molecular weight of 1000 or more, wherein the average molecular weight of polyethylene glycol is 1000-.
In a preferred embodiment, the polyvinyl alcohol composition further comprises an antioxidant, wherein the antioxidant accounts for 0.05 to 0.3 percent of the weight of the composition, and is preferably 0.15 to 0.25 percent of the weight of the composition.
In a preferred embodiment, the antioxidant is selected from antioxidant 1010 and/or antioxidant 168, preferably antioxidant 1010 and antioxidant 168, wherein the mass ratio of antioxidant 1010 to antioxidant 168 is 1-4:1, preferably 1-2: 1.
The invention further improves the comprehensive performance of the polyvinyl alcohol film by selecting the specific antioxidant, so that the polyvinyl alcohol film has higher mechanical property, better optical property and stronger stability.
In a second aspect, the present invention provides a method for preparing a polyvinyl alcohol film, which comprises melt-extruding and casting a mixture of polyvinyl alcohol, a plasticizer, water, a lubricant, and optionally an antioxidant to form a film, thereby obtaining the polyvinyl alcohol film.
In a preferred embodiment, the polyvinyl alcohol, plasticizer, water, lubricant and optional antioxidant are as described above and the invention is not described herein in detail.
In a preferred embodiment, the method of mixing the mixture is as follows: firstly, mixing the plasticizer and water at the mixing temperature of 40-80 ℃ for 0.5-2h, then adding the polyvinyl alcohol, the lubricant and the optional antioxidant for mixing, firstly mixing for 10-30min at the temperature of 50-80 ℃, and then mixing for 20-60min at the temperature of 20-40 ℃.
The penetration effect of the plasticizer in the polyvinyl alcohol can be improved by adopting a specific mixing sequence and specific mixing conditions, so that the processing performance of the polyvinyl alcohol is further improved, and the stretching rate of the polyvinyl alcohol in the subsequent stretching process is increased.
In a preferred embodiment, the melt extrusion and casting of the film is carried out in a casting machine; the temperature of the melt extrusion is 110-190 ℃, preferably 120-180 ℃, and the temperature of the casting die head is 120-190 ℃, preferably 140-170 ℃; the casting chill roll temperature of the casting film preparation is 30-70 ℃, and preferably 40-60 ℃.
In the invention, the stability of the melt extrusion process can be ensured by controlling the operating temperature of the casting machine, and meanwhile, the water content of the polyvinyl alcohol film is further reduced, the operation flow is simplified, and the processing efficiency is improved.
The preparation method of the polyvinyl alcohol film provided by the invention adopts the polyvinyl alcohol composition as the raw material, solves the problems of complex operation process and poor product performance when the polyvinyl alcohol film is prepared by a solution casting method, is simple to operate, has high product quality and is suitable for industrial popularization.
In a third aspect, the present invention provides a polyvinyl alcohol film, wherein the precipitation rate of a plasticizer after the polyvinyl alcohol film is subjected to high temperature and high humidity treatment is less than 0.5%, preferably less than 0.25%.
The high-temperature and high-humidity treatment and the plasticizer precipitation rate of the polyvinyl alcohol film of the invention are measured by the following methods: cutting a polyvinyl alcohol film into 10 x 10cm samples, placing the samples into a constant temperature and humidity box, standing the samples for 48 hours at 23 ℃ under the condition of RH 55%, and weighing the samples to obtain the initial mass (m) of the samples0). Then the sample is put into a vacuum oven, dried to constant weight at 100 ℃ and then placed for 168 hours at 80 ℃. Finally, taking out the sample, placing the sample in a constant temperature and humidity box, placing the sample for 48 hours under the conditions of 23 ℃ and RH 55%, and then weighing to obtain the mass (m) of the treated sample1). In the invention, the operation of drying to constant weight abandons the influence of moisture, the polyvinyl alcohol and the lubricant can not be separated out in the high-temperature and high-humidity treatment process, and the reduced mass before and after the treatment of the polyvinyl alcohol film is the amount of the separated-out plasticizer. The precipitation rate of the plasticizer is calculated by the following formula:
Figure BDA0002752263980000071
the invention aims to rapidly precipitate the plasticizer in a short time so as to examine the precipitation rate of the plasticizer and test the stability of the polyvinyl alcohol film. After the high-temperature and high-humidity treatment, the smaller the precipitation rate of the plasticizer, the better the stability, especially the optical stability, of the polyvinyl alcohol film.
In a preferred embodiment, the light transmittance of the polyvinyl alcohol film is 92% or more, preferably 93% or more, and the light transmittance of the polyvinyl alcohol film after the high-temperature and high-humidity treatment is not less than 90%, preferably not less than 92%.
In a preferred embodiment, the haze of the polyvinyl alcohol film is not more than 3%, preferably not more than 2.5%, and the haze of the polyvinyl alcohol film after high temperature and high humidity treatment is not more than 5%, preferably not more than 4%.
After the polyvinyl alcohol film is subjected to high-temperature and high-humidity treatment, the change of light transmittance and haze is small, so that the optical stability of the polyvinyl alcohol film is good.
In a preferred embodiment, the polyvinyl alcohol film has a water content of not more than 13%, preferably not more than 10%.
When the polyvinyl alcohol film is prepared by the current solution casting method, the film strength is poor when the water content is too high, and the film is easy to break in the stretching process, so that the stretching operation is ensured, and the separate drying operation is often required to ensure that the water content of the polyvinyl alcohol film is not higher than 15%. Because the drying process is generally slow, the production rate of the polyvinyl alcohol film is reduced, and the production period of the polyvinyl alcohol film is prolonged. The water content of the polyvinyl alcohol film provided by the invention is not more than 13%, and downstream stretching processing can be directly carried out without drying operation, so that the production flow is simplified, the production cost is saved, the production speed is increased, and the polyvinyl alcohol film is beneficial to industrial production.
In a preferred embodiment, the polyvinyl alcohol film has a thickness of 40 to 80 μm, and can be uniaxially stretched in an air atmosphere at a stretch rate of 300%/s or more, preferably 380%/s or more.
The polyvinyl alcohol film prepared by the solution casting method at present generally has the problem of poor mechanical property, and the unidirectional stretching speed which can be borne by the polyvinyl alcohol film with the thickness of 40-80 mu m is generally 50-100%/s. In the invention, the mechanical property of the polyvinyl alcohol film is obviously improved through the synergistic effect of the components and the limitation of the operation conditions in the preparation process, the polyvinyl alcohol film can bear higher stretching speed (more than 300%/s) under smaller thickness (40-80 mu m), and the production rate of the polyvinyl alcohol film is improved.
In a preferred embodiment, the polyvinyl alcohol film of the invention can be applied to the fields of optical display and functional packaging.
The present invention will be described in detail below by way of examples.
In the following examples:
polyvinyl alcohol was purchased from Chongqing Chunwei Co., Ltd, China petrochemical; the fluoropolymer is available from solvay polymers corporation under the designation 1001; polyethylene glycol PEG was purchased from sanyo japan; glyceryl monostearate, designation Atmer129, available from prochloraz company; antioxidants 1010, 168 were purchased from Ciba chemical (China) Inc., Switzerland. The multilayer extrusion casting machine is available from Labtech, Sweden, under the model LCR 400.
The water content is measured by cutting polyvinyl alcohol film into 10 × 10cm samples, weighing, and taking the weight as Wa. Putting the sample into a vacuum oven, setting the temperature at 100 ℃, taking out the sample once every 2 hours, sealing, cooling, weighing until the weight is not changed any more, and taking the sample with the final weight of Wb。
Figure BDA0002752263980000081
The method for measuring the precipitation amount of the plasticizer comprises the steps of cutting the polyvinyl alcohol film into 10 x 10cm samples, placing the samples into a constant temperature and humidity box, placing the samples for 48 hours under the conditions of 23 ℃ and RH 55%, and weighing the samples to obtain the initial mass (m) of the samples0). Then the sample is put into a vacuum ovenFirstly, drying the mixture at 100 ℃ to constant weight, and then placing the mixture at 80 ℃ for 168 hours. Finally, taking out the sample, placing the sample in a constant temperature and humidity box, placing the sample for 48 hours under the conditions of 23 ℃ and RH 55%, and then weighing to obtain the mass (m) of the treated sample1) The precipitation rate of the plasticizer is calculated by the following formula:
Figure BDA0002752263980000091
the light transmittance and haze of the polyvinyl alcohol film were measured according to the methods specified in GB/T2410-; the light transmittance and haze after the treatment were measured by the mass m in the measurement of the amount of precipitated plasticizer1The sample of (2) was tested.
A method for measuring the bearable stretching speed of polyvinyl alcohol film includes such steps as cutting the polyvinyl alcohol film, loading it in the stretching fixture of bidirectional stretching equipment, unidirectionally stretching at 150 deg.C in air atmosphere at 4 times of stretching ratio, and measuring the maximum stretching speed without breaking.
Preparation example of plasticizer
According to the formula of table 1, component a, component B and component C were mixed in proportion to obtain the corresponding plasticizers.
TABLE 1
Figure BDA0002752263980000092
Figure BDA0002752263980000101
Note: the above components A and B are metered in pure form as indicated in the table.
Example 1
(1) Mixing plasticizer E1 and water at 60 deg.C for 0.5h, adding lubricant polyethylene glycol (molecular weight 5000), antioxidant (antioxidant 1010: antioxidant 168 ═ 1:1) and polyvinyl alcohol (alcoholysis degree 99 mol%, polymerization degree 2000, particle size 400 μm), mixing at 80 deg.C for 10min, keeping temperature at 40 deg.C, stirring and mixing for 30min, and naturally cooling to room temperature to obtain polyvinyl alcohol composition; wherein the raw material feeding amount is that in the obtained polyvinyl alcohol composition, the weight fraction of the plasticizer E1 is 8%, the weight fraction of water is 18%, the weight fraction of the lubricant is 1%, the weight fraction of the antioxidant is 0.2%, and the weight fraction of the polyvinyl alcohol is 72.8%;
(2) adding the polyvinyl alcohol composition prepared in the step (1) into a multilayer extrusion casting machine for melt extrusion and casting to prepare a film, wherein the temperature of each section of the melt extrusion is 120-180 ℃, the temperature of a casting die head is 170 ℃, and the temperature of a casting chill roll is 40 ℃ to obtain the polyvinyl alcohol film, and the properties of the polyvinyl alcohol film are shown in Table 2.
Example 2
(1) Mixing plasticizer E2 and water at 60 ℃ for 0.5h, then adding lubricant polyethylene glycol (molecular weight 5000), antioxidant (antioxidant 1010: antioxidant 168 ═ 2:1) and polyvinyl alcohol (alcoholysis degree 97 mol%, polymerization degree 2700, particle size 320 mu m), mixing at 80 ℃ for 10min, keeping the temperature at 40 ℃, stirring and mixing for 30min, and naturally cooling to room temperature to obtain a polyvinyl alcohol composition; wherein the raw material feeding amount is such that in the obtained polyvinyl alcohol composition, the weight fraction of the plasticizer E2 is 5%, the weight fraction of water is 12%, the weight fraction of the lubricant is 1.8%, the weight fraction of the antioxidant is 0.2%, and the weight fraction of the polyvinyl alcohol is 81%;
(2) adding the polyvinyl alcohol composition prepared in the step (1) into a multilayer extrusion casting machine for melt extrusion and casting to prepare a film, wherein the temperature of each section of the melt extrusion is 120-180 ℃, the temperature of a casting die head is 140 ℃, and the temperature of a casting chill roll is 60 ℃, so that the polyvinyl alcohol film is obtained, and the properties of the polyvinyl alcohol film are shown in Table 2.
Example 3
Similar to the method described in example 1, with the difference that: keeping the antioxidant unchanged, adopting a plasticizer E3 to replace E1, wherein the molecular weight of the lubricant polyethylene glycol is 6000, the alcoholysis degree of the polyvinyl alcohol is 99%, the polymerization degree is 2500, and the particle size is 360 um; wherein the raw material feeding amount is such that in the obtained polyvinyl alcohol composition, the weight fraction of the plasticizer E3 is 6%, the weight fraction of water is 15%, the weight fraction of the lubricant is 1.5%, the weight fraction of the antioxidant is 0.2%, and the weight fraction of the polyvinyl alcohol is 77.3%; the properties of the polyvinyl alcohol film obtained are shown in Table 2.
Examples 4 to 5
Similar to the method described in example 1, with the difference that: the plasticizers E4-E5 were used in place of E1, while keeping the amount of the plasticizer added constant, to obtain a polyvinyl alcohol film. The properties of the polyvinyl alcohol film obtained are shown in Table 2.
Example 6
Similar to the method described in example 1, with the difference that: the usage amounts of the plasticizer E1, water, the lubricant and polyvinyl alcohol are changed, wherein the raw material feeding amounts are such that in the obtained polyvinyl alcohol composition, the weight fraction of the plasticizer E1 is 4%, the weight fraction of the water is 20%, the weight fraction of the lubricant is 2%, the weight fraction of the antioxidant is 0.2%, and the weight fraction of the polyvinyl alcohol is 73.8%; the properties of the polyvinyl alcohol film obtained are shown in Table 2.
Example 7
Similar to the method described in example 1, with the difference that: the usage amounts of the plasticizer E1, water, the lubricant and polyvinyl alcohol are changed, wherein the raw material feeding amounts are such that in the obtained polyvinyl alcohol composition, the weight fraction of the plasticizer E1 is 10%, the weight fraction of the water is 10%, the weight fraction of the lubricant is 0.5%, the weight fraction of the antioxidant is 0.2%, and the weight fraction of the polyvinyl alcohol is 79.3%; the properties of the polyvinyl alcohol film obtained are shown in Table 2.
Example 8
Similar to the method described in example 1, with the difference that: the lubricant used was a fluoropolymer and the properties of the resulting polyvinyl alcohol film are shown in table 2.
Comparative examples 1 to 5
The method according to example 1, with the difference that: the addition amount of the plasticizer is kept unchanged, the plasticizer DE1-DE5 is respectively adopted to replace E1, and the comparative examples 1-5 cannot be extruded normally in the casting process, so that corresponding films cannot be obtained.
Comparative example 6
The method according to example 1, with the difference that: the usage amounts of the plasticizer E1, water, the lubricant and polyvinyl alcohol are changed, wherein the raw material feeding amounts are such that in the obtained polyvinyl alcohol composition, the weight fraction of the plasticizer E1 is 15%, the weight fraction of the water is 30%, the weight fraction of the lubricant is 0.5%, the weight fraction of the antioxidant is 0.2%, and the weight fraction of the polyvinyl alcohol is 54.3%; the properties of the polyvinyl alcohol film obtained are shown in Table 2.
Comparative example 7
The method according to example 1, with the difference that: the alcoholysis degree of the used polyvinyl alcohol is 88%, the polymerization degree is 1700, the particle size is 180um, and the properties of the obtained polyvinyl alcohol film are shown in Table 2.
Comparative example 8
The method according to example 1, with the difference that: the molecular weight of polyethylene glycol in component A in the plasticizer E1 was 200, and the properties of the obtained polyvinyl alcohol film are shown in Table 2.
Comparative example 9
Similar to the method described in example 1, with the difference that: the lubricant used was glyceryl monostearate and the properties of the resulting polyvinyl alcohol film are shown in Table 2.
Comparative example 10
The method according to example 1, with the difference that: the plasticizer E1 contained no component C, and the properties of the resulting polyvinyl alcohol film are shown in Table 2.
Comparative example 11
A polyvinyl alcohol film was prepared according to CN109721910A example 1. The amount of plasticizer precipitated was measured as shown in Table 2.
TABLE 2
Figure BDA0002752263980000131
Figure BDA0002752263980000141
As can be seen from the data in Table 2, the polyvinyl alcohol film prepared by the method provided by the invention has high light transmittance and haze, wherein the light transmittance is more than 92%, and the haze is lower than 3%. And after high-temperature and high-humidity treatment, the change of light transmittance and haze is small, and the precipitation amount of the plasticizer is small. The film can reach the water content below 13% without drying, and can be directly subjected to other process steps such as unidirectional stretching and the like. The polyvinyl alcohol film prepared by the invention can bear the stretching speed of more than 300%/s, can be subjected to a rapid and efficient post-treatment process, and can greatly improve the production efficiency.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A polyvinyl alcohol composition, wherein the polyvinyl alcohol composition comprises polyvinyl alcohol, a plasticizer, water, and a lubricant; wherein, the plasticizer accounts for 4 to 10 percent of the weight of the composition, the water accounts for 10 to 20 percent of the weight of the composition, the lubricant accounts for 0.5 to 2 percent of the weight of the composition, and the polyvinyl alcohol accounts for 68 to 85.5 percent of the weight of the composition;
wherein the plasticizer comprises 50-80 parts by weight of component A, 10-30 parts by weight of component B and 10-20 parts by weight of component C; the component A is one or more of glycerol, polyethylene glycol and pentaerythritol; the component B is one or more of magnesium chloride, magnesium nitrate, copper sulfate and sodium acetate; the component C is one or more of potassium iodide, zinc nitrate, lithium iodide, cobalt nitrate and cobalt sulfate.
2. The polyvinyl alcohol composition according to claim 1, wherein the plasticizer is present in an amount of 5 to 8% by weight of the composition, and the water is present in an amount of 12 to 18% by weight of the composition; the lubricant accounts for 1 to 1.8 percent of the weight of the composition, and the polyvinyl alcohol accounts for 72.2 to 82 percent of the weight of the composition.
3. The polyvinyl alcohol composition as claimed in claim 1 or 2, wherein the polyvinyl alcohol has an alcoholysis degree of 97 to 99 mol%, a polymerization degree of 2000-2700 and a particle size of 320-400 μm.
4. The polyvinyl alcohol composition according to any one of claims 1 to 3, wherein the plasticizer comprises 60 to 75 parts by weight of component A, 15 to 25 parts by weight of component B, 10 to 15 parts by weight of component C; the component A is one of a mixture of polyethylene glycol and glycerol and a mixture of polyethylene glycol and pentaerythritol; the component B is one of magnesium chloride and magnesium nitrate; the component C is one of potassium iodide, zinc nitrate and cobalt sulfate.
5. The polyvinyl alcohol composition according to any one of claims 1 to 4, wherein the polyethylene glycol in component A has an average molecular weight of 400-.
6. The polyvinyl alcohol composition according to claim 1, wherein the lubricant is selected from one or two of a polyethylene glycol-based lubricant, a fluoropolymer-based lubricant, and a silicone-based lubricant, preferably a polyethylene glycol-based lubricant;
preferably, the average molecular weight of the polyethylene glycol in the polyethylene glycol lubricant is 1000-8000, preferably 4000-6000.
7. The polyvinyl alcohol composition according to any one of claims 1 to 6, wherein the polyvinyl alcohol composition further comprises an antioxidant in an amount of 0.05 to 0.3%, preferably 0.15 to 0.25% by weight of the composition.
8. The polyvinyl alcohol composition according to claim 7, wherein the antioxidant is selected from antioxidant 1010 and/or antioxidant 168, preferably antioxidant 1010 and antioxidant 168, wherein the mass ratio of antioxidant 1010 to antioxidant 168 is 1-4:1, preferably 1-2: 1.
9. A method for preparing a polyvinyl alcohol film is characterized by comprising the steps of carrying out melt extrusion on a mixture of polyvinyl alcohol, a plasticizer, water, a lubricant and an optional antioxidant and carrying out film casting to obtain the polyvinyl alcohol film.
10. The polyvinyl alcohol film is characterized in that after the polyvinyl alcohol film is subjected to high-temperature and high-humidity treatment, the precipitation rate of a plasticizer is less than 0.5%;
preferably, the light transmittance of the polyvinyl alcohol film is more than 92%, the haze is not more than 3%, and the water content is not more than 13%;
preferably, the thickness of the polyvinyl alcohol film is 40-80 μm, and the polyvinyl alcohol film can bear the stretching speed of more than 300%/s when being subjected to unidirectional stretching in an air atmosphere.
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