CN110982259A - Completely biodegradable high-barrier polyamide-based composite film material and preparation method thereof - Google Patents
Completely biodegradable high-barrier polyamide-based composite film material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 81
- 229920002647 polyamide Polymers 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 22
- 239000012498 ultrapure water Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000004677 Nylon Substances 0.000 claims abstract description 10
- 229920001778 nylon Polymers 0.000 claims abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 8
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 7
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 7
- 239000004952 Polyamide Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 25
- 239000010419 fine particle Substances 0.000 claims description 23
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 229920006021 bio-based polyamide Polymers 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims description 5
- 229920001448 anionic polyelectrolyte Polymers 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920000867 polyelectrolyte Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010583 slow cooling Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000010292 electrical insulation Methods 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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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
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic 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
- 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
- C08J2423/08—Copolymers of ethene
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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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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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
- C08K13/04—Ingredients characterised by their shape and organic or inorganic 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Abstract
The invention relates to the technical field of film material application, in particular to a completely biodegradable high-barrier polyamide-based composite film material which is prepared from the following raw materials: biological polyamide material, glass fiber, water-soluble high-hydroxyl-density polymer, ultrapure water, nano inorganic matter, flatting agent and high molecular dispersing agent. According to the invention, the base material layer is repeatedly stretched in the longitudinal direction and the transverse direction, the permeability resistance of the base material layer is improved, the relative density and the water absorption of nylon 1010 are lower than those of nylon 6 and nylon 66, the nylon 1010 has better electrical insulation and chemical stability, high mechanical strength and higher dimensional stability, high melting point and high thermal deformation temperature, the mechanical strength and the stability of the base material plate are improved by adding the nylon 1010, the product is slowly heated by hot water after flowing through the extension, the phenomenon that the product is deformed and warped due to too fast temperature reduction is avoided, the glass fiber is added, the service life of the film material is prolonged, and the film material has outstanding substantive characteristics and remarkable progress.
Description
Technical Field
The invention relates to the technical field of film material application, in particular to a completely biodegradable high-barrier polyamide-based composite film material and a preparation method thereof.
Background
In recent years, the development of polymeric packaging materials with high barrier to gas or solvent permeation has attracted increasing attention. The barrier property of a material is generally referred to as the barrier effect of the material against oxygen and water vapor at a specified temperature and humidity, and is one of the important indicators of a packaging material. In the process of storing foods, medicines and the like, the existence and concentration of oxygen are key factors influencing the shelf life of the foods, the medicines and the like, and in recent years, the demand of high-barrier plastic packaging materials is increasing. Therefore, a completely biodegradable high-barrier polyamide-based composite film material and a preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide a completely biodegradable high-barrier polyamide-based composite film material and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
the completely biodegradable high-barrier polyamide-based composite film material is characterized by comprising the following raw materials in parts by weight:
155 parts of bio-based polyamide material, 13-27 parts of glass fiber, 22-32 parts of water-soluble high-hydroxyl-density polymer, 180 parts of ultrapure water, 2-5 parts of nano inorganic substance, 2-4 parts of flatting agent and 1-3 parts of high molecular dispersing agent.
Further, the bio-based polyamide material is prepared from nylon 6, nylon 66 and nylon 1010 according to a weight ratio of 4: 5: 3, and mixing the components in a ratio of 3.
Further, the water-soluble high hydroxyl density polymer is ethylene-polyvinyl alcohol, ethylene-vinyl alcohol copolymer according to the weight ratio of 4: 6, the molecular weight is 22000-40000, and the alcoholysis degree is 88-92%.
Further, the nano inorganic substance is prepared from nano silicon dioxide, nano aluminum oxide and montmorillonite according to the weight ratio of 3: 5: 2 in a mass ratio.
Furthermore, the leveling agent is prepared by mixing two or more than two of n-propanol, propylene glycol, glycidol and dimethyl sulfoxide according to any proportion.
Further, the polymeric dispersant is a cationic polyelectrolyte or an anionic polyelectrolyte.
A preparation method of a completely biodegradable high-barrier polyamide-based composite film material comprises the following steps:
s1, preparation of coating liquid: putting one third of ultrapure water into a stirrer, heating to 92-96 ℃ in a water bath, pouring the water-soluble high-hydroxyl-density polymer into the stirrer, stirring for 20-30min to obtain a solution of the water-soluble high-hydroxyl-density high-molecular polymer, naturally cooling the solution to 35-45 ℃, adding the leveling agent and the high-molecular dispersing agent into the stirrer, and stirring for 25-35min to obtain a coating liquid for later use;
s2, preparation of base materials: mixing a bio-based polyamide material, a nano inorganic substance and 40% of ultrapure water, stirring and reacting for 1.5-2.5h by using a magnetic stirrer, then cleaning by using ultrapure water, cleaning for 1-3 times by using acetone, removing impurities in the material, putting the material into a vacuum drying box, slowly and continuously raising the temperature to 85-95 ℃, drying until the water content is less than 0.5%, putting the dried base material into a grinder for grinding, and sieving by using a 200-mesh sieve to remove large particles to obtain fine particles;
s3, extrusion casting: extruding the fine particles obtained in the step S2 through a screw extruder, respectively stretching the fine particles for three times in the longitudinal direction and the transverse direction through a casting machine, stretching the fine particles in the longitudinal direction and the transverse direction in a staggered manner, wherein the stretching ratio is 5-10% of the original length each time, and cooling to obtain a base material film;
s4, coating: and (4) uniformly coating the coating liquid obtained in the step (S1) on two surfaces of the base material film, and drying to obtain the completely biodegradable high-barrier polyamide composite film.
Further, in the cooling manner in step S3, the product is taken out and then slowly cooled in hot water.
Further, the working temperature of the screw extruder in the step S3 is 300-315 ℃.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the base material layer is repeatedly stretched in the longitudinal direction and the transverse direction, the permeability resistance of the base material layer is improved, the relative density and the water absorption of nylon 1010 are lower than those of nylon 6 and nylon 66, the electrical insulation property and the chemical stability of the base material layer are better, the mechanical strength and the dimensional stability are high, the melting point is high, the thermal deformation temperature is high, the mechanical strength and the stability of the base material plate are improved by adding the nylon 1010, the product is slowly heated by hot water after flowing, the phenomenon that the product is deformed and warped due to too fast temperature reduction is avoided, the glass fiber is added, the service life of the film material is prolonged, the selected material can be biodegraded, and the film material is pollution-free, and has outstanding substantive characteristics and remarkable.
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.
The invention provides the following technical scheme:
example 1
The completely biodegradable high-barrier polyamide-based composite film material is characterized by comprising the following raw materials in parts by weight:
125 parts of bio-based polyamide material, 13 parts of glass fiber, 22 parts of water-soluble high-hydroxyl-density polymer, 150 parts of ultrapure water, 2 parts of nano inorganic substance, 2 parts of leveling agent and 1 part of high molecular dispersing agent.
The bio-based polyamide material is prepared from nylon 6, nylon 66 and nylon 1010 according to the weight ratio of 4: 5: 3, the water-soluble high hydroxyl density polymer is ethylene-polyvinyl alcohol, ethylene-vinyl alcohol copolymer according to the weight ratio of 4: 6, the molecular weight is 22000, the alcoholysis degree is 88%, and the nano inorganic substance is prepared by mixing nano silicon dioxide, nano aluminum oxide and montmorillonite according to the weight ratio of 3: 5: 2, the flatting agent is formed by mixing two or more than two of n-propanol, propylene glycol, glycidol and dimethyl sulfoxide according to any proportion, and the macromolecular dispersing agent is cationic polyelectrolyte or anionic polyelectrolyte.
A preparation method of a completely biodegradable high-barrier polyamide-based composite film material comprises the following steps:
s1, preparation of coating liquid: putting one third of ultrapure water into a stirrer, heating the ultrapure water to 92 ℃ in a water bath, pouring the water-soluble high-hydroxyl-density polymer into the stirrer, stirring the water-soluble high-hydroxyl-density polymer for 20min to obtain a solution of the water-soluble high-hydroxyl-density high-molecular polymer, naturally cooling the solution to 35 ℃, adding the leveling agent and the high-molecular dispersing agent into the stirrer, and stirring the mixture for 25min to obtain a coating liquid for later use;
s2, preparation of base materials: mixing a bio-based polyamide material, a nano inorganic substance and 40% of ultrapure water, stirring and reacting for 1.5h by using a magnetic stirrer, then cleaning by using ultrapure water, cleaning by using acetone for 1 time, removing internal impurities, putting into a vacuum drying box, slowly and continuously raising the temperature to 85 ℃, drying until the water content is less than 0.5%, putting the dried base material into a grinder for grinding, and sieving by using a 200-mesh sieve to remove large particles to obtain fine particles;
s3, extrusion casting: extruding the fine particles obtained in the step S2 by a screw extruder, wherein the working temperature of the screw extruder is 300 ℃, longitudinally and transversely stretching the fine particles by a casting machine for three times respectively, longitudinally and transversely stretching the fine particles in a staggered manner, wherein the stretching proportion of each time is 5 percent of the original length, cooling the fine particles to obtain a base material film, and slowly cooling the base material film in a manner that the product is taken out and then put into hot water;
s4, coating: and (4) uniformly coating the coating liquid obtained in the step (S1) on two surfaces of the base material film, and drying to obtain the completely biodegradable high-barrier polyamide composite film.
Example 2
The completely biodegradable high-barrier polyamide-based composite film material is characterized by comprising the following raw materials in parts by weight:
140 parts of bio-based polyamide material, 20 parts of glass fiber, 27 parts of water-soluble high-hydroxyl-density polymer, 165 parts of ultrapure water, 3 parts of nano inorganic substance, 3 parts of flatting agent and 2 parts of high molecular dispersing agent.
The bio-based polyamide material is prepared from nylon 6, nylon 66 and nylon 1010 according to the weight ratio of 4: 5: 3, the water-soluble high hydroxyl density polymer is ethylene-polyvinyl alcohol, ethylene-vinyl alcohol copolymer according to the weight ratio of 4: 6, the molecular weight is 31000, the alcoholysis degree is 90%, and the nano inorganic substance is prepared from nano silicon dioxide, nano aluminum oxide and montmorillonite according to the weight ratio of 3: 5: 2, the flatting agent is formed by mixing two or more than two of n-propanol, propylene glycol, glycidol and dimethyl sulfoxide according to any proportion, and the macromolecular dispersing agent is cationic polyelectrolyte or anionic polyelectrolyte.
A preparation method of a completely biodegradable high-barrier polyamide-based composite film material comprises the following steps:
s1, preparation of coating liquid: putting one third of ultrapure water into a stirrer, heating to 94 ℃ in a water bath, pouring the water-soluble high-hydroxyl-density polymer into the stirrer, stirring for 25min to obtain a solution of the water-soluble high-hydroxyl-density high-molecular polymer, naturally cooling the solution to 40 ℃, adding the leveling agent and the high-molecular dispersing agent into the stirrer, and stirring for 30min to obtain a coating liquid for later use;
s2, preparation of base materials: mixing a bio-based polyamide material, a nano inorganic substance and 40% of ultrapure water, stirring and reacting for 2 hours by using a magnetic stirrer, then cleaning with ultrapure water, cleaning with acetone for 2 times, removing internal impurities, putting into a vacuum drying box, slowly and continuously raising the temperature to 90 ℃ and drying until the water content is less than 0.5%, putting the dried base material into a grinder for grinding, and sieving with a 200-mesh sieve to remove large particles to obtain fine particles;
s3, extrusion casting: extruding the fine particles obtained in the step S2 by a screw extruder, wherein the working temperature of the screw extruder is 308 ℃, longitudinally and transversely stretching the fine particles for three times by a casting machine respectively, longitudinally and transversely stretching the fine particles in a staggered manner, wherein the stretching proportion of each time is 7 percent of the original length, cooling the fine particles to obtain a base material film, and taking out the product and slowly cooling the product in hot water;
s4, coating: and (4) uniformly coating the coating liquid obtained in the step (S1) on two surfaces of the base material film, and drying to obtain the completely biodegradable high-barrier polyamide composite film.
Example 3
The completely biodegradable high-barrier polyamide-based composite film material is characterized by comprising the following raw materials in parts by weight:
155 parts of bio-based polyamide material, 27 parts of glass fiber, 32 parts of water-soluble high-hydroxyl-density polymer, 180 parts of ultrapure water, 5 parts of nano inorganic substance, 4 parts of leveling agent and 3 parts of high molecular dispersing agent.
The bio-based polyamide material is prepared from nylon 6, nylon 66 and nylon 1010 according to the weight ratio of 4: 5: 3, the water-soluble high hydroxyl density polymer is ethylene-polyvinyl alcohol, ethylene-vinyl alcohol copolymer according to the weight ratio of 4: 6, the molecular weight is 40000, the alcoholysis degree is 92%, and the nano inorganic substance is prepared by mixing nano silicon dioxide, nano aluminum oxide and montmorillonite according to the weight ratio of 3: 5: 2, the flatting agent is formed by mixing two or more than two of n-propanol, propylene glycol, glycidol and dimethyl sulfoxide according to any proportion, and the macromolecular dispersing agent is cationic polyelectrolyte or anionic polyelectrolyte.
A preparation method of a completely biodegradable high-barrier polyamide-based composite film material comprises the following steps:
s1, preparation of coating liquid: putting one third of ultrapure water into a stirrer, heating to 96 ℃ in a water bath, pouring the water-soluble high-hydroxyl-density polymer into the stirrer, stirring for 30min to obtain a solution of the water-soluble high-hydroxyl-density high-molecular polymer, naturally cooling the solution to 45 ℃, adding the leveling agent and the high-molecular dispersing agent into the stirrer, and stirring for 35min to obtain a coating liquid for later use;
s2, preparation of base materials: mixing a bio-based polyamide material, a nano inorganic substance and 40% of ultrapure water, stirring and reacting for 2.5h by using a magnetic stirrer, then cleaning with ultrapure water, cleaning with acetone for 3 times, removing internal impurities, putting into a vacuum drying box, slowly and continuously raising the temperature to 95 ℃ and drying until the water content is less than 0.5%, putting the dried base material into a grinder for grinding, and sieving with a 200-mesh screen to remove large particles to obtain fine particles;
s3, extrusion casting: extruding the fine particles obtained in the step S2 by a screw extruder, wherein the working temperature of the screw extruder is 315 ℃, longitudinally and transversely stretching the fine particles by a casting machine for three times respectively, longitudinally and transversely stretching the fine particles in a staggered manner, wherein the stretching proportion of each time is 10 percent of the original length, cooling the fine particles to obtain a base material film, and slowly cooling the base material film in a manner that the product is taken out and then put into hot water;
s4, coating: and (4) uniformly coating the coating liquid obtained in the step (S1) on two surfaces of the base material film, and drying to obtain the completely biodegradable high-barrier polyamide composite film.
In order to embody the beneficial effects of the present invention, the following experiments were made:
two kinds of polyamide-based composite films of different brands, which are commonly used in the market, were selected as comparative examples 1 and 2, and the properties of the polyamide-based composite films obtained in examples 1 to 3 and the polyamide-based composite films of comparative examples 1 to 2 were tested to obtain the results shown in table 1 below:
TABLE 1
As can be seen from the data in Table 1, the polyamide-based composite films obtained in examples 1 to 3 of the present invention have an oxygen transmission rate of 0.1325ml/pkg. d as low as possible, have good barrier properties against gases, and have a thermal decomposition temperature of 468 ℃ as high as possible, and have good thermal stability.
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 (9)
1. The completely biodegradable high-barrier polyamide-based composite film material is characterized by comprising the following raw materials in parts by weight:
155 parts of bio-based polyamide material, 13-27 parts of glass fiber, 22-32 parts of water-soluble high-hydroxyl-density polymer, 180 parts of ultrapure water, 2-5 parts of nano inorganic substance, 2-4 parts of flatting agent and 1-3 parts of high molecular dispersing agent.
2. The fully biodegradable high-barrier polyamide-based composite film material according to claim 1, wherein: the bio-based polyamide material is prepared from nylon 6, nylon 66 and nylon 1010 according to the weight ratio of 4: 5: 3, and mixing the components in a ratio of 3.
3. The fully biodegradable high-barrier polyamide-based composite film material according to claim 1, wherein: the water-soluble high-hydroxyl-density polymer is ethylene-polyvinyl alcohol and an ethylene-vinyl alcohol copolymer, and the weight ratio of the ethylene-vinyl alcohol copolymer is 4: 6, the molecular weight is 22000-40000, and the alcoholysis degree is 88-92%.
4. The fully biodegradable high-barrier polyamide-based composite film material according to claim 1, wherein: the nano inorganic substance is prepared from nano silicon dioxide, nano aluminum oxide and montmorillonite according to the weight ratio of 3: 5: 2 in a mass ratio.
5. The fully biodegradable high-barrier polyamide-based composite film material according to claim 1, wherein: the leveling agent is formed by mixing two or more than two compositions of n-propanol, propylene glycol, glycidol and dimethyl sulfoxide according to any proportion.
6. The fully biodegradable high-barrier polyamide-based composite film material according to claim 1, wherein: the macromolecular dispersant is cationic polyelectrolyte or anionic polyelectrolyte.
7. A preparation method of a completely biodegradable high-barrier polyamide-based composite film material is characterized by comprising the following steps:
s1, preparation of coating liquid: putting one third of ultrapure water into a stirrer, heating to 92-96 ℃ in a water bath, pouring the water-soluble high-hydroxyl-density polymer into the stirrer, stirring for 20-30min to obtain a solution of the water-soluble high-hydroxyl-density high-molecular polymer, naturally cooling the solution to 35-45 ℃, adding the leveling agent and the high-molecular dispersing agent into the stirrer, and stirring for 25-35min to obtain a coating liquid for later use;
s2, preparation of base materials: mixing a bio-based polyamide material, a nano inorganic substance and 40% of ultrapure water, stirring and reacting for 1.5-2.5h by using a magnetic stirrer, then cleaning by using ultrapure water, cleaning for 1-3 times by using acetone, removing impurities in the material, putting the material into a vacuum drying box, slowly and continuously raising the temperature to 85-95 ℃, drying until the water content is less than 0.5%, putting the dried base material into a grinder for grinding, and sieving by using a 200-mesh sieve to remove large particles to obtain fine particles;
s3, extrusion casting: extruding the fine particles obtained in the step S2 through a screw extruder, respectively stretching the fine particles for three times in the longitudinal direction and the transverse direction through a casting machine, stretching the fine particles in the longitudinal direction and the transverse direction in a staggered manner, wherein the stretching ratio is 5-10% of the original length each time, and cooling to obtain a base material film;
s4, coating: and (4) uniformly coating the coating liquid obtained in the step (S1) on two surfaces of the base material film, and drying to obtain the completely biodegradable high-barrier polyamide composite film.
8. The preparation method of the completely biodegradable high-barrier polyamide-based composite film material according to claim 7, wherein the preparation method comprises the following steps: the cooling mode in step S3 is to place the product into hot water for slow cooling after the product is taken out.
9. The fully biodegradable high-barrier polyamide-based composite film material according to claim 7, wherein: the working temperature of the screw extruder in the step S3 is 300-315 ℃.
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