CN111391447A - Biodegradable environment-friendly film and preparation method thereof - Google Patents
Biodegradable environment-friendly film and preparation method thereof Download PDFInfo
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- CN111391447A CN111391447A CN201911115485.8A CN201911115485A CN111391447A CN 111391447 A CN111391447 A CN 111391447A CN 201911115485 A CN201911115485 A CN 201911115485A CN 111391447 A CN111391447 A CN 111391447A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to the technical field of agricultural film preparation, and relates to a film, in particular to a biodegradable environment-friendly film, wherein a film body of the biodegradable environment-friendly film is sequentially provided with a composite degradable outer layer, a bonding layer and a heat-sealing inner layer from outside to inside; the composite degradable outer layer is made of polylactic acid, the bonding layer is formed by mixing ethylene-vinyl alcohol copolymer and polylactic acid, and the heat-seal inner layer is formed by mixing butanediol diacid and butanediol terephthalate copolymer; the blend provided by the invention has simple preparation process and good interfacial compatibility between polymer matrixes; the blend has good mechanical property and good flexibility, and the prepared film can be fully biodegradable and can be widely applied to various film fields. And the modified polyester has the advantages of good chemical stability, transparency and surface gloss on the premise of meeting the degradation requirement.
Description
Technical Field
The invention relates to a film, in particular to a biodegradable environment-friendly film and a preparation method thereof.
Background
The degradable film has the functions and characteristics of the traditional plastic, can be split and degraded in the natural environment through the action of microorganisms in soil and water or the action of ultraviolet rays in sunlight after the service life is reached, and finally enters the ecological environment again in a reduction form to return to the nature. The domestic developed varieties comprise photodegradation, photobiodegradation, photooxidative biodegradation, high-starch-content type biodegradation, high-calcium-carbonate-filled type photooxidative degradation, full biodegradation and the like. Among which edible films and water-soluble films are most commonly used.
Edible films, such as chitosan edible packaging films, corn protein packaging films, modified cellulose edible packaging films, composite edible packaging films and the like, can be used for inner packaging of various foods, such as liners for wrapping candies and sticky cakes, or can be prepared into casings, fruit coatings, capsules and the like. It caters to the trend of modern consumption, and has a large market in food industry. In recent years, edible films have been greatly developed in countries around the world, and the edible films are more and more widely applied, but the current edible films have the defects of poor processability, mechanical strength and protection functionality compared with plastic films, high cost and the like.
The water-soluble film is a film which is soluble in water at normal temperature, and is widely used as a novel green packaging material for packaging various products such as agricultural chemicals, chemical fertilizers, pigments, dyes, detergents, water treatment agents, mineral additives, detergents, concrete additives, photographic chemicals, and horticultural chemicals in countries such as europe and the united states and japan. The water-soluble film has been widely regarded by developed countries in the world due to its environmental protection characteristics, such as complete degradation and safe and convenient use, wherein the water-soluble film with the best solubility is a polyethylene oxide film.
Therefore, the edible film and the water-soluble film are blended, the advantages of the edible film and the water-soluble film are complementary, the blending ratio of the edible film and the water-soluble film is adjusted, the blend with higher strength can be obtained, the flexibility of the blend can be improved, and the film prepared by the blend can realize full biodegradation.
Disclosure of Invention
In order to solve the technical problems, the invention provides a biodegradable environment-friendly film;
the invention is realized by the following steps:
a biodegradable environment-friendly film is characterized in that a film body of the biodegradable environment-friendly film is sequentially provided with a composite degradable outer layer, a bonding layer and a heat-sealing inner layer from outside to inside; the composite degradable outer layer is made of polylactic acid, the bonding layer is formed by mixing ethylene-vinyl alcohol copolymer and polylactic acid, and the heat-sealing inner layer is formed by mixing butanediol diacid and butanediol terephthalate copolymer.
Further, the paint mainly comprises the following components: polylactic acid, butanediol diacid ester and butanediol terephthalate, a solubilizer, an antioxidant, a light stabilizer and a filler.
Further, the light stabilizer comprises one or more of phenyl salicylate, p-tert-butyl salicylate, resorcinol benzoate, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, bisphenol A disalicylate, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, (2,2,6, 6-tetramethyl-4-piperidine) imine, a polymer of succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol, and bis-2, 2,6, 6-tetramethylpiperidinol sebacate.
Further, the solubilizer is selected from a bisoxazoline chain extender and an isocyanate chain extender with the functionality of not less than 2.
Further, the antioxidant comprises one or more of an antioxidant 168, an antioxidant 1010, an antioxidant 1076, an antioxidant 2246, an antioxidant 300, an antioxidant 330, an antioxidant 3114, an antioxidant 245, 2, 6-di-tert-butyl-p-cresol and 2,4, 6-tri-tert-butylphenol.
Further, the preparation method comprises the following steps:
(1) preparing a composite degradable outer layer: preparing polylactic acid particles into the composite degradable outer layer through a film blowing or extrusion process;
(2) preparing a bonding layer: firstly, mixing ethylene-vinyl alcohol copolymer particles and polylactic acid particles according to the weight ratio of 99: 1 to 90: 10, heating, stirring and mixing uniformly to prepare a bonding layer;
(3) preparing a heat-sealing inner layer: firstly, preparing the copolymer particles of butanediol diacid and butanediol terephthalate according to the weight ratio of 70: 30 to 50: heating, stirring and mixing uniformly according to the weight ratio of 50 to prepare a heat-sealing material; then extruding and molding the heat-sealing material to prepare the heat-sealing inner layer;
(4) compounding: and bonding the composite degradable outer layer, the bonding layer and the heat-seal inner layer together by two-time extrusion compounding process to prepare the film.
Further, the polylactic acid, the butanediol diacid ester, the butanediol terephthalate, the solubilizer, the antioxidant, the light stabilizer and the filler are dried before mixing, the drying temperature is 50-90 ℃, the drying time is 6-24h, the drying temperature of the filler is 100-130 ℃, and the drying time is 5-10 h.
The beneficial effect of above-mentioned scheme:
the blend provided by the invention has simple preparation process and good interfacial compatibility between polymer matrixes; the blend has good mechanical property and flexibility, and the prepared film can be fully biodegradable and can be widely applied to various film fields. And has the advantages of good chemical stability, transparency and surface gloss on the premise of satisfying degradation.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the description of the present invention, it should be noted that the terms "first", "second", and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
A biodegradable environment-friendly film is characterized in that a film body of the biodegradable environment-friendly film is sequentially provided with a composite degradable outer layer, a bonding layer and a heat-sealing inner layer from outside to inside; the composite degradable outer layer is made of polylactic acid, the bonding layer is formed by mixing ethylene-vinyl alcohol copolymer and polylactic acid, and the heat-sealing inner layer is formed by mixing butanediol diacid and butanediol terephthalate copolymer.
Further, the paint mainly comprises the following components: polylactic acid, butanediol diacid ester and butanediol terephthalate, a solubilizer, an antioxidant, a light stabilizer and a filler.
The preparation method comprises the following steps:
(1) preparing a composite degradable outer layer: preparing polylactic acid particles into the composite degradable outer layer through a film blowing or extrusion process;
(2) preparing a bonding layer: firstly, mixing ethylene-vinyl alcohol copolymer particles and polylactic acid particles according to the weight ratio of 99: 1 to 90: 10, heating, stirring and mixing uniformly to prepare a bonding layer;
(3) preparing a heat-sealing inner layer: firstly, preparing the copolymer particles of butanediol diacid and butanediol terephthalate according to the weight ratio of 70: 30 to 50: heating, stirring and mixing uniformly according to the weight ratio of 50 to prepare a heat-sealing material; then extruding and molding the heat-sealing material to prepare the heat-sealing inner layer;
(4) compounding: and bonding the composite degradable outer layer, the bonding layer and the heat-seal inner layer together by two-time extrusion compounding process to prepare the film.
The polylactic acid, the butanediol diacid and the butanediol terephthalate, the solubilizer, the antioxidant, the light stabilizer and the filler are dried before mixing, the drying temperature is 50-90 ℃, the drying time is 6-24h, the drying temperature of the filler is 100-130 ℃, and the drying time is 5-10h
Example one
The ethylene-vinyl alcohol copolymer particles and the polylactic acid particles are prepared according to a weight ratio of 99: 1 weight ratio, heating, stirring and mixing uniformly;
copolymer particles of butylene diacid and butylene terephthalate according to a weight ratio of 70: heating, stirring and mixing uniformly at a weight ratio of 30;
drying the polylactic acid, the butanediol diacid ester, the butanediol terephthalate, the solubilizer, the antioxidant, the light stabilizer and the filler before mixing, wherein the drying temperature is 50 ℃, the drying time is 24 hours, the drying temperature of the filler is 100 ℃, and the drying time is 10 hours
Example 2
The ethylene-vinyl alcohol copolymer particles and the polylactic acid particles are prepared according to the following weight ratio of 90: heating, stirring and mixing uniformly according to the weight ratio of 10;
copolymer particles of butylene diacid and butylene terephthalate in a weight ratio of 50: heating at a weight ratio of 50, stirring and mixing uniformly;
and before mixing, drying the polylactic acid, the butanediol diacid ester, the butanediol terephthalate, the solubilizer, the antioxidant, the light stabilizer and the filler at the drying temperature of 90 ℃ for 6 hours, and at the drying temperature of 130 ℃ for 5 hours.
Example 3
Ethylene-vinyl alcohol copolymer particles and polylactic acid particles were prepared as follows: heating, stirring and mixing uniformly according to the weight ratio of 15;
copolymer particles of butylene diacid and butylene terephthalate according to a weight ratio of 60: heating, stirring and mixing uniformly at a weight ratio of 40;
and before mixing, drying the polylactic acid, the butanediol diacid ester, the butanediol terephthalate, the solubilizer, the antioxidant, the light stabilizer and the filler at the drying temperature of 70 ℃ for 15 hours, and at the drying temperature of 115 ℃ for 7.5 hours.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A biodegradable environment-friendly film is characterized in that a film body of the biodegradable environment-friendly film is sequentially provided with a composite degradable outer layer, a bonding layer and a heat-sealing inner layer from outside to inside; the composite degradable outer layer is made of polylactic acid, the bonding layer is formed by mixing ethylene-vinyl alcohol copolymer and polylactic acid, and the heat-seal inner layer is formed by mixing butanediol diacid and butanediol terephthalate copolymer.
2. The biodegradable environmentally friendly film according to claim 1, which is characterized by consisting essentially of: polylactic acid, butanediol diacid ester and butanediol terephthalate, solubilizer, antioxidant, light stabilizer and filler.
3. The biodegradable environmentally friendly film according to claim 1, wherein the light stabilizer comprises one or more of phenyl salicylate, p-tert-butyl salicylate, resorcinol benzoate, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, bisphenol a disalicylate, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, (2,2,6, 6-tetramethyl-4-piperidine) imine, a polymer of succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol, bis-2, 2,6, 6-tetramethylpiperidinol sebacate.
4. The biodegradable, environmentally friendly film according to claim 1, wherein the solubilizing agent is selected from the group consisting of a bisoxazoline chain extender and an isocyanate chain extender having a functionality of not less than 2.
5. The biodegradable environmentally friendly film as claimed in claim 1, wherein the antioxidant comprises one or more of antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant 300, antioxidant 330, antioxidant 3114, antioxidant 245, 2, 6-di-tert-butyl-p-cresol, and 2,4, 6-tri-tert-butylphenol.
6. A method for preparing the biodegradable environmentally friendly film according to any one of claims 1 to 5, wherein the method comprises:
(1) preparing a composite degradable outer layer: preparing polylactic acid particles into the composite degradable outer layer through a film blowing or extrusion process;
(2) preparing a bonding layer: firstly, mixing ethylene-vinyl alcohol copolymer particles and polylactic acid particles according to the weight ratio of 99: 1 to 90: 10, heating, stirring and mixing uniformly to prepare a bonding layer;
(3) preparing a heat-sealing inner layer: firstly, preparing the copolymer particles of butanediol diacid and butanediol terephthalate according to the weight ratio of 70: 30 to 50: heating, stirring and mixing uniformly according to the weight ratio of 50 to prepare a heat-sealing material; then extruding and molding the heat-sealing material to prepare the heat-sealing inner layer;
(4) compounding: and bonding the composite degradable outer layer, the bonding layer and the heat-seal inner layer together by two-time extrusion compounding process to prepare the film.
7. The method for preparing biodegradable environment-friendly film according to claim 6, wherein the polylactic acid, butanediol diacid, butanediol terephthalate, solubilizer, antioxidant, light stabilizer and filler are dried before mixing, the drying temperature is 50-90 ℃, the drying time is 6-24h, the drying temperature of the filler is 100-130 ℃, and the drying time is 5-10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911115485.8A CN111391447A (en) | 2019-11-14 | 2019-11-14 | Biodegradable environment-friendly film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911115485.8A CN111391447A (en) | 2019-11-14 | 2019-11-14 | Biodegradable environment-friendly film and preparation method thereof |
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| CN111391447A true CN111391447A (en) | 2020-07-10 |
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| CN201911115485.8A Withdrawn CN111391447A (en) | 2019-11-14 | 2019-11-14 | Biodegradable environment-friendly film and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113427867A (en) * | 2021-08-16 | 2021-09-24 | 中国科学院长春应用化学研究所 | Multilayer heat-resistant high-transparency degradable polylactic acid-based film |
| CN113524831A (en) * | 2021-08-05 | 2021-10-22 | 中国科学院长春应用化学研究所 | Polylactic acid-based environment-friendly agricultural mulching film and preparation method thereof |
| CN113561604A (en) * | 2021-08-16 | 2021-10-29 | 中国科学院长春应用化学研究所 | Polylactic acid-based multifunctional multilayer composite agricultural mulching film and preparation method thereof |
-
2019
- 2019-11-14 CN CN201911115485.8A patent/CN111391447A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113524831A (en) * | 2021-08-05 | 2021-10-22 | 中国科学院长春应用化学研究所 | Polylactic acid-based environment-friendly agricultural mulching film and preparation method thereof |
| CN113427867A (en) * | 2021-08-16 | 2021-09-24 | 中国科学院长春应用化学研究所 | Multilayer heat-resistant high-transparency degradable polylactic acid-based film |
| CN113561604A (en) * | 2021-08-16 | 2021-10-29 | 中国科学院长春应用化学研究所 | Polylactic acid-based multifunctional multilayer composite agricultural mulching film and preparation method thereof |
| CN113427867B (en) * | 2021-08-16 | 2023-03-07 | 中国科学院长春应用化学研究所 | Multilayer heat-resistant high-transparency degradable polylactic acid-based film |
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Application publication date: 20200710 |