CN113429613A - Preparation method of biodegradable protective film - Google Patents

Preparation method of biodegradable protective film Download PDF

Info

Publication number
CN113429613A
CN113429613A CN202110708951.4A CN202110708951A CN113429613A CN 113429613 A CN113429613 A CN 113429613A CN 202110708951 A CN202110708951 A CN 202110708951A CN 113429613 A CN113429613 A CN 113429613A
Authority
CN
China
Prior art keywords
parts
protective film
modified layer
additive
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110708951.4A
Other languages
Chinese (zh)
Inventor
金小林
刘宏波
王述明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Srida Material Technology Co ltd
Original Assignee
Jiangsu Srida Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Srida Material Technology Co ltd filed Critical Jiangsu Srida Material Technology Co ltd
Priority to CN202110708951.4A priority Critical patent/CN113429613A/en
Publication of CN113429613A publication Critical patent/CN113429613A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/042Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/65Additives macromolecular
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/02Dextran; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/05Alcohols; Metal alcoholates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof

Abstract

The invention discloses a preparation method of a biodegradable protective film, wherein the protective film comprises a base material layer, a first modified layer and a second modified layer which are sequentially arranged from top to bottom, and the base material layer comprises the following components in parts by weight: 20-35 parts of glucan, 18-27 parts of hyaluronic acid, 15-19 parts of chondroitin sulfate, 13-16 parts of methyl polyglycerol fatty acid ester tridecyl ester and 17-21 parts of additive. The protective film prepared by the invention has good biodegradability, and has high tensile strength, water resistance and flexibility.

Description

Preparation method of biodegradable protective film
Technical Field
The invention belongs to the technical field of processing of protective films, and particularly relates to a preparation method of a biodegradable protective film.
Background
Along with the development of scientific technology, the application and production scale of protective films are continuously enlarged, the protective films are widely applied to automobile glass, door and window glass, display screens, mobile phone shells and the like, the protective films have a good use effect, but a large amount of protective film waste materials are generated at the same time, if the protective films are directly discarded in soil after being used, the pollution to the soil environment can be caused, great harm is brought to the life of people, in order to relieve the pollution of waste plastics to the environment, the protective films can be prepared by adopting biodegradable materials, certain defects exist in the existing degradable environment-friendly release films during use, the toughness is poor, the films are easy to break due to pulling during use, inconvenience is brought to the use of the degradable environment-friendly release films, and therefore, the preparation method of the traditional biodegradable protective films is necessary to be improved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to improve the preparation method of the biodegradable protective film, which not only has good biodegradability, but also has higher tensile strength, water resistance and flexibility.
In order to achieve the above object, the present invention adopts the following technical solutions:
the preparation method of the biodegradable protective film comprises a base material layer, a first modified layer and a second modified layer which are sequentially arranged from top to bottom, wherein the base material layer comprises the following components in parts by weight: 20-35 parts of glucan, 18-27 parts of hyaluronic acid, 15-19 parts of chondroitin sulfate, 13-16 parts of methyl polyglycerol fatty acid ester tridecyl ester and 17-21 parts of additive, wherein the first modification layer comprises the following components in parts by weight: 33-42 parts of polybutylene succinate, 26-31 parts of polylactic acid, 14-20 parts of polyvinyl alcohol, 10-13 parts of citric acid and 7-9 parts of a polymerization initiator, wherein the second modification layer comprises the following components in parts by weight: 23-28 parts of nano silicon dioxide, 15-21 parts of aluminum hydroxide, 11-13 parts of ethyl acetate and 4-8 parts of polyglycerol fatty acid ester.
Preferably, the additive comprises the following components in a mass ratio of (5-8): (3-4): (2-3) methanol, trifluoroacetic acid and sodium silicate.
Still preferably, the preparation steps of the aforementioned additive are as follows: dividing methanol into two equal parts, adding weighed trifluoroacetic acid, sodium silicate and the first part of methanol into a reaction container, and continuously stirring for 15-25 min to obtain the additive.
More preferably, the preparation step of the substrate layer is as follows: putting required amounts of dextran, hyaluronic acid, chondroitin sulfate and methyl polyglycerol fatty acid ester tridecyl ester into a reaction container, continuously stirring and mixing for 10-15 min, slowly adding an additive, continuously stirring until the additive is added, slowly adding a second portion of methanol, and continuously stirring until the methanol is added to obtain a mixture; putting the mixture into a double-screw extruder for mixing and melting to obtain a mixed material, cooling after mixing is finished, and granulating after cooling to room temperature; and (3) drying the obtained particles in drying equipment, and then placing the particles in a film blowing machine for film blowing to obtain a substrate layer.
Further preferably, the temperature of the reaction vessel before the raw materials are put therein is 50 to 60 ℃, the temperature of the reaction vessel is kept raised under continuous stirring after the raw materials are added, and the temperature raising rate is 2 to 3 ℃/min.
Specifically, the preparation steps of the first modified layer are as follows: placing polybutylene succinate, polylactic acid and polyvinyl alcohol into a reaction vessel, reacting at 65-70 ℃ for 20-30 min, adding citric acid and a polymerization initiator, raising the temperature to 80-95 ℃, and reacting for 30-45 min to obtain the first modified layer coating.
Preferably, the polymerization initiator is one of benzoyl peroxide, azobisisobutyronitrile and tert-butyl peroxybenzoate.
Still preferably, the preparation steps of the second modified layer are as follows: and (3) placing the nano silicon dioxide, the aluminum hydroxide, the ethyl acetate and the polyglycerol fatty acid ester into a reaction vessel, placing the reaction vessel at the temperature of 75-90 ℃, and reacting for 35-50 min to obtain the second modified layer coating.
More preferably, the preparation steps of the protective film are as follows: preheating the prepared substrate layer, coating a first modified layer coating on the lower surface of the substrate layer when the substrate layer is heated to 45-55 ℃, and reacting at 85-95 ℃ for 0.5-1.5 h to form a first modified layer; and coating a second modified layer coating on the lower surface of the first modified layer, reacting at 85-95 ℃ for 0.5-1.5 h to form a second modified layer, cooling, and cutting to obtain the protective film.
The invention has the advantages that:
(1) the protective film prepared by the invention has good biodegradability, high tensile strength, water resistance and flexibility, is not easy to tear in the using process, and effectively improves the product quality;
(2) the dextran, the hyaluronic acid and the chondroitin sulfate have good degradability and biocompatibility, and degraded products are nontoxic, so that the problem of environmental pollution is effectively avoided; the added trifluoroacetic acid, sodium silicate and methanol can reduce intramolecular and intermolecular hydrogen bonds formed among glucan, hyaluronic acid and chondroitin sulfate, and the formation of the hydrogen bonds can be further limited by keeping the temperature rise in the preparation process of the base material layer so as to reduce the influence of the hydrogen bonds on the melting process, thereby effectively promoting the preparation process of the base material layer;
(3) the lower surface of the base material layer is coated with a first modified layer coating, wherein polybutylene succinate, polylactic acid and polyvinyl alcohol react under the action of citric acid and a polymerization initiator to form a polymerization modified system, the adhesion force is good, and the water resistance and flexibility of the protective film can be effectively improved after the protective film is combined with the base material layer;
(4) the nano silicon dioxide and the aluminum hydroxide added into the second modified layer have good interface binding force, and the ethyl acetate and the polyglycerol fatty acid ester can be chemically bonded, so that the use strength of the protective film is effectively improved.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Example 1
The preparation method of the biodegradable protective film comprises a base material layer, a first modified layer and a second modified layer which are sequentially arranged from top to bottom, wherein the base material layer comprises the following components in parts by weight: 20 parts of glucan, 18 parts of hyaluronic acid, 15 parts of chondroitin sulfate, 13 parts of methyl polyglycerol fatty acid ester tridecyl ester and 17 parts of additive, wherein the first modified layer comprises the following components in parts by weight: 33 parts of polybutylene succinate, 26 parts of polylactic acid, 14 parts of polyvinyl alcohol, 10 parts of citric acid and 7 parts of polymerization initiator benzoyl peroxide, wherein the second modification layer comprises the following components in parts by weight: 23 parts of nano silicon dioxide, 15 parts of aluminum hydroxide, 11 parts of ethyl acetate and 4 parts of polyglycerol fatty acid ester.
Wherein the additive comprises the following components in percentage by mass: 3: 2, and sodium silicate, the preparation steps of the additive are as follows: dividing methanol into two equal parts, adding weighed trifluoroacetic acid, sodium silicate and the first part of methanol into a reaction vessel, and continuously stirring for 15min to obtain the additive.
The preparation steps of the substrate layer are as follows: putting required amounts of dextran, hyaluronic acid, chondroitin sulfate and methyl polyglycerol fatty acid ester tridecyl ester into a reaction container, wherein the initial temperature of the reaction container is 50-60 ℃, adding all raw materials, keeping heating while continuously stirring, keeping the heating rate at 2-3 ℃/min, continuously stirring and mixing for 10-15 min, slowly adding an additive, continuously stirring until the additive is added, slowly adding a second part of methanol, and continuously stirring until the methanol is added to obtain a mixture; putting the mixture into a double-screw extruder for mixing and melting to obtain a mixed material, cooling after mixing is finished, and granulating after cooling to room temperature; and (3) drying the obtained particles in drying equipment, and then placing the particles in a film blowing machine for film blowing to obtain a substrate layer.
The first modified layer was prepared as follows: placing polybutylene succinate, polylactic acid and polyvinyl alcohol into a reaction vessel, reacting at 65-70 ℃ for 20-30 min, adding citric acid and a polymerization initiator, raising the temperature to 80-95 ℃, and reacting for 30-45 min to obtain the first modified layer coating.
The preparation steps of the second modified layer are as follows: and (3) placing the nano silicon dioxide, the aluminum hydroxide, the ethyl acetate and the polyglycerol fatty acid ester into a reaction vessel, placing the reaction vessel at the temperature of 75-90 ℃, and reacting for 35-50 min to obtain the second modified layer coating.
The preparation steps of the protective film are as follows: preheating the prepared substrate layer, coating a first modified layer coating on the lower surface of the substrate layer when the substrate layer is heated to 45-55 ℃, and reacting at 85-95 ℃ for 0.5-1.5 h to form a first modified layer; and coating a second modified layer coating on the lower surface of the first modified layer, reacting at 85-95 ℃ for 0.5-1.5 h to form a second modified layer, cooling, and cutting to obtain the protective film.
Example 2
The preparation method of the biodegradable protective film comprises a base material layer, a first modified layer and a second modified layer which are sequentially arranged from top to bottom, wherein the base material layer comprises the following components in parts by weight: 35 parts of glucan, 27 parts of hyaluronic acid, 19 parts of chondroitin sulfate, 16 parts of methyl polyglycerol fatty acid ester tridecyl ester and 21 parts of additive, wherein the first modified layer comprises the following components in parts by weight: 42 parts of polybutylene succinate, 31 parts of polylactic acid, 20 parts of polyvinyl alcohol, 13 parts of citric acid and 9 parts of azodiisobutyronitrile serving as a polymerization initiator, wherein the second modification layer comprises the following components in parts by weight: 28 parts of nano silicon dioxide, 21 parts of aluminum hydroxide, 13 parts of ethyl acetate and 8 parts of polyglycerol fatty acid ester.
Wherein the additive comprises the following components in percentage by mass: 4: 3 of methanol, trifluoroacetic acid and sodium silicate, the preparation steps of the additive are as follows: dividing methanol into two equal parts, adding weighed trifluoroacetic acid, sodium silicate and the first part of methanol into a reaction container, and continuously stirring for 15-25 min to obtain the additive.
The preparation steps of the substrate layer are as follows: putting required amounts of dextran, hyaluronic acid, chondroitin sulfate and methyl polyglycerol fatty acid ester tridecyl ester into a reaction container, wherein the initial temperature of the reaction container is 50-60 ℃, adding all raw materials, keeping heating while continuously stirring, keeping the heating rate at 2-3 ℃/min, continuously stirring and mixing for 10-15 min, slowly adding an additive, continuously stirring until the additive is added, slowly adding a second part of methanol, and continuously stirring until the methanol is added to obtain a mixture; putting the mixture into a double-screw extruder for mixing and melting to obtain a mixed material, cooling after mixing is finished, and granulating after cooling to room temperature; and (3) drying the obtained particles in drying equipment, and then placing the particles in a film blowing machine for film blowing to obtain a substrate layer.
The first modified layer was prepared as follows: placing polybutylene succinate, polylactic acid and polyvinyl alcohol into a reaction vessel, reacting at 65-70 ℃ for 20-30 min, adding citric acid and a polymerization initiator, raising the temperature to 80-95 ℃, and reacting for 30-45 min to obtain the first modified layer coating.
The preparation steps of the second modified layer are as follows: and (3) placing the nano silicon dioxide, the aluminum hydroxide, the ethyl acetate and the polyglycerol fatty acid ester into a reaction vessel, placing the reaction vessel at the temperature of 75-90 ℃, and reacting for 35-50 min to obtain the second modified layer coating.
The preparation steps of the protective film are as follows: preheating the prepared substrate layer, coating a first modified layer coating on the lower surface of the substrate layer when the substrate layer is heated to 45-55 ℃, and reacting at 85-95 ℃ for 0.5-1.5 h to form a first modified layer; and coating a second modified layer coating on the lower surface of the first modified layer, reacting at 85-95 ℃ for 0.5-1.5 h to form a second modified layer, cooling, and cutting to obtain the protective film.
Example 3
The preparation method of the biodegradable protective film comprises a base material layer, a first modified layer and a second modified layer which are sequentially arranged from top to bottom, wherein the base material layer comprises the following components in parts by weight: 25 parts of glucan, 22 parts of hyaluronic acid, 17 parts of chondroitin sulfate, 15 parts of methyl polyglycerol fatty acid ester tridecyl ester and 19 parts of additive, wherein the first modified layer comprises the following components in parts by weight: 37 parts of polybutylene succinate, 28 parts of polylactic acid, 17 parts of polyvinyl alcohol, 12 parts of citric acid and 8 parts of a polymerization initiator, wherein the polymerization initiator is one of benzoyl peroxide, azobisisobutyronitrile and tert-butyl peroxybenzoate. The second modified layer comprises the following components in parts by weight: 26 parts of nano silicon dioxide, 18 parts of aluminum hydroxide, 12 parts of ethyl acetate and 6 parts of polyglycerol fatty acid ester.
Wherein the additive comprises the following components in percentage by mass: 3: 2, and sodium silicate, the preparation steps of the additive are as follows: dividing methanol into two equal parts, adding weighed trifluoroacetic acid, sodium silicate and the first part of methanol into a reaction container, and continuously stirring for 15-25 min to obtain the additive.
The preparation steps of the substrate layer are as follows: putting required amounts of dextran, hyaluronic acid, chondroitin sulfate and methyl polyglycerol fatty acid ester tridecyl ester into a reaction container, wherein the initial temperature of the reaction container is 50-60 ℃, adding all raw materials, keeping heating while continuously stirring, keeping the heating rate at 2-3 ℃/min, continuously stirring and mixing for 10-15 min, slowly adding an additive, continuously stirring until the additive is added, slowly adding a second part of methanol, and continuously stirring until the methanol is added to obtain a mixture; putting the mixture into a double-screw extruder for mixing and melting to obtain a mixed material, cooling after mixing is finished, and granulating after cooling to room temperature; and (3) drying the obtained particles in drying equipment, and then placing the particles in a film blowing machine for film blowing to obtain a substrate layer.
The first modified layer was prepared as follows: placing polybutylene succinate, polylactic acid and polyvinyl alcohol into a reaction vessel, reacting at 65-70 ℃ for 20-30 min, adding citric acid and a polymerization initiator, raising the temperature to 80-95 ℃, and reacting for 30-45 min to obtain the first modified layer coating.
The preparation steps of the second modified layer are as follows: and (3) placing the nano silicon dioxide, the aluminum hydroxide, the ethyl acetate and the polyglycerol fatty acid ester into a reaction vessel, placing the reaction vessel at the temperature of 75-90 ℃, and reacting for 35-50 min to obtain the second modified layer coating.
The preparation steps of the protective film are as follows: preheating the prepared substrate layer, coating a first modified layer coating on the lower surface of the substrate layer when the substrate layer is heated to 45-55 ℃, and reacting at 85-95 ℃ for 0.5-1.5 h to form a first modified layer; and coating a second modified layer coating on the lower surface of the first modified layer, reacting at 85-95 ℃ for 0.5-1.5 h to form a second modified layer, cooling, and cutting to obtain the protective film.
Comparative example 1
This comparative example is similar to the preparation procedure in example 1 except that the protective film has only the base material layer and does not have the first modified layer and the second modified layer.
Comparative example 2
This comparative example is similar to the preparation procedure in example 1 except that the substrate layer of the protective film has no additive.
Comparative example 3
The common degradable protective film sold in the market is selected for the comparative example.
Performance test
Taking the protective films in example 1, example 2, example 3, comparative example 1, comparative example 2 and comparative example 3 as test samples, respectively, testing the tensile strength and the elongation at break of each sample by referring to the standard GB/T1040.3-2006, taking a proper amount of the samples to be placed in humid soil at normal temperature, and recording the mass loss rate of the test samples after 30 days and 60 days as degradability, wherein the test results are shown in the following table:
Figure 755581DEST_PATH_IMAGE001
from the table above, the tensile strength, elongation at break and degradation performance of the protective films prepared in examples 1-3 are all obviously higher than those of comparative example 3, which shows that the preparation method of the invention improves the service strength and degradation performance of the protective films. The tensile strength and elongation at break of comparative example 1 were reduced compared to example 1, indicating that the first modified layer and the second modified layer of the present invention effectively improve the service strength of the protective film. Compared with the example 1 and the comparative example 2, the tensile degradation performance is obviously reduced, which shows that intramolecular and intermolecular hydrogen bonds are formed among the glucan, the hyaluronic acid and the chondroitin sulfate in the comparative example 2, the hydrogen bonds influence the melting process and reduce the performance of preparing the base material layer, so that the additive effectively promotes the melting process of preparing the base material layer.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.

Claims (9)

1. The preparation method of the biodegradable protective film is characterized in that the protective film comprises a base material layer, a first modified layer and a second modified layer which are sequentially arranged from top to bottom, wherein the base material layer comprises the following components in parts by weight: 20-35 parts of glucan, 18-27 parts of hyaluronic acid, 15-19 parts of chondroitin sulfate, 13-16 parts of methyl polyglycerol fatty acid ester tridecyl ester and 17-21 parts of additive, wherein the first modification layer comprises the following components in parts by weight: 33-42 parts of polybutylene succinate, 26-31 parts of polylactic acid, 14-20 parts of polyvinyl alcohol, 10-13 parts of citric acid and 7-9 parts of a polymerization initiator, wherein the second modification layer comprises the following components in parts by weight: 23-28 parts of nano silicon dioxide, 15-21 parts of aluminum hydroxide, 11-13 parts of ethyl acetate and 4-8 parts of polyglycerol fatty acid ester.
2. The method for preparing a biodegradable protective film according to claim 1, wherein the additive comprises the following components in a mass ratio of (5-8): (3-4): (2-3) methanol, trifluoroacetic acid and sodium silicate.
3. The method for preparing a biodegradable protective film according to claim 2, wherein the preparation steps of the additive are as follows: dividing methanol into two equal parts, adding weighed trifluoroacetic acid, sodium silicate and the first part of methanol into a reaction container, and continuously stirring for 15-25 min to obtain the additive.
4. The method for preparing a biodegradable protective film according to claim 3, wherein the substrate layer is prepared by the following steps: putting required amounts of dextran, hyaluronic acid, chondroitin sulfate and methyl polyglycerol fatty acid ester tridecyl ester into a reaction container, continuously stirring and mixing for 10-15 min, slowly adding an additive, continuously stirring until the additive is added, slowly adding a second portion of methanol, and continuously stirring until the methanol is added to obtain a mixture; putting the mixture into a double-screw extruder for mixing and melting to obtain a mixed material, cooling after mixing is finished, and granulating after cooling to room temperature; and (3) drying the obtained particles in drying equipment, and then placing the particles in a film blowing machine for film blowing to obtain a substrate layer.
5. The method for preparing a biodegradable protective film according to claim 4, wherein the temperature of the reaction vessel before the raw materials are put in is 50-60 ℃, the raw materials are added and then the temperature is kept raised under continuous stirring, and the temperature raising rate is 2-3 ℃/min.
6. The method for preparing a biodegradable protective film according to claim 1, wherein the first modified layer is prepared by the following steps: placing polybutylene succinate, polylactic acid and polyvinyl alcohol into a reaction vessel, reacting at 65-70 ℃ for 20-30 min, adding citric acid and a polymerization initiator, raising the temperature to 80-95 ℃, and reacting for 30-45 min to obtain the first modified layer coating.
7. The method as claimed in claim 1, wherein the polymerization initiator is one of benzoyl peroxide, azobisisobutyronitrile and tert-butyl peroxybenzoate.
8. The method for preparing a biodegradable protective film according to claim 1, wherein the second modified layer is prepared by the following steps: and (3) placing the nano silicon dioxide, the aluminum hydroxide, the ethyl acetate and the polyglycerol fatty acid ester into a reaction vessel, placing the reaction vessel at the temperature of 75-90 ℃, and reacting for 35-50 min to obtain the second modified layer coating.
9. The method for preparing a biodegradable protective film according to any one of claims 1-8, wherein the protective film is prepared by the following steps: preheating the prepared substrate layer, coating a first modified layer coating on the lower surface of the substrate layer when the substrate layer is heated to 45-55 ℃, and reacting at 85-95 ℃ for 0.5-1.5 h to form a first modified layer; and coating a second modified layer coating on the lower surface of the first modified layer, reacting at 85-95 ℃ for 0.5-1.5 h to form a second modified layer, cooling, and cutting to obtain the protective film.
CN202110708951.4A 2021-06-25 2021-06-25 Preparation method of biodegradable protective film Pending CN113429613A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110708951.4A CN113429613A (en) 2021-06-25 2021-06-25 Preparation method of biodegradable protective film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110708951.4A CN113429613A (en) 2021-06-25 2021-06-25 Preparation method of biodegradable protective film

Publications (1)

Publication Number Publication Date
CN113429613A true CN113429613A (en) 2021-09-24

Family

ID=77754301

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110708951.4A Pending CN113429613A (en) 2021-06-25 2021-06-25 Preparation method of biodegradable protective film

Country Status (1)

Country Link
CN (1) CN113429613A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101052523A (en) * 2004-09-08 2007-10-10 株式会社吴羽 Multilayered polyglycolic-acid-resin sheet
CN106117618A (en) * 2016-06-23 2016-11-16 桐城市华猫软膜有限公司 A kind of agricultural mulching and preparation method thereof
CN109233162A (en) * 2018-08-27 2019-01-18 盛世瑶兰(深圳)科技有限公司 One kind being packed for environment-friendly type degradable composite membrane and preparation method thereof
CN111409346A (en) * 2020-04-28 2020-07-14 睿泊(中国)环保科技有限公司 Degradable film and preparation method thereof
CN112940325A (en) * 2021-02-24 2021-06-11 陈雅婷 Degradable plastic composite film and preparation process thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101052523A (en) * 2004-09-08 2007-10-10 株式会社吴羽 Multilayered polyglycolic-acid-resin sheet
CN106117618A (en) * 2016-06-23 2016-11-16 桐城市华猫软膜有限公司 A kind of agricultural mulching and preparation method thereof
CN109233162A (en) * 2018-08-27 2019-01-18 盛世瑶兰(深圳)科技有限公司 One kind being packed for environment-friendly type degradable composite membrane and preparation method thereof
CN111409346A (en) * 2020-04-28 2020-07-14 睿泊(中国)环保科技有限公司 Degradable film and preparation method thereof
CN112940325A (en) * 2021-02-24 2021-06-11 陈雅婷 Degradable plastic composite film and preparation process thereof

Similar Documents

Publication Publication Date Title
CN1164676C (en) Water soluble resin composition and water soluble film
CN109575311B (en) Preparation method of vinyl acetate-ethylene copolymer emulsion
CN114292364B (en) Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof
CN114379179B (en) Anti-deformation acrylic plate with heat insulation function and preparation method thereof
CN111378261A (en) Processing method of disposable lunch box
CN113429613A (en) Preparation method of biodegradable protective film
CN106854333A (en) A kind of totally biodegradable strengthens starch plastic
CN113087941A (en) Water-soluble polyvinyl alcohol film and preparation method thereof
CN111019601B (en) Low-cost biodegradable hot melt adhesive special for paper packaging and preparation method thereof
CN109810527A (en) A kind of preparation method of stalk padded coaming
CN111454391B (en) Modified PVA resin and preparation method and application thereof
JP2000327891A (en) Resin composition for calendering
CN113308100A (en) Biodegradable polylactic acid/lignin composite material, preparation method and application
CN111087825A (en) Production method of slush molding silicone rubber artware
CN111662486A (en) Method for improving tensile strength of bio-based degradable material
CN117048154B (en) PS waterproof board and preparation method thereof
CN113087987A (en) Modified rice hull powder/polyethylene wood-plastic composite material and preparation method thereof
KR20090026744A (en) Hydrophobic biodegradable material
CN116715833A (en) Preparation method and application of high-amylose/polylactic acid graft copolymer
CN110467790B (en) Long glass fiber reinforced polypropylene composite material for foaming and preparation method thereof
CN114456554B (en) Biodegradable nano microporous composite material and preparation process thereof
JPH11240941A (en) Production of hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin
CN113136054A (en) Starch/polylactic acid composite material and preparation method and application thereof
CN117887170A (en) Composite auxiliary agent master batch special for polypropylene pipe and application thereof
CN116535549A (en) Nanometer microsphere and modified polyethylene-vinyl alcohol resin and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210924