CN112140494A - Preparation method of degradable biodegradable film - Google Patents

Preparation method of degradable biodegradable film Download PDF

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Publication number
CN112140494A
CN112140494A CN202010855192.XA CN202010855192A CN112140494A CN 112140494 A CN112140494 A CN 112140494A CN 202010855192 A CN202010855192 A CN 202010855192A CN 112140494 A CN112140494 A CN 112140494A
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parts
film
biodegradable
layer
extruder
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李清让
邓宗强
邓峰
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Hunan Kelaibao Bioenergy Technology Co ltd
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Hunan Kelaibao Bioenergy Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
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    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
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    • C08K5/00—Use of organic ingredients
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    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides

Abstract

The invention discloses a preparation method of a degradable biodegradable film, which comprises the following steps: s1: preparing raw materials: the inner layer comprises the following components in parts by weight: PBAT 35-95 parts, PLA 0-30 parts, biodegradable material 10-40 parts, starch 0-30 parts, inorganic powder 0-30 parts, and modifying assistant 0-15 parts; the invention can extrude the inner layer film, the outer layer film and the middle layer film with different production requirements by controlling different working states of the extruder, improves the convenience of film blowing, reduces the cost by taking the PBAT base as the waterproof inner layer and the waterproof outer layer and taking the non-water-resistant PVA base material as the middle layer through three-layer or multi-layer co-extrusion, and reduces the cost of the whole biodegradable film by film blowing or film casting.

Description

Preparation method of degradable biodegradable film
Technical Field
The invention particularly relates to the technical field of degradable membrane preparation, and particularly relates to a preparation method of a degradable biodegradable membrane.
Background
Most of the traditional plastics have stable performance, and are not easy to degrade rapidly under the action of various environmental factors in nature, so that the waste plastics have serious harm to the environment, namely, white pollution. Accordingly, biodegradable plastics have been developed, which can be digested and decomposed into carbon dioxide, water, other biomass and inorganic substances in a short time by microorganisms, and are environmentally low-load materials.
PBAT is a biodegradable film material with the best comprehensive performance at present, but has the problems of high price and small global productivity. Polyvinyl alcohol (PVA) is also a film forming raw material with good biodegradability, but due to the hydrogen bond action of the molecular structure, the melting point is close to the decomposition temperature, the PVA film cannot be formed by thermoplastic molding, the PVA film can only be formed by water solution casting, and the PVA film forming method has low speed, high energy consumption and high cost.
Through search, the chinese patent publication No. CN110654095A discloses a biodegradable film and a method for manufacturing the same, comprising an inner layer, a middle layer, and an outer layer, wherein the middle layer is disposed between the inner layer and the outer layer. The degradation capability of the product produced by the patent method can not meet the requirements of people.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a preparation method of a degradable biodegradable film.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a degradable biodegradable film comprises the following steps:
s1: preparing raw materials:
the inner layer comprises the following components in parts by weight: PBAT 35-95 parts, PLAO 30 parts, biodegradable material 10-40 parts, starch 0-30 parts, inorganic powder 0-30 parts, and modifying assistant 0-15 parts;
the middle layer comprises the following components in parts by weight: PBATO (poly (butylene adipate-co-terephthalate)) 60 parts, PLA35 parts to 95 parts, biodegradable material 10 parts to 40 parts, starch 0 part to 30 parts, inorganic powder 0 part to 30 parts and modification auxiliary agent 1 part to 15 parts;
the outer layer comprises the following components in parts by weight: PBAT40 parts to 100 parts, PLAO parts to 35 parts, biodegradable material 10 parts to 40 parts, starch 0 part to 30 parts, inorganic powder 0 part to 30 parts, and modifying assistant 0 part to 15 parts;
s2: preparing a master batch: preparing raw materials required by an inner layer, an outer layer and a middle layer of the biodegradable film: respectively pouring PBAT, PLA, a biodegradable material, starch, inorganic powder and a modification auxiliary agent into three extruders of a three-layer co-extrusion film blowing machine according to a proportion for premixing to obtain a premix;
s3: extruding a film: adjusting the machine parameters of each part, carrying out melt extrusion on the premix through a double-screw extruder, and carrying out blow molding to form a film by adopting an up-blowing method to obtain a corresponding three-layer co-extrusion biodegradable up-blown film;
s4: obtaining a master batch: and (3) cooling, granulating and drying the extruded upward blown film to obtain the corresponding master batch.
Further, the biodegradable material is one or more of polycaprolactone, polybutylene succinate and a copolymer thereof, polylactic acid, polyhydroxyalkanoate, aliphatic aromatic copolyester or polyvinyl alcohol.
On the basis of the foregoing scheme, the modification assistant comprises at least one compatibilizer of compounds having at least two specified functional groups; or a crosslinking agent comprising at least one compound having at least two specified functional groups; or a chain extender comprising at least one compound having at least two specified functional groups.
As still further aspects of the invention, the specified functional groups include silanes, titanates, aluminates, isocyanates, peroxides, carbodiimides, isocyanurates, oxazolines, epoxides, maleic anhydride, and divinyl ether groups.
Further, in the step S3, the working temperature of the extruder is between 120 ℃ and 200 ℃, the head temperature is between 140 ℃ and 200 ℃, and the screw rotation speed: 20rpm-400 rpm; traction speed: 5.5m/min-25.5 m/min; the blow-up ratio: 1.5-3.0.
On the basis of the above scheme, in S3, the working temperature of the extruder during the extrusion of the inner film is 120 ℃ to 160 ℃, the head temperature is 140 ℃ to 180 ℃, and the screw rotation speed: 150rpm to 300 rpm.
As a further scheme of the present invention, in S3, the working temperature of the extruder during the extrusion of the outer layer film is 120 ℃ to 160 ℃, the head temperature is 140 ℃ to 180 ℃, the screw rotation speed: 150rpm to 300 rpm.
Further, in S3, the working temperature of the extruder during the middle layer film extrusion is 150 ℃ to 180 ℃, the head temperature is 170 ℃ to 200 ℃, and the screw rotation speed: 150rpm to 300 rpm.
The invention has the beneficial effects that:
1. through three-layer or multi-layer co-extrusion, the PBAT base is used as a waterproof inner layer and a waterproof outer layer, meanwhile, the cost is reduced by using the non-waterproof PVA base material as a middle layer, and the cost of the whole biodegradable film is reduced by film blowing or film casting.
2. By controlling different working states of the extruder, the inner layer film, the outer layer film and the middle layer film with different production requirements can be obtained by extrusion, and the convenience of film blowing is improved.
3. The aim of reducing the cost of the biodegradable film is achieved by using PVA (polyvinyl alcohol) material on the premise of ensuring the water resistance of the biodegradable film by increasing the source of the biodegradable material.
Drawings
FIG. 1 is a schematic flow structure diagram of a method for preparing a degradable biodegradable film according to the present invention;
FIG. 2 is a graph comparing the results of a method for preparing a biodegradable film according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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.
Examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary only for the purpose of explaining the present patent and are not to be construed as limiting the present patent.
In the description of this patent, it is noted that unless otherwise specifically stated or limited, the terms "mounted," "connected," and "disposed" are to be construed broadly and can include, for example, fixedly connected, disposed, detachably connected, disposed, or integrally connected and disposed. The specific meaning of the above terms in this patent may be understood by those of ordinary skill in the art as appropriate.
Example 1
Referring to fig. 1 and 2, a method for preparing a degradable biodegradable film includes the steps of:
s1: preparing raw materials:
the inner layer comprises the following components in parts by weight: 65 parts of PBAT, 15 parts of PLA, 25 parts of biodegradable material, 15 parts of starch, 15 parts of inorganic powder and 10 parts of modified auxiliary agent; wherein, the inorganic powder adopts heavy calcium carbonate, the modification auxiliary agent adopts 1.5 parts of epoxy chain extender ADR-4370F, 1.8 parts of aluminate coupling agent DL4111.8 parts, 1 part of processing lubricant (ethylene bis stearamide), 4.5 parts of slipping agent (erucamide) and 1.2 parts of heat stabilizer (zinc stearate);
the middle layer comprises the following components in parts by weight: 45 parts of PBAT, 60 parts of PLA, 25 parts of biodegradable material, 15 parts of starch, 15 parts of inorganic powder and 10 parts of modified auxiliary agent; the modified auxiliary agent is: 0.5 part of processing lubricant (ethylene bis stearamide), 2.5 parts of slipping agent (erucamide), 1 part of antioxidant (hindered amine), 3 parts of plasticizer (glycerol), 1.5 parts of plasticizer (formamide) and 1.5 parts of plasticizer (anhydrous calcium chloride);
the outer layer comprises the following components in parts by weight: 65 parts of PBAT, 25 parts of PLA, 25 parts of biodegradable material, 15 parts of starch, 15 parts of inorganic powder and 10 parts of modified auxiliary agent; wherein, the inorganic powder adopts heavy calcium carbonate, the modification auxiliary agent adopts 1.5 parts of epoxy chain extender ADR-4370F, 1.8 parts of aluminate coupling agent DL4111.8 parts, 1 part of processing lubricant (ethylene bis stearamide), 4.5 parts of slipping agent (erucamide) and 1.2 parts of heat stabilizer (zinc stearate);
s2: preparing a master batch: preparing raw materials required by an inner layer, an outer layer and a middle layer of the biodegradable film: respectively pouring PBAT, PLA, a biodegradable material, starch, inorganic powder and a modification auxiliary agent into three extruders of a three-layer co-extrusion film blowing machine according to a proportion for premixing to obtain a premix;
s3: extruding a film: adjusting the machine parameters of each part, carrying out melt extrusion on the premix through a double-screw extruder, and carrying out blow molding to form a film by adopting an up-blowing method to obtain a corresponding three-layer co-extrusion biodegradable up-blown film;
in S3, the working temperature of the extruder is 120 ℃ when the inner layer film is extruded, the head temperature is 140 ℃, the screw rotation speed: 200rpm, S3, the working temperature of the extruder during the extrusion of the outer layer film is 120 ℃, the head temperature is 140 ℃, the screw rotation speed: 1200rpm, S3, the working temperature of the extruder during middle layer film extrusion is 150 ℃, the head temperature is 170 ℃, the screw speed: 200 rpm;
s4: obtaining a master batch: and (3) cooling, granulating and drying the extruded upward blown film to obtain the corresponding master batch.
The biodegradable material is one or more of polycaprolactone, poly (butylene succinate) and a copolymer thereof, polylactic acid, polyhydroxyalkanoate, aliphatic aromatic copolyester or polyvinyl alcohol.
The modification assistant comprises at least one compatilizer of a compound with at least two specified functional groups; or a crosslinking agent comprising at least one compound having at least two specified functional groups; or a chain extender comprising at least one compound having at least two specified functional groups including silanes, titanates, aluminates, isocyanates, peroxides, carbodiimides, isocyanurates, oxazolines, epoxides, maleic anhydride, and divinyl ether groups.
S3, the working temperature of the extruder is 120-200 ℃, the head temperature is 140-200 ℃, the screw rotation speed: 20rpm-400 rpm; traction speed: 5.5m/min-25.5 m/min; the blow-up ratio: 1.5-3.0.
The working principle of the embodiment is as follows: after the melting point of PVA molecules and starch intermolecular hydrogen bonds is reduced by the composite plasticizer, an interpenetrating network structure is generated by hot melting the PVA and the starch molecules in the double-screw reaction extrusion process and forms an alloy with polylactic acid, and most of the composite plasticizer is extracted in vacuum for recycling to prepare the PVA-based biodegradable modified thermoplastic blown film master batch.
Example 2
Referring to fig. 1 and 2, a method for preparing a degradable biodegradable film includes the steps of:
s1: preparing raw materials:
the inner layer comprises the following components in parts by weight: 95 parts of PBAT, 30 parts of PLA, 30 parts of biodegradable material, 30 parts of starch, 30 parts of inorganic powder and 10 parts of modified auxiliary agent; wherein, the inorganic powder adopts heavy calcium carbonate, the modification auxiliary agent adopts 1.5 parts of epoxy chain extender ADR-4370F, 1.8 parts of aluminate coupling agent DL4111.8 parts, 1 part of processing lubricant (ethylene bis stearamide), 4.5 parts of slipping agent (erucamide) and 1.2 parts of heat stabilizer (zinc stearate);
the middle layer comprises the following components in parts by weight: 60 parts of PBAT, 95 parts of PLA, 30 parts of biodegradable material, 30 parts of starch, 30 parts of inorganic powder and 10 parts of modified auxiliary agent; the modified auxiliary agent is: 0.5 part of processing lubricant (ethylene bis stearamide), 2.5 parts of slipping agent (erucamide), 1 part of antioxidant (hindered amine), 3 parts of plasticizer (glycerol), 1.5 parts of plasticizer (formamide) and 1.5 parts of plasticizer (anhydrous calcium chloride)
The outer layer comprises the following components in parts by weight: 100 parts of PBAT, 35 parts of PLA, 40 parts of biodegradable material, 30 parts of starch, 30 parts of inorganic powder and 10 parts of modified auxiliary agent; wherein, the inorganic powder adopts heavy calcium carbonate, the modification auxiliary agent adopts 1.5 parts of epoxy chain extender ADR-4370F, 1.8 parts of aluminate coupling agent DL4111.8 parts, 1 part of processing lubricant (ethylene bis stearamide), 4.5 parts of slipping agent (erucamide) and 1.2 parts of heat stabilizer (zinc stearate);
s2: preparing a master batch: preparing raw materials required by an inner layer, an outer layer and a middle layer of the biodegradable film: respectively pouring PBAT, PLA, a biodegradable material, starch, inorganic powder and a modification auxiliary agent into three extruders of a three-layer co-extrusion film blowing machine according to a proportion for premixing to obtain a premix;
s3: extruding a film: adjusting the machine parameters of each part, carrying out melt extrusion on the premix through a double-screw extruder, and carrying out blow molding to form a film by adopting an up-blowing method to obtain a corresponding three-layer co-extrusion biodegradable up-blown film;
in S3, the working temperature of the extruder is 160 ℃, the head temperature is 180 ℃, the screw rotation speed: 300rpm, S3, the working temperature of the extruder during the extrusion of the outer layer film was 160 ℃, the head temperature was 180 ℃, the screw speed: 300rpm, S3, the working temperature of the extruder during middle layer film extrusion is 180 ℃, the head temperature is 200 ℃, the screw rotation speed: 300 rpm;
s4: obtaining a master batch: and (3) cooling, granulating and drying the extruded upward blown film to obtain the corresponding master batch.
The biodegradable material is one or more of polycaprolactone, poly (butylene succinate) and a copolymer thereof, polylactic acid, polyhydroxyalkanoate, aliphatic aromatic copolyester or polyvinyl alcohol.
The modification assistant comprises at least one compatilizer of a compound with at least two specified functional groups; or a crosslinking agent comprising at least one compound having at least two specified functional groups; or a chain extender comprising at least one compound having at least two specified functional groups including silanes, titanates, aluminates, isocyanates, peroxides, carbodiimides, isocyanurates, oxazolines, epoxides, maleic anhydride, and divinyl ether groups.
S3, the working temperature of the extruder is 120-200 ℃, the head temperature is 140-200 ℃, the screw rotation speed: 20rpm-400 rpm; traction speed: 5.5m/min-25.5 m/min; the blow-up ratio: 1.5-3.0.
This example is different from example 1 in that the specific gravity of the raw material was changed and the production effect of the method was observed.
After the melting point of PVA molecules and starch intermolecular hydrogen bonds is reduced by the composite plasticizer, an interpenetrating network structure is generated by hot melting the PVA and the starch molecules in the double-screw reaction extrusion process and forms an alloy with polylactic acid, and most of the composite plasticizer is extracted in vacuum for recycling to prepare the PVA-based biodegradable modified thermoplastic blown film master batch.
In the description of this patent, it is to be understood that the terms "center," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientations and positional relationships indicated in the drawings for the convenience of describing the patent and for the simplicity of description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the patent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (8)

1. A preparation method of a degradable biodegradable film is characterized by comprising the following steps:
s1: preparing raw materials:
the inner layer comprises the following components in parts by weight: PBAT 35-95 parts, PLAO 30 parts, biodegradable material 10-40 parts, starch 0-30 parts, inorganic powder 0-30 parts, and modifying assistant 0-15 parts;
the middle layer comprises the following components in parts by weight: PBATO (poly (butylene adipate-co-terephthalate)) 60 parts, PLA35 parts to 95 parts, biodegradable material 10 parts to 40 parts, starch 0 part to 30 parts, inorganic powder 0 part to 30 parts and modification auxiliary agent 1 part to 15 parts;
the outer layer comprises the following components in parts by weight: PBAT40 parts to 100 parts, PLAO parts to 35 parts, biodegradable material 10 parts to 40 parts, starch 0 part to 30 parts, inorganic powder 0 part to 30 parts, and modifying assistant 0 part to 15 parts;
s2: preparing a master batch: preparing raw materials required by an inner layer, an outer layer and a middle layer of the biodegradable film: respectively pouring PBAT, PLA, a biodegradable material, starch, inorganic powder and a modification auxiliary agent into three extruders of a three-layer co-extrusion film blowing machine according to a proportion for premixing to obtain a premix;
s3: extruding a film: adjusting the machine parameters of each part, carrying out melt extrusion on the premix through a double-screw extruder, and carrying out blow molding to form a film by adopting an up-blowing method to obtain a corresponding three-layer co-extrusion biodegradable up-blown film;
s4: obtaining a master batch: and (3) cooling, granulating and drying the extruded upward blown film to obtain the corresponding master batch.
2. The method of claim 1, wherein the biodegradable film is prepared by: the biodegradable material is one or more of polycaprolactone, poly (butylene succinate) and a copolymer thereof, polylactic acid, polyhydroxyalkanoate, aliphatic aromatic copolyester or polyvinyl alcohol.
3. The method of claim 1, wherein the biodegradable film is prepared by: the modification assistant comprises at least one compatilizer of a compound with at least two specified functional groups; or a crosslinking agent comprising at least one compound having at least two specified functional groups; or a chain extender comprising at least one compound having at least two specified functional groups.
4. A method of making a degradable biodegradable film according to claim 3 wherein: specific functional groups include silanes, titanates, aluminates, isocyanates, peroxides, carbodiimides, isocyanurates, oxazolines, epoxides, maleic anhydride, and divinyl ether groups.
5. The method of claim 1, wherein the biodegradable film is prepared by: in the S3, the working temperature of the extruder is between 120 ℃ and 200 ℃, the head temperature is between 140 ℃ and 200 ℃, and the screw rotation speed is as follows: 20rpm-400 rpm; traction speed: 5.5m/min-25.5 m/min; the blow-up ratio: 1.5-3.0.
6. The method of claim 1, wherein the biodegradable film is prepared by: in the S3, the working temperature of the extruder is between 120 ℃ and 160 ℃ when the inner layer film is extruded, the head temperature is between 140 ℃ and 180 ℃, and the rotating speed of the screw is as follows: 150rpm to 300 rpm.
7. The method of claim 1, wherein the biodegradable film is prepared by: in S3, the working temperature of the extruder is 120-160 ℃ when the outer layer film is extruded, the head temperature is 140-180 ℃, and the screw rotation speed is as follows: 150rpm to 300 rpm.
8. The method of claim 1, wherein the biodegradable film is prepared by: in the S3, the working temperature of the extruder is between 150 ℃ and 180 ℃ when the middle layer film is extruded, the head temperature is between 170 ℃ and 200 ℃, and the rotating speed of the screw is as follows: 150rpm to 300 rpm.
CN202010855192.XA 2020-08-21 2020-08-21 Preparation method of degradable biodegradable film Withdrawn CN112140494A (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN113085319A (en) * 2021-03-16 2021-07-09 晋江市新迪新材料科技有限公司 Full-biodegradable composite material for tableware and tableware using same
CN113861659A (en) * 2021-10-09 2021-12-31 南京五瑞生物降解新材料研究院有限公司 Bio-based degradable membrane and preparation process thereof
CN114292424A (en) * 2021-12-30 2022-04-08 江苏华盛材料科技集团有限公司 Nano-modified high-barrier biodegradable mulching film
CN114407471A (en) * 2022-01-24 2022-04-29 珠海横琴辉泽丰包装科技有限公司 Three-layer co-extrusion biodegradable automatic packaging film material and manufacturing method thereof
WO2023245997A1 (en) * 2022-08-16 2023-12-28 北京蓝晶微生物科技有限公司 Marine degradable polyhydroxyalkanoate composition, molded body and preparation method therefor

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113085319A (en) * 2021-03-16 2021-07-09 晋江市新迪新材料科技有限公司 Full-biodegradable composite material for tableware and tableware using same
CN113861659A (en) * 2021-10-09 2021-12-31 南京五瑞生物降解新材料研究院有限公司 Bio-based degradable membrane and preparation process thereof
CN114292424A (en) * 2021-12-30 2022-04-08 江苏华盛材料科技集团有限公司 Nano-modified high-barrier biodegradable mulching film
CN114407471A (en) * 2022-01-24 2022-04-29 珠海横琴辉泽丰包装科技有限公司 Three-layer co-extrusion biodegradable automatic packaging film material and manufacturing method thereof
CN114407471B (en) * 2022-01-24 2023-11-17 珠海横琴辉泽丰包装科技有限公司 Three-layer co-extrusion biodegradable automatic packaging film material and manufacturing method thereof
WO2023245997A1 (en) * 2022-08-16 2023-12-28 北京蓝晶微生物科技有限公司 Marine degradable polyhydroxyalkanoate composition, molded body and preparation method therefor

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