CN117719191A - Preparation method of biodegradable PBAT and TPU composite film - Google Patents
Preparation method of biodegradable PBAT and TPU composite film Download PDFInfo
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- CN117719191A CN117719191A CN202311737529.7A CN202311737529A CN117719191A CN 117719191 A CN117719191 A CN 117719191A CN 202311737529 A CN202311737529 A CN 202311737529A CN 117719191 A CN117719191 A CN 117719191A
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Biological Depolymerization Polymers (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a preparation method of a biodegradable PBAT and TPU composite film, which comprises the steps of firstly preparing a TPU/hot melt adhesive composite film by using a 0.1-5 mm biodegradable PBAT/TPU single-layer film and a 0.012-1 mm hot melt adhesive film, preparing a PU layer by using polyurethane resin, DMF, MEK, carbon black and a hydrolysis resistant agent as raw materials, preparing a PU and polyurethane bonding layer by using polyurethane bonding resin, a hydrolysis resistant agent and the PU layer as raw materials, then laminating the TPU/hot melt adhesive composite film, the PU layer, the PU and polyurethane bonding layer and the bonding layer through a laminating wheel to prepare a PBAT and TPU composite film semi-finished product, and finally separating the PBAT and TPU composite film semi-finished product from release paper to prepare the biodegradable PBAT and TPU composite film.
Description
Technical Field
The invention belongs to the technical field of shoe materials, bags and building materials, and particularly relates to a preparation method of a biodegradable PBAT and TPU composite film.
Background
Polyurethane films are a film-like product made of polyurethane materials. Polyurethane is a polymeric material made by reacting an Isocyanate (Isocyanate) with a Polyol (Polyol). Polyurethane has good flexibility, wear resistance, chemical and mechanical properties, and the degradation effect of the polyurethane film is not ideal.
According to the search, the Chinese patent document application number is 202011618100.2, a preparation method of a biodegradable composite film is disclosed, which comprises the steps of S1, uniformly stirring polyethylene and a degradable additive to obtain a composite material, wherein the content of the polyethylene is 98-99.5%, the content of the degradable additive is 0.5-2%, S2, adding the stirred composite material into a screw extruder for extrusion, S3, blow molding the extruded composite material through a blow molding machine, the width of the blow molded film is 1-2m, S4, putting the blow molded film on a winding machine for winding, S5, printing on one side or two sides of the wound film by using a printing machine, S6, cutting the printed film by using a cutting machine, S7, detecting the cut film, and packaging the qualified film. The film manufactured by the process is easy to biodegrade, reduces the pollution of plastic raw materials to the environment, and is more environment-friendly.
The Chinese patent document application number is 202310643340.5, which discloses a high heat conduction modified polyurethane composite film and a preparation method thereof, wherein the method comprises the following steps: TPU solution: adding the modified graphene and the nano-sheets into polyurethane particles, and then defoaming by using a vacuum oven; polytetrafluoroethylene plate: pouring the prepared TPU solution into a polytetrafluoroethylene mould, and horizontally pushing the TPU solution by using a dry glass rod; and (3) film preparation: taking out the polytetrafluoroethylene mould, uncovering the film, and obtaining the polyurethane heat conduction composite film. According to the high-heat-conductivity modified polyurethane composite film and the preparation method thereof, the modified graphene is used as a heat-conducting 'skeleton', the nano-sheets play a role of bridging in the composite material, and the mixed use of the nano-sheets and the dopamine hydrochloride modified graphene enables the heat-conducting filler to be distributed more tightly, so that the number of heat conduction networks in the composite film is increased, more phonon transmission paths are established, and a more compact heat conduction network is formed in the composite film.
However, although the two polyurethane films can be subjected to certain biodegradation, the degradation rate of the material is not ideal due to the fact that a large amount of non-degradable materials are used, so that a preparation method of a biodegradable PBAT and TPU composite film is needed to improve the degradability of the polyurethane film.
Disclosure of Invention
The invention aims to provide a preparation method of a biodegradable PBAT and TPU composite film, which is characterized in that the biodegradable PBAT and TPU composite film manufactured by the method has the advantages of functional surface, controllable thickness, designable texture, good elasticity, strength, bonding fastness and high-low temperature stability, and good biodegradability compared with the common polyurethane film in mechanical strength, so as to solve the problems in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a biodegradable PBAT and TPU composite film comprises the following steps:
s1, preparing a 0.1-5 mm biodegradable PBAT/TPU single-layer film by casting and extruding a TPU master batch modified by PBAT, preparing a 0.012-1 mm hot melt adhesive film by casting and extruding a hot melt adhesive master batch, and forming a TPU/hot melt adhesive composite film by laminating with the hot melt adhesive film as a lower layer and the biodegradable PBAT/TPU film as an upper layer;
s2, preparing a uniform thermoplastic PU coating according to 70-100 parts of polyurethane resin, 20-50 parts of DMF, 20-50 parts of MEK, 1-5 parts of carbon black and 0.3-1.5 parts of hydrolysis resistance agent, and preparing a PU layer by taking the thermoplastic PU coating as a raw material, wherein the total thickness of the PU layer is 0.02-0.08mm;
s3, preparing a uniform thermoplastic polyurethane coating according to 70-100 parts of polyurethane adhesive resin and 0.1-2 parts of hydrolysis inhibitor, and preparing a PU and polyurethane bonding layer by taking the polyurethane coating as a raw material, wherein the total thickness of the PU and polyurethane bonding layer is 0.2-0.5mm;
s4, bonding the TPU/hot melt adhesive composite film, the PU layer, the PU, the polyurethane bonding layer and the bonding layer through a bonding wheel, and drying the bonded product at the temperature of 40-160 ℃ in a mode of increasing and decreasing the using temperature of a bridge type oven to form a PBAT and TPU composite film semi-finished product;
s5, separating the PBAT and TPU composite film semi-finished product from the release paper to obtain the biodegradable PBAT and TPU composite film, wherein the total thickness of the biodegradable PBAT and TPU composite film is 0.32-0.6 mm.
Preferably, in step S1, the PBAT modified TPU master batch is a material prepared by mixing a biodegradable material with thermoplastic polyurethane, wherein the biodegradable material is one of polybutylene succinate, poly 3-hydroxyalkanoate, polylactic acid and poly epsilon-caprolactone, polyhydroxyalkanoates (PHAs), cellulose degrading bacteria, cellulose enzymes and polyethylene glycol, and the degradability of the TPU can be improved by modifying and combining the PBAT with the TPU; the thermoplastic polyurethane is provided as one of a polyester type TPU, a polyether type TPU and a polycaprolactone type TPU.
Preferably, the biodegradable PBAT/TPU single-layer film comprises the following steps:
a1, preparing the following raw materials: TPU master batch modified by PBAT, plasticizer and stabilizer;
a2, putting the TPU master batch modified by the PBAT into a hopper of an extruder, and adjusting the temperature, pressure and extrusion speed of the extruder according to the thickness of the required film;
a3, extruding the melted PBAT/TPU material into a film through a die head of an extruder through an extrusion nozzle, and controlling the thickness of the film to be in a range of 0.1mm-5mm by adjusting the extrusion speed of the extruder and the opening size of the die head;
a4, arranging a cooling device at the outlet of the extruder, and cooling the film to quickly solidify the film;
and A5, cutting the cooled and solidified film into a required size and shape by using a cutting machine to obtain the biodegradable PBAT/TPU single-layer film.
Preferably, the hot melt adhesive master batch is one of ethylene vinyl acetate, polyester, polypropylene and polyamide, and a certain proportion of plasticizer, stabilizer and pigment are added according to the need to adjust the viscosity, curing speed and color of the hot melt adhesive master batch when the hot melt adhesive master batch is prepared.
Preferably, the hot melt adhesive film comprises the following steps in preparation:
b1, placing hot melt adhesive master batches into a hopper in an extruder, and adjusting the temperature, pressure and extrusion speed of the extruder according to the thickness of a required film;
b2, extruding the melted hot melt adhesive master batch into a film through a die head of an extruder through an extrusion nozzle, and controlling the thickness of the film within the range of 0.012mm-1mm by adjusting the extrusion speed of the extruder and the opening size of the die head;
b3, arranging a cooling device at the outlet of the extruder, and cooling the film to quickly solidify the film;
and B4, cutting the cooled and solidified film into a required size and shape by using a cutting machine to obtain the hot melt adhesive film.
Preferably, when the TPU/hot melt adhesive composite film is prepared, firstly cutting the hot melt film and the biodegradable PBAT/TPU film into the same size, then carrying out plasma surface treatment on the hot melt film, stacking the treated hot melt adhesive film and the biodegradable PBAT/TPU film together, then carrying out hot pressing and compounding on the stacked films through a hot pressing roller to obtain the composite film, and finally cooling the composite film, thus obtaining the TPU/hot melt adhesive composite film after cooling.
Preferably, in step S2, during the preparation of the PU layer, 80 parts of polyurethane resin, 35 parts of DMF, 35 parts of MEK, 3 parts of carbon black and 0.8 part of hydrolysis-resistant agent are prepared into a uniform thermoplastic PU coating, the fully mixed polyurethane coating is uniformly coated on a release surface of a polyester release film with a residual adhesive force of 30-70% by using a slit coating head of a bridge coater, and the coated product is dried at a use temperature of 40-160 ℃ in a manner of increasing and decreasing the use temperature of a bridge oven, so that the PU layer is prepared.
Preferably, in step S3, when the PU and polyurethane bonding layer is prepared, a thermoplastic polyurethane coating is uniformly prepared according to 80 parts of polyurethane bonding resin and 1.2 parts of hydrolysis-resistant agent, the thermoplastic PU and polyurethane bonding layer coating after being fully mixed is uniformly coated on the surface of the PU layer by using a slit coating head of a bridge coater, and the coated product is baked to a semi-dry state by using a mode of increasing and decreasing the using temperature of a bridge oven to form the PU and polyurethane bonding layer.
Preferably, in step S4, when the semi-finished product of the PBAT and TPU composite film is prepared, the sizes of the TPU/hot melt adhesive composite film, the PU layer, the PU and polyurethane bonding layer and the bonding layer are cut into the same size, then parameters of temperature, pressure and speed of the bonding wheel are adjusted, the bonding layer is placed on a workbench, then the PU layer is placed on the bonding layer, smooth bonding of the two is ensured, the TPU/hot melt adhesive composite film is placed on the PU layer, then the PU and polyurethane bonding layer is placed on the TPU/hot melt adhesive composite film, the stacked materials are fed into the bonding wheel, and the bonding wheel provides thermal pressure and friction force to bond the materials together.
Compared with the prior art, the preparation method of the biodegradable PBAT and TPU composite film provided by the invention has the following advantages:
the invention prepares TPU/hot melt adhesive composite film by 0.1mm-5mm biodegradable PBAT/TPU single-layer film and 0.012mm-1mm hot melt adhesive film, prepares PU layer by polyurethane resin, DMF, MEK, carbon black and hydrolysis inhibitor, prepares PU and polyurethane bonding layer by polyurethane bonding resin, hydrolysis inhibitor and PU layer as raw materials, prepares PBAT and TPU composite film semi-finished product by bonding TPU/hot melt adhesive composite film, PU layer, PU and polyurethane bonding layer and bonding layer through bonding wheel, and finally separates the PBAT and TPU composite film semi-finished product from release paper to prepare biodegradable PBAT and TPU composite film.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a schematic illustration of the lamination of the PBAT and TPU composite film prepared by the invention;
in the figure: 1. a PU layer; 2. a polyurethane adhesive layer; 3. TPU/hot melt adhesive composite film layer.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The invention provides a preparation method of a biodegradable PBAT and TPU composite film shown in figures 1-2, which comprises the following steps:
s1, preparing a 0.1-5 mm biodegradable PBAT/TPU single-layer film by casting and extruding a TPU master batch modified by PBAT, preparing a 0.012-1 mm hot melt adhesive film by casting and extruding a hot melt adhesive master batch, and forming a TPU/hot melt adhesive composite film by laminating with the hot melt adhesive film as a lower layer and the biodegradable PBAT/TPU film as an upper layer;
the PBAT modified TPU master batch is prepared by mixing a biodegradable material with thermoplastic polyurethane, wherein the biodegradable material is one of polybutylene succinate, poly (3-hydroxyalkanoate), polylactic acid, poly epsilon-caprolactone, polyhydroxyalkanoates (PHAs), cellulose degrading bacteria, cellulose and polyethylene glycol, and the PBAT and the TPU are modified and combined to improve the degradability of the TPU, improve the environmental friendliness of the material, and the degradability of the PBAT enables the modified TPU master batch to be degraded in the use process, reduces the pollution to the environment, and meanwhile, the addition of the PBAT can also increase the toughness and the softness of the TPU and improve the plasticity and the processing performance of the material. The thermoplastic polyurethane is provided as one of a polyester type TPU, a polyether type TPU and a polycaprolactone type TPU.
The preparation of the biodegradable PBAT/TPU single-layer film comprises the following steps:
a1, preparing the following raw materials: TPU master batch modified by PBAT, plasticizer and stabilizer;
a2, putting the TPU master batch modified by the PBAT into a hopper of an extruder, and adjusting the temperature, pressure and extrusion speed of the extruder according to the thickness of the required film;
a3, extruding the melted PBAT/TPU material into a film through a die head of an extruder through an extrusion nozzle, and controlling the thickness of the film to be in a range of 0.1mm-5mm by adjusting the extrusion speed of the extruder and the opening size of the die head;
a4, arranging a cooling device at the outlet of the extruder, and cooling the film to quickly solidify the film;
and A5, cutting the cooled and solidified film into a required size and shape by using a cutting machine to obtain the biodegradable PBAT/TPU single-layer film.
The hot melt adhesive master batch is one of ethylene vinyl acetate, polyester, polypropylene and polyamide, and a certain proportion of plasticizer, stabilizer and pigment are added according to the need to adjust the viscosity, curing speed and color of the hot melt adhesive master batch when the hot melt adhesive master batch is prepared.
The hot melt adhesive film comprises the following steps:
b1, placing hot melt adhesive master batches into a hopper in an extruder, and adjusting the temperature, pressure and extrusion speed of the extruder according to the thickness of a required film;
b2, extruding the melted hot melt adhesive master batch into a film through a die head of an extruder through an extrusion nozzle, and controlling the thickness of the film within the range of 0.012mm-1mm by adjusting the extrusion speed of the extruder and the opening size of the die head;
b3, arranging a cooling device at the outlet of the extruder, and cooling the film to quickly solidify the film;
and B4, cutting the cooled and solidified film into a required size and shape by using a cutting machine to obtain the hot melt adhesive film.
When the TPU/hot melt adhesive composite film is prepared, firstly cutting a hot melt film and a biodegradable PBAT/TPU film into the same size, then carrying out plasma surface treatment on the hot melt film, stacking the treated hot melt adhesive film and the biodegradable PBAT/TPU film together, then carrying out hot pressing and compounding on the stacked films through a hot pressing roller to obtain the composite film, finally cooling the composite film, and obtaining the TPU/hot melt adhesive composite film after cooling.
S2, preparing a uniform thermoplastic PU coating according to 80 parts of polyurethane resin, 35 parts of DMF, 35 parts of MEK, 3 parts of carbon black and 0.8 part of hydrolysis resistance agent, and preparing a PU layer by taking the thermoplastic PU coating as a raw material, wherein the total thickness of the PU layer is 0.02-0.08mm; the carbon black is added, and the strength, hardness and wear resistance of the composite film can be improved by utilizing the high dispersibility and larger specific surface area so as to increase the surface tensile strength and scratch resistance of the film; the addition of carbon black can improve the strength and stability of the composite film, so that the composite film is more difficult to break in the use process, the service life of the material is prolonged, and the application field of the degradable film is expanded.
When the PU layer is prepared, 80 parts of polyurethane resin, 35 parts of DMF, 35 parts of MEK, 3 parts of carbon black and 0.8 part of hydrolysis-resistant agent are prepared into uniform thermoplastic PU coating, the fully mixed polyurethane coating is uniformly coated on a polyester release film release surface with the residual adhesive force of 30-70% by using a slit coating head of a bridge coater, and the coated product is dried at the use temperature of 40-160 ℃ in a mode of increasing and decreasing the use temperature of a bridge oven, so that the PU layer is prepared.
S3, preparing a thermoplastic polyurethane coating uniformly according to 80 parts of polyurethane adhesive resin and 1.2 parts of hydrolysis resistance agent, and preparing a PU and polyurethane bonding layer by taking the polyurethane coating as a raw material, wherein the total thickness of the PU and polyurethane bonding layer is 0.2-0.5mm;
when the PU and polyurethane bonding layer is prepared, uniformly preparing thermoplastic polyurethane coating according to 80 parts of polyurethane bonding resin and 1.2 parts of hydrolysis-resistant agent, uniformly coating the fully mixed thermoplastic PU and polyurethane bonding layer coating on the surface of the PU layer by using a slit coating head of a bridge coater, and baking the coated product to a semi-dry state by using a mode of increasing and decreasing the using temperature of a bridge oven to form the PU and polyurethane bonding layer.
S4, bonding the TPU/hot melt adhesive composite film, the PU layer, the PU, the polyurethane bonding layer and the bonding layer through a bonding wheel, and drying the bonded product at the temperature of 40-160 ℃ in a mode of increasing and decreasing the using temperature of a bridge type oven to form a PBAT and TPU composite film semi-finished product;
when the PBAT and TPU composite film semi-finished product is prepared, firstly cutting the sizes of the TPU/hot melt adhesive composite film, the PU layer, the PU and polyurethane bonding layer and the bonding layer into the same size, then adjusting parameters of temperature, pressure and speed of the bonding wheel, placing the bonding layer on a workbench, then placing the PU layer on the bonding layer to ensure that the TPU layer and the bonding layer are flatly bonded, then placing the TPU/hot melt adhesive composite film on the PU layer, then placing the PU and polyurethane bonding layer on the TPU/hot melt adhesive composite film, sending the stacked materials into the bonding wheel, and enabling the bonding wheel to provide hot pressure and friction force to bond the materials together.
S5, separating the PBAT and TPU composite film semi-finished product from the release paper to obtain the biodegradable PBAT and TPU composite film, wherein the total thickness of the biodegradable PBAT and TPU composite film is 0.32-0.6 mm.
Example 2
The same points are not repeated, and the difference from embodiment 1 is that:
s2, preparing uniform thermoplastic PU coating according to 70 parts of polyurethane resin, 20 parts of DMF, 20 parts of MEK, 1 part of carbon black and 0.3 part of hydrolysis resistance agent, and preparing a PU layer by taking the thermoplastic PU coating as a raw material, wherein the total thickness of the PU layer is 0.02-0.08mm;
when the PU layer is prepared, 70 parts of polyurethane resin, 20 parts of DMF, 20 parts of MEK, 1 part of carbon black and 0.3 part of hydrolysis-resistant agent are prepared into uniform thermoplastic PU coating, the fully mixed polyurethane coating is uniformly coated on a polyester release film release surface with the residual adhesive force of 30-70% by using a slit coating head of a bridge coater, and the coated product is dried at the use temperature of 40-160 ℃ in a mode of increasing and decreasing the use temperature of a bridge oven, so that the PU layer is prepared.
S3, preparing a thermoplastic polyurethane coating uniformly according to 70 parts of polyurethane adhesive resin and 0.1 part of hydrolysis resistance agent, and preparing a PU and polyurethane bonding layer by taking the polyurethane coating as a raw material, wherein the total thickness of the PU and polyurethane bonding layer is 0.2-0.5mm;
when the PU and polyurethane bonding layer is prepared, uniformly preparing thermoplastic polyurethane coating according to 70 parts of polyurethane bonding resin and 0.1 part of hydrolysis-resistant agent, uniformly coating the fully mixed thermoplastic PU and polyurethane bonding layer coating on the surface of the PU layer by using a slit coating head of a bridge coater, and baking the coated product to a semi-dry state by using a mode of increasing and decreasing the using temperature of a bridge oven to form the PU and polyurethane bonding layer.
Example 3
The same points are not repeated, and the difference from embodiment 1 is that:
s2, preparing a uniform thermoplastic PU coating according to 100 parts of polyurethane resin, 50 parts of DMF, 50 parts of MEK, 5 parts of carbon black and 1.5 parts of hydrolysis resistance agent, and preparing a PU layer by taking the thermoplastic PU coating as a raw material, wherein the total thickness of the PU layer is 0.02-0.08mm;
when the PU layer is prepared, 100 parts of polyurethane resin, 50 parts of DMF, 50 parts of MEK, 5 parts of carbon black and 1.5 parts of hydrolysis-resistant agent are prepared into uniform thermoplastic PU coating, the fully mixed polyurethane coating is uniformly coated on a polyester release film release surface with the residual adhesive force of 30-70% by using a slit coating head of a bridge coater, and the coated product is dried at the use temperature of 40-160 ℃ in a mode of increasing and decreasing the use temperature of a bridge oven, so that the PU layer is prepared.
S3, preparing a uniform thermoplastic polyurethane coating according to 100 parts of polyurethane adhesive resin and 2 parts of hydrolysis inhibitor, and preparing a PU and polyurethane bonding layer by taking the polyurethane coating as a raw material, wherein the total thickness of the PU and polyurethane bonding layer is 0.2-0.5mm;
when the PU and polyurethane bonding layer is prepared, a thermoplastic polyurethane coating is uniformly prepared according to 100 parts of polyurethane bonding resin and 2 parts of hydrolysis inhibitor, the thermoplastic PU and polyurethane bonding layer coating after being fully mixed is uniformly coated on the surface of the PU layer by using a slit coating head of a bridge coater, and the coated product is baked to a semi-dry state by using a mode of increasing and decreasing the using temperature of a bridge oven to form the PU and polyurethane bonding layer.
The PBAT and TPU composite films were prepared according to the methods provided in example 1, example 2 and example 3, and the polyurethane films prepared by the methods provided in comparative examples 1 and 2 were tested for their respective properties, with the test results being tabulated below:
comparative example 1 was used in the manner provided in example 1, but unlike example 1, the use of biodegradable materials was eliminated, i.e., a monolayer film was prepared directly using thermoplastic polyurethane, and the following steps were the same as those provided in example 1 and will not be described in detail.
Comparative example 2 was carried out in the manner as provided in example 2, but in contrast to example 2, the use of biodegradable materials was eliminated, namely, a monolayer film was produced directly using thermoplastic polyurethane, and the following steps were the same as those provided in example 1 and will not be described in detail.
From the table data, the elongation at break, tearing force, folding endurance and adhesive strength in the examples 1, 2 and 3 are similar to those in the comparative examples 1 and 2, so that it is demonstrated that the PBAT and TPU composite film provided by the invention has good elasticity, strength, adhesive fastness and high and low temperature stability, and the mechanical strength is equivalent to that of the common polyurethane film, and the biodegradation rate in the examples 1, 2 and 3 is obviously improved compared with that in the comparative examples 1 and 2.
In conclusion, firstly, a 0.1-5 mm biodegradable PBAT/TPU single-layer film and a 0.012-1 mm hot melt adhesive film are used for preparing a TPU/hot melt adhesive composite film, then polyurethane resin, DMF, MEK, carbon black and a hydrolysis inhibitor are used as raw materials for preparing a PU layer, polyurethane adhesive resin, a hydrolysis inhibitor and the PU layer are used as raw materials for preparing a PU and polyurethane bonding layer, and then the TPU/hot melt adhesive composite film, the PU layer, the PU and polyurethane bonding layer and the bonding layer are bonded through a bonding wheel for preparing a PBAT and TPU composite film semi-finished product, and finally the PBAT and TPU composite film semi-finished product is separated from release paper to prepare the biodegradable PBAT and TPU composite film.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (9)
1. A preparation method of a biodegradable PBAT and TPU composite film is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a 0.1-5 mm biodegradable PBAT/TPU single-layer film by casting and extruding a TPU master batch modified by PBAT, preparing a 0.012-1 mm hot melt adhesive film by casting and extruding a hot melt adhesive master batch, and forming a TPU/hot melt adhesive composite film by laminating with the hot melt adhesive film as a lower layer and the biodegradable PBAT/TPU film as an upper layer;
s2, preparing a uniform thermoplastic PU coating according to 70-100 parts of polyurethane resin, 20-50 parts of DMF, 20-50 parts of MEK, 1-5 parts of carbon black and 0.3-1.5 parts of hydrolysis resistance agent, and preparing a PU layer by taking the thermoplastic PU coating as a raw material, wherein the total thickness of the PU layer is 0.02-0.08mm;
s3, preparing a uniform thermoplastic polyurethane coating according to 70-100 parts of polyurethane adhesive resin and 0.1-2 parts of hydrolysis inhibitor, and preparing a PU and polyurethane bonding layer by taking the polyurethane coating as a raw material, wherein the total thickness of the PU and polyurethane bonding layer is 0.2-0.5mm;
s4, bonding the TPU/hot melt adhesive composite film, the PU layer, the PU, the polyurethane bonding layer and the bonding layer through a bonding wheel, and drying the bonded product at the temperature of 40-160 ℃ in a mode of increasing and decreasing the using temperature of a bridge type oven to form a PBAT and TPU composite film semi-finished product;
s5, separating the PBAT and TPU composite film semi-finished product from the release paper to obtain the biodegradable PBAT and TPU composite film, wherein the total thickness of the biodegradable PBAT and TPU composite film is 0.32-0.6 mm.
2. The method for preparing the biodegradable PBAT and TPU composite film according to claim 1, which is characterized in that: in the step S1, the TPU master batch modified by the PBAT is a material prepared by mixing a biodegradable material with thermoplastic polyurethane, wherein the biodegradable material is one of polybutylene succinate, poly (3-hydroxy alkanoate), polylactic acid, poly epsilon-caprolactone, polyhydroxyalkanoates (PHAs), cellulose degrading bacteria, cellulose and polyethylene glycol, and the degradability of the TPU can be improved by modifying and combining the PBAT with the TPU; the thermoplastic polyurethane is provided as one of a polyester type TPU, a polyether type TPU and a polycaprolactone type TPU.
3. The method for preparing the biodegradable PBAT and TPU composite film according to claim 2, which is characterized in that: the biodegradable PBAT/TPU single-layer film comprises the following steps:
a1, preparing the following raw materials: TPU master batch modified by PBAT, plasticizer and stabilizer;
a2, putting the TPU master batch modified by the PBAT into a hopper of an extruder, and adjusting the temperature, pressure and extrusion speed of the extruder according to the thickness of the required film;
a3, extruding the melted PBAT/TPU material into a film through a die head of an extruder through an extrusion nozzle, and controlling the thickness of the film to be in a range of 0.1mm-5mm by adjusting the extrusion speed of the extruder and the opening size of the die head;
a4, arranging a cooling device at the outlet of the extruder, and cooling the film to quickly solidify the film;
and A5, cutting the cooled and solidified film into a required size and shape by using a cutting machine to obtain the biodegradable PBAT/TPU single-layer film.
4. The method for preparing the biodegradable PBAT and TPU composite film according to claim 3, wherein the method comprises the following steps: the hot melt adhesive master batch is one of ethylene vinyl acetate, polyester, polypropylene and polyamide, and a certain proportion of plasticizer, stabilizer and pigment are added according to the need to adjust the viscosity, curing speed and color of the hot melt adhesive master batch when the hot melt adhesive master batch is prepared.
5. The method for preparing the biodegradable PBAT and TPU composite film according to claim 4, wherein the method comprises the following steps: the hot melt adhesive film comprises the following steps in preparation:
b1, placing hot melt adhesive master batches into a hopper in an extruder, and adjusting the temperature, pressure and extrusion speed of the extruder according to the thickness of a required film;
b2, extruding the melted hot melt adhesive master batch into a film through a die head of an extruder through an extrusion nozzle, and controlling the thickness of the film within the range of 0.012mm-1mm by adjusting the extrusion speed of the extruder and the opening size of the die head;
b3, arranging a cooling device at the outlet of the extruder, and cooling the film to quickly solidify the film;
and B4, cutting the cooled and solidified film into a required size and shape by using a cutting machine to obtain the hot melt adhesive film.
6. The method for preparing the biodegradable PBAT and TPU composite film according to claim 5, wherein the method comprises the following steps: when the TPU/hot melt adhesive composite film is prepared, firstly cutting a hot melt film and a biodegradable PBAT/TPU film into the same size, then carrying out plasma surface treatment on the hot melt film, stacking the treated hot melt adhesive film and the biodegradable PBAT/TPU film together, carrying out hot pressing and compounding on the stacked films through a hot pressing roller to obtain the composite film, and finally cooling the composite film, thus obtaining the TPU/hot melt adhesive composite film after cooling.
7. The method for preparing the biodegradable PBAT and TPU composite film according to claim 6, wherein the method comprises the following steps: in the step S2, when the PU layer is prepared, 80 parts of polyurethane resin, 35 parts of DMF, 35 parts of MEK, 3 parts of carbon black and 0.8 part of hydrolysis-resistant agent are prepared into uniform thermoplastic PU coating, the fully mixed polyurethane coating is uniformly coated on a polyester release film release surface with the residual adhesive force of 30-70% by using a slit coating head of a bridge coater, and the coated product is dried at the use temperature of 40-160 ℃ in a mode of increasing and decreasing the use temperature of a bridge oven, so that the PU layer is prepared.
8. The method for preparing the biodegradable PBAT and TPU composite film according to claim 7, wherein the method comprises the following steps: in the step S3, when the PU and polyurethane bonding layer is prepared, uniformly preparing thermoplastic polyurethane coating according to 80 parts of polyurethane bonding resin and 1.2 parts of hydrolysis-resistant agent, uniformly coating the thermoplastic PU and polyurethane bonding layer coating after being fully mixed on the surface of the PU layer by using a slit coating head of a bridge coater, and baking the coated product to a semi-dry state by using a mode of increasing and decreasing the using temperature of a bridge oven to form the PU and polyurethane bonding layer.
9. The method for preparing the biodegradable PBAT and TPU composite film according to claim 8, which is characterized in that: in step S4, when the semi-finished product of the PBAT and TPU composite film is prepared, firstly cutting the sizes of the TPU/hot melt adhesive composite film, the PU layer, the PU and polyurethane bonding layer and the bonding layer into the same size, then adjusting parameters of temperature, pressure and speed of the bonding wheel, placing the bonding layer on a workbench, then placing the PU layer on the bonding layer to ensure that the two layers are flatly bonded, placing the TPU/hot melt adhesive composite film on the PU layer, then placing the PU and polyurethane bonding layer on the TPU/hot melt adhesive composite film, and sending the stacked materials into the bonding wheel, wherein the bonding wheel provides hot pressure and friction force to bond the materials together.
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