CN112341795A - Degradable TPU membrane - Google Patents
Degradable TPU membrane Download PDFInfo
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- CN112341795A CN112341795A CN202011357049.4A CN202011357049A CN112341795A CN 112341795 A CN112341795 A CN 112341795A CN 202011357049 A CN202011357049 A CN 202011357049A CN 112341795 A CN112341795 A CN 112341795A
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- 239000012528 membrane Substances 0.000 title description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 79
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 229940118662 aluminum carbonate Drugs 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 16
- 239000004626 polylactic acid Substances 0.000 claims abstract description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005011 phenolic resin Substances 0.000 claims abstract description 14
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 14
- 108010010803 Gelatin Proteins 0.000 claims abstract description 13
- 229920000159 gelatin Polymers 0.000 claims abstract description 13
- 239000008273 gelatin Substances 0.000 claims abstract description 13
- 235000019322 gelatine Nutrition 0.000 claims abstract description 13
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 13
- -1 acrylate ester Chemical class 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 6
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 45
- 238000001816 cooling Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 15
- 238000005266 casting Methods 0.000 claims description 10
- 238000007493 shaping process Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 230000037303 wrinkles Effects 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical group 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 17
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000001681 protective effect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 8
- 244000005700 microbiome Species 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0856—Iron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a degradable TPU film, which comprises the following raw materials in parts by weight: the material comprises the following raw materials in parts by weight: thermoplastic polyurethane: 100-120 parts; polylactic acid: 20-40 parts; aluminum carbonate: 10-20 parts; gelatin: 30-40 parts; acrylate ester: 20-30 parts of a solvent; phenolic resin: 60-80 parts; curing agent: 15-25 parts; reduced iron powder: 5-15 parts; polyhydroxyalkanoate: 100-120 parts; water: 15-35 parts of raw materials, and putting the raw materials into a reaction kettle for reaction according to the steps. The invention increases the degradation speed of the TPU film, and can form a protective film on the TPU film through the coating prepared by the phenolic resin and the curing agent, thereby greatly increasing the corrosion resistance and prolonging the service life.
Description
Technical Field
The invention relates to the field of chemical products, in particular to a degradable TPU film.
Background
The TPU is increasingly popular with people due to the excellent performance and the environmental protection concept, not only has the excellent characteristics of high tension, high tensile force, toughness and aging resistance, but also is a mature environmental protection material, and at present, the TPU is widely applied to: shoe materials, ready-made clothes, inflatable toys, aquatic and underwater sports equipment, medical equipment, fitness equipment, automobile seat materials, umbrellas, leather suitcases, leather bags and the like.
The current market TPU film is difficult to degrade, serious ecological pollution can be caused, the use of the TPU film is greatly limited, and the existing degradable TPU film has low self corrosion resistance and short service life due to the degradation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a degradable TPU film, which solves the problems that the TPU film is difficult to degrade and has low corrosion resistance.
The invention mainly aims to provide a degradable TPU film, which comprises the following raw materials in parts by weight: thermoplastic polyurethane: 100-120 parts; polylactic acid: 20-40 parts; aluminum carbonate: 10-20 parts; gelatin: 30-40 parts; acrylate ester: 20-30 parts of a solvent; phenolic resin: 60-80 parts; curing agent: 15-25 parts; reduced iron powder: 5-15 parts; polyhydroxyalkanoate: 100-120 parts; water: 15-35 parts;
the preparation method of the degradable TPU film comprises the following steps:
the method comprises the following steps: preheating a reaction kettle at 60-80 ℃ for 30 minutes according to parts by weight, adding phenolic resin into the preheated reaction kettle, cooling to 40 ℃, stirring for 40 minutes at 400 r/min under 300-80 ℃, stopping heating, immediately adding a curing agent into the reaction kettle after cooling to 30 ℃, stirring at 800 r/min under 600-80 ℃, and taking out after 30 minutes to obtain the coating;
step two: cutting thermoplastic polyurethane and polylactic acid into blocks with the size of about 10 multiplied by 10 mm according to the parts by weight, grinding and crushing aluminum carbonate and reduced iron powder with the size of 200-300 meshes, and sieving the crushed materials once by using a sieve;
step three: according to the weight parts, respectively adding thermoplastic polyurethane, polylactic acid and gelatin into a solvent bottle, heating the solvent bottle with bath water at 50 ℃ for 30-40 minutes, and continuously stirring the solvent bottle at 80-120 r/min to obtain a solution A, a solution B and a solution C;
step four: respectively filtering the solution A, the solution B and the solution C according to the parts by weight, respectively heating the filtered substances in bath water at 80 ℃ for 5-15 minutes, and respectively adding the solution A, the solution B and the solution C again to prevent waste;
step five: pouring the solution A and the solution B into a reaction bottle in sequence according to parts by weight, stirring for 30 minutes at normal temperature of 50-70 r/min to obtain a solution D, adding acrylate into the solution C, and stirring for 30-40 minutes at 50 r/min to obtain a solution E;
step six: preheating the reaction kettle at 60-80 ℃ for 30 minutes according to parts by weight, adding the solution D and half of water into the reaction kettle, cooling to 40 ℃, stirring at 600 r/min for 20 minutes, adding aluminum carbonate into the reaction kettle at 50 ℃, 500 and 600 r/min, and stirring for 20 minutes;
step seven: adding the solution E and the other half part of water into a reaction kettle according to parts by weight, heating to 70 ℃, stirring for 30-40 minutes at 600 r/min, heating the reaction kettle to 100 ℃ for 1-3 hours, and evaporating redundant moisture in the internal solvent;
step eight: reducing the temperature of the reaction kettle to 10 ℃ according to the parts by weight, adding reduced iron powder into the reaction kettle, stirring at 800 r/min for 40-60 minutes, and obtaining slurry;
step nine: the prepared slurry is put into a casting machine, and the casting machine is used for uniformly coating the slurry on the base band, wherein the thickness of the base band is 300-500 microns;
step ten: drying and shaping the slurry coated on the base belt into a film at 50 ℃ by a fan heater, continuously drying for 10-20 minutes, cooling the dried film under the driving of a cooling roller to prevent wrinkles, and shaping again;
step eleven: spraying the coating prepared in the step one on the upper surface and the lower surface of the film cooled by the cooling roller, wherein the thickness of the coating is 50-150 microns, and drying the coating for 20-30 minutes at 50 ℃ by using a warm air blower;
step twelve: and rolling the dried film to obtain the degradable TPU film.
Preferably, the solvent bottle in the third step and the reaction bottle in the fifth step are both made of ceramics or glass containers.
Preferably, the mesh number of the sieve in the second step is 250 meshes, and the mesh number of the filter screen in the fourth step is 100 meshes.
Preferably, a refrigerating sheet is arranged inside the cooling roller in the step ten, and the model of the refrigerating sheet is TEC 1-12706.
Preferably, the reaction kettle in the first step is made of stainless steel, an anchor stirrer is arranged in the reaction kettle, and the pressure in the reaction kettle is 200PA/m in each step3。
Preferably, the reduced iron powder is prepared by reducing iron oxide fine powder heated to 700 ℃ or higher, and the curing agent in the first step is isocyanate.
Advantageous effects
1. According to the degradable TPU film provided by the invention, the TPU film can be degraded by microorganisms through the addition of the poly-emulsion, the gelatin and the acrylic ester, and the added reduced iron powder can react with water and oxygen in the air, so that the degradation temperature is increased, a good living environment is improved for the microorganisms, and the degradation speed of the TPU film can be further increased.
2. According to the degradable TPU film, the coating prepared from the phenolic resin and the curing agent can form a protective film on the TPU film, so that the corrosion resistance of the TPU film can be improved, and the TPU film is prevented from being degraded in use, and further the service life is prevented from being influenced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
a degradable TPU film comprises the following raw materials in parts by weight: thermoplastic polyurethane: 100 parts of (A); polylactic acid: 20 parts of (1); aluminum carbonate: 10 parts of (A); gelatin: 30 parts of (1); acrylate ester: 20 parts of (1); phenolic resin: 60 parts; curing agent: 15 parts of (1); reduced iron powder: 5 parts of a mixture; polyhydroxyalkanoate: 100 parts of (A); water: 15 parts.
The preparation method of the degradable TPU film comprises the following steps:
the method comprises the following steps: preheating a reaction kettle at 60 ℃ for 30 minutes according to parts by weight, adding phenolic resin into the preheated reaction kettle, cooling to 40 ℃, stirring for 40 minutes at 300 r/min, stopping heating, immediately adding a curing agent into the reaction kettle after the internal temperature is reduced to 30 ℃, stirring at 600 r/min, continuing for 30 minutes, and taking out to obtain the coating;
step two: cutting thermoplastic polyurethane and polylactic acid into blocks with the size of about 10 multiplied by 10 mm according to the parts by weight, grinding and crushing aluminum carbonate and reduced iron powder with the size of 200 meshes, and sieving the crushed materials once by a sieve;
step three: respectively adding thermoplastic polyurethane, polylactic acid and gelatin into 50 ℃ bath water in a solvent bottle, heating for 30 minutes, continuously stirring at 80 r/minute during heating, and finally obtaining a solution A, a solution B and a solution C;
step four: respectively filtering the solution A, the solution B and the solution C according to the parts by weight, respectively heating the filtered substances in bath water at 80 ℃ for 5 minutes, and respectively adding the solution A, the solution B and the solution C again to prevent waste;
step five: pouring the solution A and the solution B into a reaction bottle in sequence according to parts by weight, stirring for 30 minutes at normal temperature of 50 r/min to obtain a solution D, adding acrylic ester into the solution C, and stirring for 30 minutes at 50 r/min to obtain a solution E;
step six: preheating a reaction kettle at 60 ℃ for 30 minutes according to parts by weight, adding the solution D and half of water into the reaction kettle, cooling to 40 ℃ and stirring at 500 r/min for 20 minutes, adding aluminum carbonate into the reaction kettle at 50 ℃ and stirring at 500 r/min for 20 minutes;
step seven: adding the solution E and the other half part of water into a reaction kettle according to the parts by weight, heating to 70 ℃, stirring for 30 minutes at 600 r/min, heating the reaction kettle to 100 ℃ for 1 hour, and evaporating redundant water in the internal solvent;
step eight: reducing the temperature of the reaction kettle to 10 ℃ according to the parts by weight, adding reduced iron powder into the reaction kettle, stirring at 800 r/min for 40 minutes, and finishing to obtain slurry;
step nine: placing the prepared slurry into a casting machine, and uniformly coating the slurry on the base band through the casting machine, wherein the thickness of the slurry is 300 microns;
step ten: drying and shaping the slurry coated on the base belt into a film at 50 ℃ by a fan heater, continuously drying for 10 minutes, cooling the dried film under the driving of a cooling roller to prevent wrinkles from appearing, and shaping again;
step eleven: spraying the coating prepared in the step one on the upper surface and the lower surface of the film cooled by the cooling roller, wherein the thickness of the coating is 50 microns, and drying the coating for 20 minutes at 50 ℃ by using a warm air blower;
step twelve: and rolling the dried film to obtain the degradable TPU film.
Example two:
a degradable TPU film comprises the following raw materials in parts by weight: thermoplastic polyurethane: 110 parts of (A); polylactic acid: 30 parts of (1); aluminum carbonate: 15 parts of (1); gelatin: 35 parts of (B); acrylate ester: 25 parts of (1); phenolic resin: 70 parts of (B); curing agent: 20 parts of (1); reduced iron powder: 10 parts of (A); polyhydroxyalkanoate: 110 parts of (A); water: and 20 parts.
The preparation method of the degradable TPU film comprises the following steps:
the method comprises the following steps: preheating a reaction kettle at 70 ℃ for 30 minutes according to parts by weight, adding phenolic resin into the preheated reaction kettle, cooling to 40 ℃, stirring for 40 minutes at 350 r/min, stopping heating, immediately adding a curing agent into the reaction kettle after the internal temperature is reduced to 30 ℃, stirring for 700 r/min, and taking out after 30 minutes to obtain the coating;
step two: cutting thermoplastic polyurethane and polylactic acid into blocks with the size of about 10 multiplied by 10 mm according to the parts by weight, grinding and crushing aluminum carbonate and reduced iron powder with the size of 250 meshes, and sieving the crushed materials once by using a sieve;
step three: according to the weight parts, respectively adding thermoplastic polyurethane, polylactic acid and gelatin into a solvent bottle, heating the mixture in bath water at 50 ℃ for 35 minutes, continuously stirring the mixture at 100 r/min, and finally obtaining a solution A, a solution B and a solution C;
step four: respectively filtering the solution A, the solution B and the solution C according to the parts by weight, respectively heating the filtered substances in bath water at 80 ℃ for 10 minutes, and respectively adding the solution A, the solution B and the solution C again to prevent waste;
step five: pouring the solution A and the solution B into a reaction bottle in sequence according to parts by weight, stirring the solution A and the solution B for 30 minutes at normal temperature of 60 r/min to obtain a solution D, adding acrylic ester into the solution C, and stirring the solution C for 35 minutes at 50 r/min to obtain a solution E;
step six: preheating a reaction kettle at 80 ℃ for 30 minutes according to parts by weight, adding the solution D and half of water into the reaction kettle, cooling to 40 ℃ and 550 r/min, stirring for 20 minutes, adding aluminum carbonate into the reaction kettle at 50 ℃ and 550 r/min, and stirring for 20 minutes;
step seven: adding the solution E and the other half part of water into a reaction kettle according to parts by weight, heating to 70 ℃, stirring for 35 minutes at 600 r/min, heating the reaction kettle to 100 ℃ for 2 hours, and evaporating redundant water in the internal solvent;
step eight: reducing the temperature of the reaction kettle to 10 ℃ according to the parts by weight, adding reduced iron powder into the reaction kettle, stirring at 800 r/min for 50 minutes, and finishing to obtain slurry;
step nine: placing the prepared slurry into a casting machine, and uniformly coating the slurry on the base band through the casting machine, wherein the thickness of the slurry is 400 microns;
step ten: drying and shaping the slurry coated on the base belt into a film at 50 ℃ by a fan heater, continuously drying for 15 minutes, cooling the dried film under the driving of a cooling roller to prevent wrinkles from appearing, and shaping again;
step eleven: spraying the coating prepared in the step one on the upper surface and the lower surface of the film cooled by the cooling roller, wherein the thickness of the coating is 100 microns, and drying the coating for 25 minutes at 50 ℃ by using a warm air blower;
step twelve: and rolling the dried film to obtain the degradable TPU film.
Example three:
a degradable TPU film comprises the following raw materials in parts by weight: thermoplastic polyurethane: 120 parts of (A); polylactic acid: 40 parts of a mixture; aluminum carbonate: 20 parts of (1); gelatin: 40 parts of a mixture; acrylate ester: 30 parts of (1); phenolic resin: 80 parts of a mixture; curing agent: 25 parts of (1); reduced iron powder: 15 parts of (1); polyhydroxyalkanoate: 120 parts of (A); water: 35 parts of (A).
The preparation method of the degradable TPU film comprises the following steps:
the method comprises the following steps: according to the weight parts, after a reaction kettle is preheated at the temperature of 80 ℃ for 30 minutes, adding phenolic resin into the preheated reaction kettle, cooling to 40 ℃, stirring for 40 minutes at the speed of 400 r/minute, stopping heating, immediately adding a curing agent into the reaction kettle after the internal temperature of the reaction kettle is reduced to 30 ℃, stirring for 800 r/minute, and taking out after the internal temperature of the reaction kettle is reduced to 30 minutes to obtain the coating;
step two: cutting thermoplastic polyurethane and polylactic acid into blocks with the size of about 10 multiplied by 10 mm according to the parts by weight, grinding and crushing aluminum carbonate and reduced iron powder with the size of 300 meshes, and sieving the crushed materials once by using a sieve;
step three: respectively adding thermoplastic polyurethane, polylactic acid and gelatin into a solvent bottle, heating the mixture for 40 minutes in bath water at 50 ℃ while continuously stirring the mixture for 120 r/minute according to the parts by weight, and finally obtaining a solution A, a solution B and a solution C;
step four: respectively filtering the solution A, the solution B and the solution C according to the parts by weight, respectively heating the filtered substances in bath water at 80 ℃ for 15 minutes, and respectively adding the solution A, the solution B and the solution C again to prevent waste;
step five: pouring the solution A and the solution B into a reaction bottle in sequence according to parts by weight, stirring for 30 minutes at normal temperature of 70 r/min to obtain a solution D, adding acrylic ester into the solution C, and stirring for 40 minutes at 50 r/min to obtain a solution E;
step six: preheating a reaction kettle at 80 ℃ for 30 minutes according to parts by weight, adding the solution D and half of water into the reaction kettle, cooling to 40 ℃ and stirring at 600 r/min for 20 minutes, and adding aluminum carbonate into the reaction kettle at 50 ℃ and 600 r/min and stirring for 20 minutes;
step seven: adding the solution E and the other half part of water into a reaction kettle according to parts by weight, heating to 70 ℃, stirring for 40 minutes at 600 r/min, heating the reaction kettle to 100 ℃ for 3 hours, and evaporating redundant moisture in the internal solvent;
step eight: reducing the temperature of the reaction kettle to 10 ℃ according to the parts by weight, adding reduced iron powder into the reaction kettle, stirring at 800 r/min for 60 minutes, and finishing to obtain slurry;
step nine: placing the prepared slurry into a casting machine, and uniformly coating the slurry on the base band through the casting machine, wherein the thickness of the slurry is 500 microns;
step ten: drying and shaping the slurry coated on the base belt into a film at 50 ℃ by a fan heater, continuously drying for 20 minutes, cooling the dried film under the driving of a cooling roller to prevent wrinkles from appearing, and shaping again;
step eleven: spraying the coating prepared in the step one on the upper surface and the lower surface of the film cooled by the cooling roller, wherein the thickness of the coating is 150 microns, and drying the coating for 30 minutes at 50 ℃ by using a warm air blower;
step twelve: and rolling the dried film to obtain the degradable TPU film.
The preparation method of the embodiment has the advantages that the mixing sequence and the mixing conditions of all the substances are reasonable, so that the materials are fully mixed, the corrosion resistance is good when the preparation method is used, and the degradation speed is high when the preparation method is degraded.
The experiment is as follows:
equal amounts of example one, example two and example three and a common degradable TPU film were placed in the same degradable environment for 5 hours, 10 hours and 15 hours, respectively, and the data were recorded, requiring the topcoat to be scraped off.
As a result: the TPU film in the first example has no obvious reaction within 5 hours in a degradation environment, and has slight degradation reaction within 10 hours and 15 hours, the TPU film in the second example has no obvious reaction within 5 hours in the degradation environment, and has slight degradation reaction within 10 hours, and has moderate degradation reaction within 15 hours, the TPU film in the third example has slight reaction within 5 hours in the degradation environment, and has moderate degradation reaction within 10 hours and 15 hours, and the common degradable TPU film has no obvious reaction within 5 hours and 10 hours in the degradation environment, and has slight degradation reaction within 15 hours, so that the prepared TPU film in the third example has better degradability, and the degradation speed of the degradable TPU film is higher than that of the common degradable TPU film.
Experiment two:
equal amounts of example one, example two and example three and a common degradable TPU film were placed in a corrosive environment for 5 hours, 10 hours and 15 hours, respectively, and the data was recorded.
As a result: the TPU film in the first example has no obvious reaction after 5 hours in a corrosive environment, the TPU film has slight corrosion after 10 hours and 15 hours, the TPU film in the second example has no obvious reaction after 5 hours and 10 hours in the corrosive environment, the TPU film has slight corrosion after 15 hours, the TPU film in the third example has no obvious reaction after 5 hours, 10 hours and 15 hours in the corrosive environment, and the common degradable TPU film has corrosion after 5 hours, 10 hours and 15 hours in the corrosive environment, so that the TPU film prepared in the third example has better corrosion resistance and longer service life, and compared with the common degradable TPU film, the corrosion resistance of the degradable TPU film disclosed by the invention is far greater than that of the common degradable TPU film.
The invention has the beneficial effects that: during the preparation process, the added poly-emulsion, the added gelatin and the added acrylic ester can degrade the TPU film by microorganisms, the added reduced iron powder can react with water and oxygen in the air to increase the temperature during degradation, improve the good living environment for the microorganisms and further increase the degradation speed of the TPU film, and the coating prepared by the phenolic resin and the curing agent can form a protective film on the TPU film, so that the corrosion resistance of the TPU film can be increased, and the TPU film is prevented from being degraded during use, thereby further influencing the service life.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A degradable TPU film characterized by: the material comprises the following raw materials in parts by weight: thermoplastic polyurethane: 100-120 parts; polylactic acid: 20-40 parts; aluminum carbonate: 10-20 parts; gelatin: 30-40 parts; acrylate ester: 20-30 parts of a solvent; phenolic resin: 60-80 parts; curing agent: 15-25 parts; reduced iron powder: 5-15 parts; polyhydroxyalkanoate: 100-120 parts; water: 15-35 parts;
the preparation method of the degradable TPU film comprises the following steps:
the method comprises the following steps: preheating a reaction kettle at 60-80 ℃ for 30 minutes according to parts by weight, adding phenolic resin into the preheated reaction kettle, cooling to 40 ℃, stirring for 40 minutes at 400 r/min under 300-80 ℃, stopping heating, immediately adding a curing agent into the reaction kettle after cooling to 30 ℃, stirring at 800 r/min under 600-80 ℃, and taking out after 30 minutes to obtain the coating;
step two: cutting thermoplastic polyurethane and polylactic acid into blocks with the size of about 10 multiplied by 10 mm according to the parts by weight, grinding and crushing aluminum carbonate and reduced iron powder with the size of 200-300 meshes, and sieving the crushed materials once by using a sieve;
step three: according to the weight parts, respectively adding thermoplastic polyurethane, polylactic acid and gelatin into a solvent bottle, heating the solvent bottle with bath water at 50 ℃ for 30-40 minutes, and continuously stirring the solvent bottle at 80-120 r/min to obtain a solution A, a solution B and a solution C;
step four: respectively filtering the solution A, the solution B and the solution C according to the parts by weight, respectively heating the filtered substances in bath water at 80 ℃ for 5-15 minutes, and respectively adding the solution A, the solution B and the solution C again to prevent waste;
step five: pouring the solution A and the solution B into a reaction bottle in sequence according to parts by weight, stirring for 30 minutes at normal temperature of 50-70 r/min to obtain a solution D, adding acrylate into the solution C, and stirring for 30-40 minutes at 50 r/min to obtain a solution E;
step six: preheating the reaction kettle at 60-80 ℃ for 30 minutes according to parts by weight, adding the solution D and half of water into the reaction kettle, cooling to 40 ℃, stirring at 600 r/min for 20 minutes, adding aluminum carbonate into the reaction kettle at 50 ℃, 500 and 600 r/min, and stirring for 20 minutes;
step seven: adding the solution E and the other half part of water into a reaction kettle according to parts by weight, heating to 70 ℃, stirring for 30-40 minutes at 600 r/min, heating the reaction kettle to 100 ℃ for 1-3 hours, and evaporating redundant moisture in the internal solvent;
step eight: reducing the temperature of the reaction kettle to 10 ℃ according to the parts by weight, adding reduced iron powder into the reaction kettle, stirring at 800 r/min for 40-60 minutes, and obtaining slurry;
step nine: the prepared slurry is put into a casting machine, and the casting machine is used for uniformly coating the slurry on the base band, wherein the thickness of the base band is 300-500 microns;
step ten: drying and shaping the slurry coated on the base belt into a film at 50 ℃ by a fan heater, continuously drying for 10-20 minutes, cooling the dried film under the driving of a cooling roller to prevent wrinkles, and shaping again;
step eleven: spraying the coating prepared in the step one on the upper surface and the lower surface of the film cooled by the cooling roller, wherein the thickness of the coating is 50-150 microns, and drying the coating for 20-30 minutes at 50 ℃ by using a warm air blower;
step twelve: and rolling the dried film to obtain the degradable TPU film.
2. A degradable TPU film according to claim 1 wherein: and the solvent bottle in the third step and the reaction bottle in the fifth step are both made of ceramic or glass containers.
3. A degradable TPU film according to claim 1 wherein: the mesh number of the sieve in the second step is 250 meshes, and the mesh number of the filter screen in the fourth step is 100 meshes.
4. A degradable TPU film according to claim 1 wherein: and a refrigerating piece is arranged in the cooling roller in the step ten, and the model of the refrigerating piece is TEC 1-12706.
5. A degradable TPU film according to claim 1 wherein: the reaction kettle in the first step is made of stainless steel, an anchor stirrer is arranged in the reaction kettle, and the pressure in the reaction kettle is 200PA/m in each step3。
6. A degradable TPU film according to claim 1 wherein: the reduced iron powder is prepared by reducing iron oxide fine powder heated to a temperature of above 700 ℃, and the curing agent in the step one is isocyanate.
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