CN116426099A - Seawater degradation film and preparation method thereof - Google Patents
Seawater degradation film and preparation method thereof Download PDFInfo
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- CN116426099A CN116426099A CN202310441598.7A CN202310441598A CN116426099A CN 116426099 A CN116426099 A CN 116426099A CN 202310441598 A CN202310441598 A CN 202310441598A CN 116426099 A CN116426099 A CN 116426099A
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- 230000015556 catabolic process Effects 0.000 title claims abstract description 91
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 91
- 239000013535 sea water Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 51
- 229920000379 polypropylene carbonate Polymers 0.000 claims abstract description 28
- 229920002261 Corn starch Polymers 0.000 claims abstract description 19
- 239000008120 corn starch Substances 0.000 claims abstract description 19
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 52
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 229920000881 Modified starch Polymers 0.000 claims description 27
- 238000010096 film blowing Methods 0.000 claims description 27
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 20
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 16
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 16
- 239000001361 adipic acid Substances 0.000 claims description 12
- 235000011037 adipic acid Nutrition 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 10
- 235000019698 starch Nutrition 0.000 claims description 10
- 239000008107 starch Substances 0.000 claims description 10
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
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- 239000003607 modifier Substances 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
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- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
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- 229920005586 poly(adipic acid) Polymers 0.000 claims description 3
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- -1 polypropylene carbonate Polymers 0.000 claims description 3
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 abstract description 27
- 101710108497 p-hydroxybenzoate hydroxylase Proteins 0.000 abstract description 25
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- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
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- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 description 3
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- DHTGRDDBCWWKQJ-UHFFFAOYSA-N 2-(2,2-dihydroxyethoxy)ethane-1,1-diol Chemical compound OC(O)COCC(O)O DHTGRDDBCWWKQJ-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical group OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
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- 150000002466 imines Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- 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
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- 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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- Chemical & Material Sciences (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)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides a seawater degradation film and a preparation method thereof, and relates to the technical field of biodegradable films; the seawater degradation film provided by the invention takes the bio-based seawater degradation materials PLGA, PHBH and corn starch as main base materials, so that the carbon emission of the material is greatly reduced while the seawater degradation characteristic is ensured; meanwhile, a biodegradable material with a longer degradation period, including low-carbon-emission PPC and PBAT with excellent flexibility, is added into a formula system to ensure that the finally prepared film has the shelf life meeting the circulation requirement; in addition, the invention is based on a degradation material multielement composite modification technology, and selects the organic peroxide as a reactive additive to break through and solve the compatibility problem between PLGA, PHBH, PPC, PBAT and corn starch multiphase interfaces, and provides a guarantee for the processing stability of PLGA and PHBH, thus preparing the composite material with excellent mechanical properties.
Description
Technical Field
The invention relates to the technical field of biodegradable films, in particular to a seawater degradable film and a preparation method thereof.
Background
It is counted that over 800 ten thousand tons of plastic are abandoned in the ocean every year, accounting for 80% of ocean waste. Such large amounts of waste plastics entering the ocean can seriously jeopardize the safety of marine organisms, and have been reported heretofore in considerable numbers, and are found in the bodies of sea animals such as turtles, sharks and the like. In addition, over time, plastic waste in the ocean can become microplastic, enter sea salt, and eventually become enriched in humans, and it has been reported that a large number of microplastic has been found in human blood. Thus, the management of plastic pollution in the ocean has been hampered.
The popularization and use of seawater degradation materials are considered as the most fundamental and effective way to solve marine plastic pollution, so research on seawater degradation materials has become a focus of attention for many scientific researchers in recent years. For example, the invention patent with application publication number CN113307959A improves the hydrophilic performance of PBS by introducing an imine structure into the main chain of the PBS, reduces the seawater degradation activation energy of the PBS, and thus improves the seawater degradation rate of the PBS. The prepared PBS copolyester material is degradable in seawater, adjustable in period and good in application prospect. The invention patent with application publication number of CN113121803A improves the seawater non-enzymatic hydrolysis of PEF by introducing a glycolic acid structure into the PEF main chain, and improves the seawater enzymatic hydrolysis of PEF by introducing a caprolactone structure. The invention patent with application publication number of CN108624020A is prepared by uniformly mixing thermoplastic modified polyvinyl alcohol, polyester and compatilizer according to a certain proportion, extruding, granulating, and injection molding to obtain the seawater degradation material with adjustable service cycle and degradation cycle.
The invention provides the seawater degradation material with good comprehensive performance, but the seawater degradation material takes petroleum-based resin as a base material, and the whole carbon emission is higher.
Disclosure of Invention
The invention aims to solve the technical problems that: in order to solve the problem of high carbon emission of the seawater degradation material in the prior art, the invention provides the seawater degradation film which takes bio-based seawater degradation materials PLGA, PHBH and corn starch as main base materials, thereby greatly reducing the carbon emission of the material while ensuring the seawater degradation characteristic and solving the problem of high carbon emission of the seawater degradation material in the prior art.
The technical scheme adopted for solving the technical problems is as follows:
the seawater degradation film comprises the following components in parts by weight:
alternatively, the polylactic acid-glycolic acid copolymer has a molecular weight M W More than or equal to 60000, the mass content of GA in the molecular structural unit is more than or equal to 80 percent, the melt flow rate MFR is less than or equal to 7g/10min (190 ℃,2.16 KG), and the melting point is less than or equal to 175 ℃.
Alternatively, the molecular weight M of the 3-hydroxybutyrate-co-3-hydroxycaproate W More than or equal to 50000, the melt flow rate MFR is less than or equal to 5g/10min (165 ℃,5 KG), and the melting point is less than or equal to 150 ℃.
Optionally, the plasticizer is selected from at least one of glycerin and sorbitol.
Optionally, the starch treating agent is at least one selected from stearic acid and polyhydroxy macromolecule super-dispersion modifying agents.
Optionally, the organic peroxide is
MH。
Optionally, the ethylene-vinyl acetate copolymer is
2504。
Optionally, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:2.
Another object of the present invention is to provide a method for preparing the seawater degradation film as described above, comprising the steps of:
s1: adding corn starch and starch treating agent into a high-speed mixer according to the formula amount, and mixing at a rotating speed of 200 rpm; adding plasticizer, and mixing at 600 rpm; finally, adipic acid and citric acid are added and mixed at the rotating speed of 200rpm to prepare plasticized and modified corn starch;
s2: adding polylactic acid-glycollic acid copolymer, 3-hydroxybutyrate-co-3-hydroxycaproic acid ester, polypropylene carbonate, poly (adipic acid)/butylene terephthalate, organic peroxide and white oil into a stirrer with a fixed rotating speed of 80rpm according to the formula amount, and mixing; then adding ethylene-vinyl acetate copolymer and antioxidant, mixing; finally, adding the plasticized and modified corn starch, mixing, and uniformly stirring to prepare a mixed master batch;
s3: adding the mixed master batch into a parallel double-screw extruder, carrying out melt blending and air cooling granulation to prepare a seawater degradation film blowing material;
s4: and (3) blowing the seawater degradation film blowing material to form a seawater degradation film.
The beneficial effects of the invention are as follows:
the seawater degradation film provided by the invention takes the bio-based seawater degradation materials PLGA, PHBH and corn starch as main base materials, so that the carbon emission of the material is greatly reduced while the seawater degradation characteristic is ensured; meanwhile, a biodegradable material with a longer degradation period, including low-carbon-emission PPC and PBAT with excellent flexibility, is added into a formula system to ensure that the finally prepared film has the shelf life meeting the circulation requirement; after the film is abandoned into the sea, most of the material can be degraded by seawater to form film fragments of PPC and PBAT, and the film fragments have the characteristic of biodegradation, so that the film fragments cannot harm marine ecology and finally cannot form microplastic; in addition, the invention is based on a degradation material multielement composite modification technology, and selects the organic peroxide as a reactive additive to break through and solve the compatibility problem between PLGA, PHBH, PPC, PBAT and corn starch multiphase interfaces, and provides a guarantee for the processing stability of PLGA and PHBH, thus preparing the composite material with excellent mechanical properties.
Detailed Description
The present invention will now be described in further detail. The embodiments described below are exemplary and intended to illustrate the invention and should not be construed as limiting the invention, as all other embodiments, based on which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of the invention.
In order to solve the problem of high carbon emission of the seawater degradation material in the prior art, the invention provides a seawater degradation film, which comprises the following components in parts by weight:
the seawater degradation film provided by the invention takes the bio-based seawater degradation materials PLGA, PHBH and corn starch as main base materials, so that the carbon emission of the material is greatly reduced while the seawater degradation characteristic is ensured; meanwhile, a biodegradable material with a longer degradation period, including low-carbon-emission PPC and PBAT with excellent flexibility, is added into a formula system to ensure that the finally prepared film has the shelf life meeting the circulation requirement; after the film is abandoned into the sea, most of the material can be degraded by seawater to form film fragments of PPC and PBAT, and the film fragments have the characteristic of biodegradation, so that the film fragments cannot harm marine ecology and finally cannot form microplastic; in addition, the invention is based on a degradation material multielement composite modification technology, and selects the organic peroxide as a reactive additive to break through and solve the compatibility problem between PLGA, PHBH, PPC, PBAT and corn starch multiphase interfaces, and provides a guarantee for the processing stability of PLGA and PHBH, thus preparing the composite material with excellent mechanical properties.
In order to achieve both the degradation performance and the mechanical property of the seawater degradation film, the molecular weight M of the polylactic acid-glycollic acid copolymer is optimized W More than or equal to 60000, the mass content of GA in the molecular structural unit is more than or equal to 80%, the melt flow rate MFR is less than or equal to 7g/10min (190 ℃,2.16 KG), and the melting point is less than or equal to 175 ℃; preferably 3-hydroxybutyrate-co-3-hydroxycaproic acid ester, molecular weight M W More than or equal to 50000, the melt flow rate MFR is less than or equal to 5g/10min (165 ℃,5 KG), and the melting point is less than or equal to 150 ℃.
The plasticizer is preferably at least one selected from glycerol and sorbitol; preferably, the starch treating agent is at least one selected from stearic acid and polyhydroxy macromolecule super-dispersing modifier, and particularly preferably, the polyhydroxy macromolecule super-dispersing modifier is JL-G02FX-P.
The preferred organic peroxides of the present invention are of the Acomax variety
MH; preferably the ethylene-vinyl acetate copolymer is +.>
2504; preferably, the antioxidant is a mixture of the antioxidant 1010 and the antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:2.
Another object of the present invention is to provide a method for preparing the seawater degradation film as described above, comprising the steps of:
s1: adding corn starch and starch treating agent into a high-speed mixer according to the formula amount, and mixing at a rotating speed of 200rpm, preferably for 2min; adding plasticizer, mixing at 600rpm, preferably for 8min; finally, adipic acid and citric acid are added and mixed at a rotating speed of 200rpm, preferably for 1min, so as to prepare plasticized and modified corn starch;
s2: adding polylactic acid-glycollic acid copolymer, 3-hydroxybutyrate-co-3-hydroxycaproic acid ester, polypropylene carbonate, poly (adipic acid)/butylene terephthalate), organic peroxide and white oil into a stirrer with a fixed rotating speed of 80rpm according to the formula amount, and mixing, preferably mixing for 30s; then adding ethylene-vinyl acetate copolymer and antioxidant, mixing, preferably mixing for 30s; finally adding plasticized and modified corn starch, mixing, preferably mixing for 1 minute, and uniformly stirring to prepare a mixed master batch;
s3: adding the mixed master batch into a parallel double-screw extruder, carrying out melt blending and air cooling granulation to prepare a seawater degradation blown film material; preferably, the temperature of the 1-9 region of the twin-screw extruder is set to be 130 ℃,180 ℃,180 ℃,180 ℃,175 ℃,170 ℃,170 ℃,170 ℃,170 ℃ and 170 ℃ in the step, and the temperature of the machine head is set to be 170 ℃;
s4: blowing the seawater degradation film blowing material to form a seawater degradation film; preferably, a common high-pressure PE film blowing machine is adopted for film blowing molding, the temperature of a 1-5 region of the film blowing machine is 130 ℃,180 ℃,180 ℃,180 ℃,180 ℃ and 175 ℃ of a die head temperature, and finally the seawater degradation film with the thickness of 40 mu m and the breadth of 600mm is obtained.
Because the decomposition temperature of the pure starch is lower than the plasticizing temperature and the processing fluidity is not possessed, the step S1 of the invention increases the plasticity of the starch by plasticizing and modifying the corn starch, thereby being convenient for the subsequent blow molding; in the step, adipic acid and citric acid are compounded to esterify hydroxyl groups in starch, so that the hydrophobicity is improved.
The preparation method of the seawater degradation film provided by the invention has a simple process; in the preparation process, biological-based seawater degradation materials PLGA, PHBH and corn starch are used as main base materials, so that the carbon emission of the material is greatly reduced while the seawater degradation characteristic is ensured; meanwhile, a biodegradable material with a longer degradation period, including low-carbon-emission PPC and PBAT with excellent flexibility, is added into a formula system to ensure that the finally prepared film has the shelf life meeting the circulation requirement; after the film is abandoned into the sea, most of the material can be degraded by seawater to form film fragments of PPC and PBAT, and the film fragments have the characteristic of biodegradation, so that the film fragments cannot harm marine ecology and finally cannot form microplastic; in addition, the invention is based on a degradation material multielement composite modification technology, and the compatibility problem between PLGA, PHBH, PPC, PBAT and corn starch multiphase interfaces is solved by selecting the organic peroxide as a reactive auxiliary agent, and the invention provides a guarantee for the processing stability of PLGA and PHBH, so as to prepare the composite material with excellent mechanical properties; during the preparation, ethylene-vinyl acetate copolymer is added as sealing agent to improve the heat sealing performance of the film.
Compared with the traditional film bag, the low-carbon seawater degradation film provided by the invention has the advantages that the seawater degradation weight loss rate of more than 40% in 3 months can be achieved, degradation products cannot harm marine ecology, micro plastics cannot be formed finally, meanwhile, the shelf life can meet the circulation requirements of production, sales and use, and the low-carbon seawater degradation film has important significance for solving the marine pollution problem caused by waste plastics.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
Example 1
The embodiment provides a preparation method of a seawater degradation membrane, which comprises the following steps:
s1: adding 20 parts by weight of corn starch and 0.1 part by weight of stearic acid into a high-speed mixer, and mixing for 2 minutes at a rotating speed of 200 rpm; then adding 5 parts by weight of glycerol, and mixing for 8min at 600 rpm; finally, adding 0.2 weight part of adipic acid and 0.2 weight part of citric acid, and mixing for 1min at a rotating speed of 200rpm to prepare plasticized and modified corn starch;
s2: 10 parts by weight of PLGA, 15 parts by weight of PHBH, 10 parts by weight of PPC, 45 parts by weight of PBAT, 0.2 parts by weight
MH and 0.3 parts by weight of white oil were added to a mixer with a fixed rotation speed of 80rpm and mixed for 30 seconds; then add 2 parts by weight ∈>
2504. 0.1 part by weight of antioxidant 1010 and 0.2 part by weight of antioxidant 168, for 30 seconds; finally, adding the plasticized and modified corn starch prepared in the step S1, mixing for 1 minute, and uniformly stirring to prepare a mixed master batch;
s3: adding the mixed master batch prepared in the step S2 into a parallel double-screw extruder, setting the temperature of a 1-9 region of the double-screw extruder to be 130 ℃,180 ℃,180 ℃,175 ℃,170 ℃,170 ℃,170 ℃,170 ℃ and the temperature of a machine head to be 170 ℃, carrying out melt blending and air-cooling granulation, and preparing the seawater degradation blown film material;
s4: and (3) carrying out film blowing molding on the film blowing material prepared in the step (S3) by adopting a common high-pressure PE film blowing machine, setting the temperature of a 1-5 region of the film blowing machine to be 130 ℃,180 ℃,180 ℃,180 ℃,180 ℃ and 175 ℃ at the die head temperature, and finally obtaining the low-seawater degradation film with the thickness of 40 mu m and the breadth of 600mm.
Example 2
The embodiment provides a preparation method of a seawater degradation membrane, which comprises the following steps:
s1: firstly, adding 20 parts by weight of corn starch and 0.1 part by weight of polyhydroxy macromolecule super-dispersion modifier JL-G02FX-P into a high-speed mixer, and mixing for 2 minutes at a rotating speed of 200 rpm; adding 5 parts by weight of sorbitol, and mixing for 8min at 600 rpm; finally, adding 0.2 weight part of adipic acid and 0.2 weight part of citric acid, and mixing for 1min at a rotating speed of 200rpm to prepare plasticized and modified corn starch;
s2: 15 parts by weight of PLGA, 20 parts by weight of PHBH, 10 parts by weight of PPC, 35 parts by weight of PBAT, 0.2 parts by weight
MH and 0.3 parts by weight of white oil were added to a mixer with a fixed rotation speed of 80rpm and mixed for 30 seconds; then add 2 parts by weight ∈>
2504. 0.1 part by weight of antioxidant 1010 and 0.2 part by weight of antioxidant 168, for 30 seconds; finally, adding the plasticized and modified corn starch prepared in the step S1, mixing for 1 minute, and uniformly stirring to prepare a mixed master batch;
s3: adding the mixed master batch prepared in the step S2 into a parallel double-screw extruder, setting the temperature of a 1-9 region of the double-screw extruder to be 130 ℃,180 ℃,180 ℃,175 ℃,170 ℃,170 ℃,170 ℃,170 ℃ and the temperature of a machine head to be 170 ℃, carrying out melt blending and air-cooling granulation, and preparing the seawater degradation blown film material;
s4: and (3) carrying out film blowing molding on the film blowing material prepared in the step (S3) by adopting a common high-pressure PE film blowing machine, wherein the temperature of a 1-5 region of the film blowing machine is 130 ℃,180 ℃,180 ℃,180 ℃,180 ℃ and 175 ℃ of a die head temperature, and finally obtaining the seawater degradation film with the thickness of 40 mu m and the breadth of 600mm.
Example 3
The embodiment provides a preparation method of a seawater degradation membrane, which comprises the following steps:
s1: adding 20 parts by weight of corn starch, 0.05 part by weight of polyhydroxy macromolecule super-dispersion modifier JL-G02FX-P and 0.05 part by weight of stearic acid into a high-speed mixer, and mixing for 2 minutes at a rotating speed of 200 rpm; then adding 2 parts by weight of glycerol and 3 parts by weight of sorbitol, and mixing for 8 minutes at 600 rpm; finally, adding 0.2 weight part of adipic acid and 0.2 weight part of citric acid, and mixing for 1min at a rotating speed of 200rpm to prepare plasticized and modified corn starch;
s2: 20 parts by weight of PLGA, 25 parts by weight of PHBH, 10 parts by weight of PPC, 25 parts by weight of PBAT, 0.2 parts by weight
MH and 0.3 parts by weight of white oil were added to a mixer with a fixed rotation speed of 80rpm and mixed for 30 seconds; then add 2 parts by weight ∈>
2504. 0.1 part by weight of antioxidant 1010 and 0.2 part by weight of antioxidant 168, for 30 seconds; finally, adding the plasticized and modified corn starch prepared in the step S1, mixing for 1 minute, and uniformly stirring to prepare a mixed master batch;
s3: adding the mixed master batch prepared in the step S2 into a parallel double-screw extruder, setting the temperature of a 1-9 region of the double-screw extruder to be 130 ℃,180 ℃,180 ℃,175 ℃,170 ℃,170 ℃,170 ℃,170 ℃ and the temperature of a machine head to be 170 ℃, carrying out melt blending and air-cooling granulation, and preparing the seawater degradation blown film material;
s4: the film blowing material prepared in the step S3 is subjected to film blowing molding by adopting a common high-pressure PE film blowing machine, the temperature of a 1-5 region of the film blowing machine is set to be 130 ℃,180 ℃,180 ℃,180 ℃,180 ℃ and the die head temperature is set to be 175 ℃; finally, the seawater degradation film with the thickness of 40 mu m and the breadth of 600mm is obtained.
Comparative example 1
The comparative example provides a preparation method of a seawater degradation membrane, comprising the following steps:
s1: adding 20 parts by weight of corn starch, 0.05 part by weight of polyhydroxy macromolecule super-dispersion modifier JL-G02FX-P and 0.05 part by weight of stearic acid into a high-speed mixer, and mixing for 2 minutes at a rotating speed of 200 rpm; then adding 2 parts by weight of glycerol and 3 parts by weight of sorbitol, and mixing for 8 minutes at 600 rpm; finally, adding 0.2 weight part of adipic acid and 0.2 weight part of citric acid, and mixing for 1min at a rotating speed of 200rpm to prepare plasticized and modified corn starch;
s2: 30 parts by weight of PLGA, 50 parts by weight of PHBH, 0.2 parts by weight
MH and 0.3 parts by weight of white oil were added to a mixer with a fixed rotation speed of 80rpm and mixed for 30 seconds; then add 2 parts by weight ∈>
2504. 0.1 part by weight of antioxidant 1010 and 0.2 part by weight of antioxidant 168, for 30 seconds; finally, adding the plasticized and modified corn starch prepared in the step S1, mixing for 1 minute, and uniformly stirring to prepare a mixed master batch;
s3: adding the mixed master batch prepared in the step S2 into a parallel double-screw extruder, setting the temperature of a 1-9 region of the double-screw extruder to be 130 ℃,180 ℃,180 ℃,175 ℃,170 ℃,170 ℃,170 ℃,170 ℃ and the temperature of a machine head to be 170 ℃, carrying out melt blending and air-cooling granulation, and preparing the seawater degradation blown film material;
s4: the film blowing material prepared in the step S3 is subjected to film blowing molding by adopting a common high-pressure PE film blowing machine, the temperature of a 1-5 region of the film blowing machine is set to be 130 ℃,180 ℃,180 ℃,180 ℃,180 ℃ and the die head temperature is set to be 175 ℃; finally, the seawater degradation film with the thickness of 40 mu m and the breadth of 600mm is obtained.
Comparative example 2
The difference between this comparative example and example 3 is that the following is the procedure S2:
45 parts by weight of PLGA, 10 parts by weight of PPC, 25 parts by weight of PBAT, 0.2 part by weight
MH and 0.3 parts by weight of white oil were added to a mixer with a fixed rotation speed of 80rpm and mixed for 30 seconds; then 2 parts by weight of
2504. 0.1 part by weight of antioxidant 1010 and 0.2 part by weight of antioxidant 168, for 30 seconds; and finally, adding the plasticized and modified corn starch prepared in the step S1, mixing for 1 minute, and uniformly stirring to prepare the mixed master batch.
Comparative example 3
The difference between this comparative example and example 3 is that the following is the procedure S2:
45 parts by weight of PHBH, 10 parts by weight of PPC, 25 parts by weight of PBAT, 0.2 part by weight
MH and 0.3 parts by weight of white oil were added to a mixer with a fixed rotation speed of 80rpm and mixed for 30 seconds; then 2 parts by weight of
2504. 0.1 part by weight of antioxidant 1010 and 0.2 part by weight of antioxidant 168, for 30 seconds; and finally, adding the plasticized and modified corn starch prepared in the step S1, mixing for 1 minute, and uniformly stirring to prepare the mixed master batch.
Comparative example 4
The difference between this comparative example and example 3 is that the following is the procedure S2:
20 parts by weight of PLGA, 25 parts by weight of PHBH, 35 parts by weight of PPC, 0.2 part by weight
MH and 0.3 parts by weight of white oil were added to a mixer with a fixed rotation speed of 80rpm and mixed for 30 seconds; then 2 parts by weight of
2504. 0.1 part by weight of antioxidant 1010 and 0.2 part by weight of antioxidant 168, for 30 seconds; finally adding the plasticizing modified jade prepared in the step S1Rice starch is mixed for 1 minute, and the mixture is stirred uniformly to prepare the mixed master batch.
Comparative example 5
The difference between this comparative example and example 3 is that the following is the procedure S2:
20 parts by weight of PLGA, 25 parts by weight of PHBH, 35 parts by weight of PBAT, 0.2 parts by weight
MH and 0.3 parts by weight of white oil were added to a mixer with a fixed rotation speed of 80rpm and mixed for 30 seconds; then 2 parts by weight of
2504. 0.1 part by weight of antioxidant 1010 and 0.2 part by weight of antioxidant 168, for 30 seconds; and finally, adding the plasticized and modified corn starch prepared in the step S1, mixing for 1 minute, and uniformly stirring to prepare the mixed master batch.
Comparative example 6
The difference between this comparative example and example 3 is that the following is the procedure S2:
20 parts by weight of polylactic acid PLA, 25 parts by weight of PHBH, 10 parts by weight of PPC, 25 parts by weight of PBAT and 0.2 part by weight
MH and 0.3 parts by weight of white oil were added to a mixer with a fixed rotation speed of 80rpm and mixed for 30 seconds; then add 2 parts by weight ∈>
2504. 0.1 part by weight of antioxidant 1010 and 0.2 part by weight of antioxidant 168, for 30 seconds; and finally, adding the plasticized and modified corn starch prepared in the step S1, mixing for 1 minute, and uniformly stirring to prepare the mixed master batch.
Comparative example 7
The difference between this comparative example and example 3 is that the following is the procedure S2:
20 parts by weight of PLGA, 25 parts by weight of PHBH, 10 parts by weight of PPC, 25 parts by weight of PBAT, 0.2 part by weight of p-benzeneAdding diphenol dihydroxyethyl ether and 0.3 part by weight of white oil into a stirrer with a fixed rotating speed of 80rpm, and mixing for 30 seconds; then 2 parts by weight of
2504. 0.1 part by weight of antioxidant 1010 and 0.2 part by weight of antioxidant 168, for 30 seconds; and finally, adding the plasticized and modified corn starch prepared in the step S1, mixing for 1 minute, and uniformly stirring to prepare the mixed master batch.
Comparative example 8
The difference between this comparative example and example 3 is that step S1 is as follows:
adding 20 parts by weight of corn starch, 0.05 part by weight of polyhydroxy macromolecule super-dispersion modifier JL-G02FX-P and 0.05 part by weight of stearic acid into a high-speed mixer, and mixing for 2 minutes at a rotating speed of 200 rpm; then adding 2 parts by weight of glycerol and 3 parts by weight of sorbitol, and mixing for 8 minutes at 600 rpm; finally, 0.4 weight part of adipic acid is added and mixed for 1min at a rotation speed of 200rpm to prepare the plasticized and modified corn starch.
Comparative example 9
The difference between this comparative example and example 3 is that step S1 is as follows:
adding 20 parts by weight of corn starch, 0.05 part by weight of polyhydroxy macromolecule super-dispersion modifier JL-G02FX-P and 0.05 part by weight of stearic acid into a high-speed mixer, and mixing for 2 minutes at a rotating speed of 200 rpm; then adding 2 parts by weight of glycerol and 3 parts by weight of sorbitol, and mixing for 8 minutes at 600 rpm; finally, 0.4 weight part of citric acid is added and mixed for 1min at a rotation speed of 200rpm to prepare the plasticizing modified corn starch.
Comparative example 10
The low-density polyethylene (FB 3000 of LG company) is blown by a common PE film blowing machine, and the temperature of each area of the film blowing machine is 145 ℃. The thickness of the film was 40 μm and the width was 600mm.
The physical and mechanical properties (including tensile strength, elongation at break and heat seal strength) of the seawater-degradable films prepared in each of the above examples and comparative examples were tested. The physical and mechanical properties were tested on a universal tensile tester (CMT-4304, shenzhen Sansi Co., ltd.) in which the tensile strength and elongation at break were measured according to GB/T1040.3-2006 at a test rate of 250mm/min and the heat seal strength was measured according to QB/T2358-1998 at a test rate of 300mm/min.
The test results are shown in Table 1.
TABLE 1
As shown in the data of the table, compared with the traditional PE film, the seawater degradation film provided by the invention has obviously excellent transverse and longitudinal tensile strength, the elongation at break is basically equivalent to the heat sealing strength, and the mechanical property can meet the normal use requirement; compared with the example 3, the comparative example 1 is not added with PPC and PBAT, and the data of the comparative example show that the addition of the biodegradable materials PPC and PBAT can obviously improve the transverse and longitudinal elongation at break and the heat sealing strength of the prepared film, but can cause the reduction of the transverse and longitudinal tensile strength; comparative example 2 compared to example 3, without PHBH added, the film provided in comparative example 2 had an increased transverse-longitudinal tensile strength, but decreased transverse-longitudinal elongation at break, and also had a decreased heat seal strength; comparative example 3 the film provided in comparative example 3, in which no PLGA was added, exhibited a small increase in both the transverse-machine-direction elongation at break and the heat seal strength, but the transverse-machine-direction tensile strength was decreased, as compared with example 3; comparative example 4 the film provided in comparative example 4 had increased heat seal strength but decreased transverse direction tensile strength and elongation at break compared to example 3 without the addition of PBAT; comparative example 5 the film provided in comparative example 5 had increased transverse-machine direction tensile strength and breaking productivity but decreased heat seal strength compared to example 3 without the addition of PPC; comparative example 6 compared to example 3, the substitution of PLGA with PLA provided a film of comparative example 6 which has significantly increased transverse-machine direction fracture productivity and more excellent heat seal strength, but has transverse-machine direction tensile strengthObviously reduces; comparative example 7 compared to example 3, hydroquinone dihydroxyethyl ether was substituted
MH, the transverse and longitudinal tensile strength and the elongation at break of the film provided in comparative example 7 are obviously reduced, and the heat sealing strength is also reduced; comparative example 8 compared with example 3, no citric acid was added during the preparation of the plasticized modified corn starch, and the film provided in comparative example 8 did not show significant changes in transverse-machine direction tensile strength, transverse-machine direction fracture productivity, and heat seal strength; comparative example 9 the films provided in comparative example 9 were free of significant changes in transverse-machine tensile strength, transverse-machine fracture productivity and heat seal strength, as compared to example 3, without the addition of adipic acid during the preparation of the plasticized modified corn starch.
The seawater degradation performance and the shelf life of the seawater degradation films prepared in the examples and the comparative examples are tested, the seawater degradation performance is tested by adopting a weightlessness method, a film sample is placed in a seawater (taken from yellow sea near Qingdao) tank, seawater is replaced once a week, the test time is 3 months, samples are respectively sampled every 15 days, the samples are taken out and dried to constant weight, and the detection results are shown in Table 2 in detail; shelf life testing was performed in a constant temperature and humidity laboratory (temperature 25 ℃, humidity 50% RH), test period was 10 months, samples were taken for 5 films every 2 months, and the change in transverse tensile strength was tested (test method see above), and the test results are shown in Table 3.
TABLE 2
Note that: the "+" section indicates that the test film begins to undergo fragmentation
As can be seen from the data in Table 2, examples 1 to 3 of the present invention were preparedThe film has obvious seawater degradation characteristic, the seawater degradation weight loss rate within 3 months can reach more than 40%, and the seawater degradation speed and degree of the film are obviously reduced along with the increase of the proportion of PBAT and PPC in a formula system. Compared with the example 3, the comparative example 2 has no PHBH added, and the weight loss rate is slightly lower when the film seawater degradation time provided by the comparative example 2 is the same; comparative example 3 compared with example 3, no PLGA was added, and the weight loss rate was slightly higher when the film seawater degradation time provided in comparative example 3 was the same; comparative example 4 compared with example 3, there was no addition of PBAT, the film provided in comparative example 4 (no significant change in weight loss rate when the seawater degradation time was the same, the film provided in comparative example 5 did not significantly change in weight loss rate when the seawater degradation time was the same, no addition of PPC, the film provided in comparative example 5, the film provided in comparative example 6 was PLGA replaced with PLA compared with example 3, the film provided in comparative example 6 was significantly reduced in weight loss rate when the seawater degradation time was the same, the film provided in comparative example 7 was hydroquinone dihydroxyethyl ether replaced with hydroquinone compared with example 3)
MH, comparative example 7 provided film seawater degradation time the same, no obvious change in the weight loss rate; compared with the example 3, the comparative example 8 has no citric acid added in the preparation process of the plasticizing modified corn starch, and the weight loss rate is not obviously changed when the film provided by the comparative example 8 has the same seawater degradation time; comparative example 9 compared with example 3, adipic acid is not added in the preparation process of plasticized modified corn starch, and when the film provided in comparative example 9 has the same seawater degradation time, the weight loss rate is not changed obviously; the traditional PE film is soaked in seawater for 3 months, and no obvious degradation weightlessness phenomenon exists. />
TABLE 3 Table 3
As can be seen from the data in table 3, over timeThe films prepared in examples 1 to 3 and comparative example 1 all show a decreasing trend in transverse tensile strength, wherein the films prepared in examples 1 to 3 still have certain mechanical properties after 10 months, and the film prepared in comparative example 1 has completely lost mechanical properties after 6 months, so that the use requirement cannot be met; compared with the example 3, the film provided in the comparative example 2 has higher transverse tensile strength reduction speed without PHBH, which means that the film has higher degradation speed and shorter shelf life, and is difficult to meet the use requirement; comparative example 3 compared to example 3 without addition of PLGA, comparative example 3 provided a film with a slower rate of decrease in transverse tensile strength, a slower degradation rate, and a longer shelf life; comparative example 4 the film provided in comparative example 4, without the addition of PBAT, had no significant change in the rate of decrease in transverse tensile strength compared to example 3, and the shelf life of the resulting film was comparable to example 3; comparative example 5 the film provided in comparative example 5, without the addition of PPC, showed no significant change in the rate of decrease in transverse tensile strength compared to example 3, and the shelf life of the resulting film was comparable to example 3; comparative example 6 compared with example 3, the PLGA was replaced with PLA, and the film provided in comparative example 6 was significantly slower in the decrease in transverse tensile strength and significantly longer in shelf life; comparative example 7 compared to example 3, hydroquinone dihydroxyethyl ether was substituted
MH, the film provided in comparative example 7 has a faster rate of decrease in transverse tensile strength, which means that the film has a faster degradation rate and a shorter shelf life, and is difficult to meet the use requirements; compared with the example 3, the comparative example 8 has no citric acid added in the preparation process of the plasticizing modified corn starch, and the film provided by the comparative example 8 has higher transverse tensile strength reduction speed, which indicates that the film has higher degradation speed and shorter shelf life, and is difficult to meet the use requirement; compared with the example 3, the comparative example 9 has no adipic acid added in the preparation process of the plasticizing modified corn starch, and the film provided by the comparative example 9 has higher transverse tensile strength reduction speed, which indicates that the film has higher degradation speed and shorter shelf life, and is difficult to meet the use requirement; the PE film prepared in comparative example 10 showed no significant decrease in mechanical properties over a 10 month test period.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (10)
1. The seawater degradation film is characterized by comprising the following components in parts by weight:
2. the seawater-degradable film of claim 1, wherein the polylactic acid-glycolic acid copolymer has a molecular weight M W More than or equal to 60000, the mass content of GA in the molecular structural unit is more than or equal to 80 percent, the melt flow rate MFR is less than or equal to 7g/10min (190 ℃,2.16 KG), and the melting point is less than or equal to 175 ℃.
3. The seawater-degradable film of claim 1, wherein the molecular weight M of 3-hydroxybutyrate-co-3-hydroxycaproate W More than or equal to 50000, the melt flow rate MFR is less than or equal to 5g/10min (165 ℃,5 KG), and the melting point is less than or equal to 150 ℃.
4. The seawater-degradable film of claim 1, wherein the plasticizer is selected from at least one of glycerin and sorbitol.
5. The seawater-degradable film of claim 1, wherein the starch treating agent is selected from at least one of stearic acid and a polyhydroxy polymeric super-dispersion modifier.
6. The seawater-degradable film of claim 1, wherein the organic peroxide is
MH。
7. The seawater-degradable film of claim 1, wherein the ethylene-vinyl acetate copolymer is
2504。
8. The seawater-degradable film of claim 1, wherein the antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:2.
9. A method for producing a seawater degradation membrane as claimed in any one of claims 1 to 8, comprising the steps of:
s1: adding corn starch and starch treating agent into a high-speed mixer according to the formula amount, and mixing at a rotating speed of 200 rpm; adding plasticizer, and mixing at 600 rpm; finally, adipic acid and citric acid are added and mixed at the rotating speed of 200rpm to prepare plasticized and modified corn starch;
s2: adding polylactic acid-glycollic acid copolymer, 3-hydroxybutyrate-co-3-hydroxycaproic acid ester, polypropylene carbonate, poly (adipic acid)/butylene terephthalate, organic peroxide and white oil into a stirrer with a fixed rotating speed of 80rpm according to the formula amount, and mixing; then adding ethylene-vinyl acetate copolymer and antioxidant, mixing; finally, adding the plasticized and modified corn starch, mixing, and uniformly stirring to prepare a mixed master batch;
s3: adding the mixed master batch into a parallel double-screw extruder, carrying out melt blending and air cooling granulation to prepare a seawater degradation film blowing material;
s4: and (3) blowing the seawater degradation film blowing material to form a seawater degradation film.
10. The method for producing a seawater-degradable film as claimed in claim 9, wherein the temperature of the 1-9 region of the twin-screw extruder is set to 130 ℃,180 ℃,180 ℃,180 ℃,175 ℃,170 ℃,170 ℃,170 ℃,170 ℃,170 ℃ and 170 ℃ at a head temperature of 170 ℃ in the step S3; in the step S4, the temperature of the 1-5 region of the film blowing machine is 130 ℃,180 ℃,180 ℃,180 ℃ and the die head temperature is 175 ℃.
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