CN112430385A - Fully-degradable membrane material and preparation and application thereof - Google Patents
Fully-degradable membrane material and preparation and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000012528 membrane Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920002472 Starch Polymers 0.000 claims abstract description 26
- 239000008107 starch Substances 0.000 claims abstract description 23
- 235000019698 starch Nutrition 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 4
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 239000012785 packaging film Substances 0.000 claims abstract description 3
- 229920006280 packaging film Polymers 0.000 claims abstract description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910021389 graphene Inorganic materials 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 239000007900 aqueous suspension Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 229920002261 Corn starch Polymers 0.000 claims description 5
- 239000003242 anti bacterial agent Substances 0.000 claims description 5
- 239000008120 corn starch Substances 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229920001592 potato starch Polymers 0.000 claims description 4
- 244000017020 Ipomoea batatas Species 0.000 claims description 3
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 3
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- XLDBGFGREOMWSL-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediimine Chemical group CC(C)C1=CC=CC(C(C)C)=C1N=C=NC1=C(C(C)C)C=CC=C1C(C)C XLDBGFGREOMWSL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- AZQGFVRDZTUHBU-UHFFFAOYSA-N isocyanic acid;triethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OCC)(OCC)OCC AZQGFVRDZTUHBU-UHFFFAOYSA-N 0.000 claims 1
- XFMVUVPRNCKJOF-UHFFFAOYSA-N trimethoxy(propyl)silane;urea Chemical compound NC(N)=O.CCC[Si](OC)(OC)OC XFMVUVPRNCKJOF-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
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- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 4
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- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000004302 potassium sorbate Substances 0.000 description 2
- 235000010241 potassium sorbate Nutrition 0.000 description 2
- 229940069338 potassium sorbate Drugs 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- 240000003291 Armoracia rusticana Species 0.000 description 1
- 235000011330 Armoracia rusticana Nutrition 0.000 description 1
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
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- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
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- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229920000704 biodegradable plastic Polymers 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-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
- C08J2367/04—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
- 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
- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
-
- 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
- C08J2467/02—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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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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)
Abstract
The invention relates to a fully degradable membrane material and preparation and application thereof, wherein the membrane material is prepared from the following raw materials in parts by weight: 50-70 parts of PLA, 30-50 parts of natural starch, 8-20 parts of PBAT, 2-6 parts of a functional stabilizer, 6-15 parts of a plasticizer, 1-5 parts of a compatilizer and 0.5-2 parts of an anti-hydrolysis agent; when in preparation, the PLA, the natural starch, the PBAT and the functional stabilizer are melted and blended at the temperature of 180-200 ℃ according to the weight part, the blending time is 10-20 minutes, then other auxiliary agents are added according to the weight part, the mixture is blended at the temperature of 170-180 ℃ for 5-10 minutes, and then the mixture is extruded and granulated. The material of the invention can be used for preparing packaging films, mulching films, preservative films and sticking films. Compared with the prior art, the fully degradable film material has good film forming property, excellent flexibility and environment-friendly raw materials, and the prepared film material has good heat insulation, moisture resistance, bacteria resistance, water resistance and the like, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, and relates to a fully-degradable film material and preparation and application thereof.
Background
With the rapid development of world economy, people enjoy polymer materials to bring convenience to our lives and improve the quality of life, and people are aware of the harm to the environment caused by the abandoned non-degradable polymer materials, and the damage to the ecological environment caused by 'white pollution' is not negligible, so people need to urgently find an environment-friendly universal plastic substitute.
Starch is widely applied to the main raw material for preparing environment-friendly degradable plastics at present, and the starch-based degradable plastics are the most promising biodegradable plastics capable of replacing petroleum-based plastics at present. However, the hydrophilicity of starch itself causes the starch-based plastic to have disadvantages in thermal stability, water resistance and mechanical properties.
Besides starch, polylactic acid (PLA for short) is a novel thermoplastic aliphatic polyester, has higher strength, certain biocompatibility and heat resistance, is prepared from lactic acid which is a raw material and has wide sources, and is mainly obtained by fermenting substances containing starch and cellulose, such as corn, sugarcane, beet, straw and the like. The final decomposition products of the polylactic acid in nature are carbon dioxide and water, and the polylactic acid has no pollution to the environment and has sustainable development. Polylactic acid is an environment-friendly material, and can fundamentally solve the ecological problem caused by plastic pollution in the long run. However, polylactic acid has high rigidity, so that the material mainly prepared from the polylactic acid has the technical defects of serious brittleness, poor impact toughness, poor thermal stability and the like, and the popularization and the application of the polylactic acid in the field of degradable film materials are greatly limited.
Disclosure of Invention
The invention aims to overcome the technical problems of poor thermal stability, poor water resistance and poor mechanical property of the existing thermoplastic degradable material based on polylactic acid and/or starch, and provides a fully degradable film material which is green, environment-friendly, good in flexibility, easy to form a film, and good in heat insulation, moisture resistance, bacteria resistance, water resistance and the like.
The purpose of the invention can be realized by the following technical scheme:
according to one aspect of the invention, the fully degradable membrane material is prepared from the following raw materials in parts by weight: 50-70 parts of PLA, 30-50 parts of natural starch, 8-20 parts of PBAT, 2-6 parts of a functional stabilizer, 6-15 parts of a plasticizer, 1-5 parts of a compatilizer and 0.5-2 parts of an anti-hydrolysis agent.
As an embodiment, the functional stabilizer is PLA particles modified with graphene oxide, and the amount of the added graphene oxide is 1-10wt% based on the mass of the PLA particles.
As an embodiment, the preparation method of the graphene oxide-modified PLA particles is: preparing a graphene oxide aqueous suspension with the content of 2-5 wt%, mixing the graphene oxide aqueous suspension, a silane coupling agent and PLA particles with the particle size D50 of 40-80 mu m, magnetically stirring for 1-2 hours at 80-90 ℃, performing ultrasonic treatment for 2-4 hours at 50-60 ℃, and performing centrifugal separation, drying and grinding.
As an embodiment, the graphene oxide aqueous suspension is prepared by the following method: fully grinding and dispersing the graphene oxide and the deionized water at the rotating speed of 20000-plus 30000 r/min for 20-60 minutes below 10 ℃, and then carrying out ultrasonic oscillation at the temperature of 50 ℃, wherein the frequency of the ultrasonic oscillation is controlled to be 2000MHz, and the ultrasonic oscillation is carried out for 20-30 minutes, so as to obtain the graphene oxide water suspension.
In one embodiment, the silane coupling agent is added in an amount of 0.2 to 1.6 wt% based on the mass of the PLA particles, and the silane coupling agent is selected from at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, isocyanatopropyltriethoxysilane, and ureidopropyltrimethoxysilane.
As an embodiment, the graphene oxide-modified PLA particles have a D50 ≦ 20 μm.
As an embodiment, the native starch is selected from at least one of sweet potato starch, tapioca starch, corn starch or wheat starch.
In one embodiment, the plasticizer is at least one selected from epoxidized soybean oil, glycerin, and polyethylene glycol, the compatibilizer is a maleic anhydride grafted compatibilizer, and the hydrolysis resistant agent is selected from bis (2, 6-diisopropylphenyl) carbodiimide.
Preferably, the compatibilizer can be selected from ABS-g-MAH with a grafting ratio of 1.2-1.5%.
As an embodiment, the raw materials also comprise 1-3 parts of lubricant and 0.1-1 part of antibacterial agent.
Preferably, the lubricant is selected from at least one of polyethylene wax, paraffin wax, liquid wax or polypropylene wax.
The antibacterial agent is at least one selected from potassium sorbate, chitosan, chitin, mustard, castor oil or horseradish.
According to another aspect of the invention, the preparation method of the fully degradable membrane material is provided, melting and blending PLA, natural starch, PBAT, the functional stabilizer and the hydrolysis resistant agent according to the parts by weight at the temperature of 180-200 ℃ for 10-20 minutes, then adding other auxiliary agents according to the parts by weight, blending at the temperature of 170-180 ℃ for 5-10 minutes, and then extruding and granulating to obtain the material.
According to another aspect of the invention, the application of the fully degradable film material is provided, and the material can be used for preparing film materials such as packaging films, mulching films, preservative films, sticking films and the like.
As an embodiment, the fully degradable film material can be blown into a film by a blow molding process at 190 ℃ at 170 ℃ and the blow-up ratio can be controlled to be 1.5-3.0.
The fully degradable film material of the invention is not only suitable for blow molding, including single-layer blow molding and multilayer coextrusion blow molding, but also suitable for preparing sheets, pipes and other extrusion molding processes.
Compared with the prior art, the invention has the following characteristics:
1) the film material takes PLA and natural starch as main film forming substances, and introduces polybutylene terephthalate-adipate (PBAT for short), which can effectively improve the flexibility of PLA and natural starch base materials and reduce the rigidity of a material system;
2) the functional stabilizer (namely PLA particles modified by graphene oxide) is also introduced into the components of the membrane material, the graphene oxide has rich oxygen-containing functional groups and has better chemical activity, the graphene oxide can be combined to the surface of the PLA particles through a silane coupling agent, the PLA particles can play a role of a dispersing carrier, the graphene oxide can be favorably and uniformly dispersed in a material system, the large-scale agglomeration phenomenon of the graphene oxide can be effectively avoided, the introduction of the graphene oxide can not only obviously improve the thermal stability of the material system, but also play a certain role of blocking in the material system, the permeation of external oxygen or moisture to the material system can be favorably blocked or reduced, the moisture resistance of the material system can be effectively improved, and the heat exchange through the material system can be favorably blocked or reduced, has better heat preservation and insulation effects;
3) the functional stabilizer in the film material component is mainly PLA particles, has better rigidity, is favorable for keeping the film forming stiffness of the material system when being introduced into the material system, and is favorable for inhibiting the thermal degradation of the raw material components in the melting and blending process, improving the hydrolysis resistance of the final film forming and properly prolonging the service life of the film forming;
4) the preparation process of the membrane material is simple in steps, low in energy consumption, easy to obtain raw materials, good in environmental protection performance, good in flexibility of the prepared membrane product, good in heat insulation, moisture resistance, bacteria resistance, water resistance and the like, can be completely degraded within a period of time through composting after being used, cannot cause burden on the environment, and has good environmental benefits.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed embodiment and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. For example, "a range of from 1 to 10" should be understood to mean every and every possible number in succession between about 1 and about 10. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to only a few specific points, it is to be understood that any and all data points within the range are to be considered explicitly stated.
As used herein, the term "about" when used to modify a numerical value means within + -5% of the error margin measured for that value.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
The present invention will be described in detail with reference to specific examples.
The following table 1 shows the components and their contents in parts by weight in the materials of examples 1-5 and comparative examples 1-2:
table 1 raw material formulation
| Item | PLA | Natural starch | PBAT | Functional stabilizer | Plasticizer | Compatilizer | Hydrolysis-resistant agent | Lubricant agent | Antibacterial agent |
| Example 1 | 50 portions of | 30 portions of | 8 portions of | 2 portions of | 6 portions of | 1 part of | 0.5 portion | / | / |
| Example 2 | 58 portions of | 32 portions of | 10 portions of | 3 portions of | 8 portions of | 2 portions of | 0.8 portion of | / | 0.1 part |
| Example 3 | 60 portions of | 40 portions of | 12 portions of | 5 portions of | 12 portions of | 3 portions of | 1 part of | 1 part of | / |
| Example 4 | 70 portions of | 30 portions of | 16 portions of | 4 portions of | 10 portions of | 5 portions of | 1.4 parts of | 2 portions of | 0.6 part |
| Example 5 | 62 portions of | 48 portions of | 20 portions of | 6 portions of | 15 portions of | 5 portions of | 2 portions of | 3 portions of | 1 part of |
| Comparative example 1 | 70 portions of | 30 portions of | / | / | 10 portions of | 5 portions of | 1.4 parts of | 2 portions of | 0.6 part |
| Comparative example 2 | 70 portions of | 30 portions of | 16 portions of | / | 10 portions of | 5 portions of | 1.4 parts of | 2 portions of | 0.6 part |
Note: PLA in Table 1 is a commercially available polylactic acid with a trademark of 4032D;
the weight average molecular weight of the PBAT in table 1 was about 8 ten thousand.
Table 2 below shows the raw material types in the materials of examples 1-5 and comparative examples 1-2:
TABLE 2 types of materials
| Item | Natural starch | Functional stabilizer | Plasticizer | Compatilizer | Hydrolysis-resistant agent | Lubricant agent | Antibacterial agent |
| Example 1 | Sweet potato starch | The addition amount of the graphene oxide is 1wt% | Glycerol | ABS-g-MAH (graft ratio) 1.2%） | Bis (2, 6-diisopropylphenyl) carbodiimide Amines as pesticides | / | / |
| Example 2 | Potato starch | The addition amount of the graphene oxide is 4wt% | Glycerol | ABS-g-MAH (graft ratio) 1.2%） | Bis (2, 6-diisopropylphenyl) carbodiimide Amines as pesticides | / | Castor oil |
| Example 3 | Cassava starch | The addition amount of the graphene oxide is 8wt% | PEG-400 | ABS-g-MAH (graft ratio) 1.5%） | Bis (2, 6-diisopropylphenyl) carbodiimide Amines as pesticides | Paraffin wax | / |
| Example 4 | Corn starch | The addition amount of the graphene oxide is 6wt% | Epoxidized soybean oil | ABS-g-MAH (graft ratio) 1.3%） | Bis (2, 6-diisopropylphenyl) carbodiimide Amines as pesticides | Polyethylene wax | Mustard |
| Example 5 | Wheat starch | The addition amount of the graphene oxide is 10wt% | PEG-400 | ABS-g-MAH (graft ratio) 1.5%） | Bis (2, 6-diisopropylphenyl) carbodiimide Amines as pesticides | Liquid wax | Potassium sorbate |
| Comparative example 1 | Corn starch | / | Epoxidized soybean oil | ABS-g-MAH (graft)Rate of change 1.3%） | Bis (2, 6-diisopropylphenyl) carbodiimide Amines as pesticides | Polyethylene wax | Mustard |
| Comparative example 2 | Corn starch | / | Epoxidized soybean oil | ABS-g-MAH (graft ratio) 1.3%） | Bis (2, 6-diisopropylphenyl) carbodiimide Amines as pesticides | Polyethylene wax | Mustard |
In the above embodiment, the adopted functional stabilizer is a PLA particle modified by graphene oxide, and the specific preparation method is as follows:
the first step is as follows: fully grinding and dispersing the graphene oxide and the deionized water at 20000-30000 rpm (for example, 20000 rpm in example 1, 26000 rpm in examples 2-4 and 30000 rpm in example 5) at 10 ℃ or below for 20-60 minutes (for example, 20 minutes in example 1, 60 minutes in example 2 and 35 minutes in examples 3-5), then, performing ultrasonic vibration at 50 ℃ for 20 to 30 minutes (for example, 20 minutes for example 1, 30 minutes for example 2, and 25 minutes for examples 3 to 5) while controlling the frequency of the ultrasonic vibration at 2000MHz, and preparing an aqueous graphene oxide suspension having a content of 2 to 5 wt% (for example, 2 wt% for example 1, 3 wt% for example 2, and 5 wt% for examples 3 to 5);
the second step is that: adding PLA particles with the particle size D50 of 40-80 mu m and a silane coupling agent into graphene oxide water suspension (about 10 g of PLA particles are added into each 100 mL of the suspension), magnetically stirring the mixture for 2 hours at 90 ℃, then carrying out ultrasonic treatment for 2 hours at 60 ℃, then carrying out centrifugal separation and drying on the mixture, and grinding the mixture until the particle size D50 is less than or equal to 20 mu m to obtain the graphene oxide modified PLA particles.
In the second step, the PLA particles, the kinds of the silane coupling agent and the addition amounts thereof used are as shown in table 3 below:
TABLE 3
Based on the above raw material formulations of examples 1-5, the membrane material was prepared by the following method:
PLA, natural starch, PBAT, a functional stabilizer and an anti-hydrolysis agent are melt-blended at 180 ℃ and 200 ℃ (for example, 180 ℃ in example 1, 200 ℃ in examples 2 to 3 and 190 ℃ in examples 4 to 5) in parts by weight for 10 to 20 minutes (for example, 20 minutes in example 1, 10 minutes in examples 2 to 3 and 15 minutes in examples 4 to 5), and then other auxiliary agents are added in parts by weight and blended at 170 ℃ and 180 ℃ (for example, 170 ℃ in example 1, 180 ℃ in examples 2 to 3 and 172 ℃ in examples 4 to 5) for 5 to 10 minutes (for example, 10 minutes in example 1, 5 minutes in examples 2 to 3 and 8 minutes in examples 4 to 5), and then extrusion granulation is carried out, so that the film material is prepared.
Comparative examples 1-2 membrane materials were prepared using the following method:
the raw materials of the components are melted and blended at 180 ℃ according to the weight parts, the blending time is 20 minutes, and then the film material is prepared by extrusion granulation.
The film materials prepared based on the above examples 1-5 and comparative examples 1-2 can be blown into films by a blow molding process at 180 c, wherein the blow-up ratio can be controlled to about 2.5, and films having a thickness of about 40 μm can be prepared.
The films made based on the film materials of examples 1-5 and comparative examples 1-2 were subjected to mechanical property tests, the results of which are shown in table 4 below:
TABLE 4 results of mechanical testing
Films made based on the film materials of examples 1-5 and comparative examples 1-2 were subjected to barrier performance testing, the results of which are shown in table 5 below:
table 5 results of barrier testing
The above-described films based on the membrane materials of examples 1 to 5 were evaluated for their degradation properties with reference to the standard GB/T19277.1-2011 "determination of the capacity of the material to decompose aerobically and biologically at the end of controlled composting", and the results show: the film can be degraded into harmless micromolecules within 4-10 months in a compost environment.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Furthermore, it should be understood that the various aspects recited, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.
Claims (10)
1. The fully degradable film material is characterized by being prepared from the following raw materials in parts by weight: 50-70 parts of PLA, 30-50 parts of natural starch, 8-20 parts of PBAT, 2-6 parts of a functional stabilizer, 6-15 parts of a plasticizer, 1-5 parts of a compatilizer and 0.5-2 parts of an anti-hydrolysis agent.
2. The fully degradable membrane material of claim 1, wherein the functional stabilizer is PLA particles modified by graphene oxide, and the amount of the added graphene oxide is 1-10wt% based on the mass of the PLA particles.
3. The fully degradable film material as claimed in claim 2, wherein the preparation method of the graphene oxide modified PLA particle is as follows: preparing a graphene oxide aqueous suspension with the content of 2-5 wt%, mixing the graphene oxide aqueous suspension, a silane coupling agent and PLA particles with the particle size D50 of 40-80 mu m, magnetically stirring for 1-2 hours at 80-90 ℃, performing ultrasonic treatment for 2-4 hours at 50-60 ℃, and performing centrifugal separation, drying and grinding.
4. The fully degradable membrane material as claimed in claim 3, wherein the preparation method of the graphene oxide aqueous suspension is as follows: fully grinding and dispersing the graphene oxide and the deionized water at the rotating speed of 20000-plus 30000 r/min for 20-60 minutes below 10 ℃, and then carrying out ultrasonic oscillation at the temperature of 50 ℃, wherein the frequency of the ultrasonic oscillation is controlled to be 2000MHz, and the ultrasonic oscillation is carried out for 20-30 minutes, so as to obtain the graphene oxide water suspension.
5. The fully degradable film material of claim 3, wherein the silane coupling agent is added in an amount of 0.2-1.6 wt% based on the mass of the PLA particles, and the silane coupling agent is selected from at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, isocyanate propyltriethoxysilane, and urea propyltrimethoxysilane.
6. The fully degradable film material of claim 3, wherein said graphene oxide modified PLA particles have D50 ≤ 20 μm.
7. The fully degradable film material of claim 1, wherein said natural starch is at least one selected from sweet potato starch, tapioca starch, corn starch and wheat starch, said plasticizer is at least one selected from epoxidized soybean oil, glycerin or polyethylene glycol, said compatibilizer is maleic anhydride graft compatibilizer, and said hydrolysis-resistant agent is selected from bis (2, 6-diisopropylphenyl) carbodiimide.
8. The fully degradable film material of claim 1, wherein the raw materials further comprise 1-3 parts of lubricant and 0.1-1 part of antibacterial agent.
9. The method for preparing fully degradable film material as claimed in any one of claims 1 to 8, wherein the PLA, the natural starch, the PBAT and the functional stabilizer are melt blended at 180 ℃ for 10-20 minutes, then other auxiliary agents are added according to the weight portion, blended at 170 ℃ and 180 ℃ for 5-10 minutes, and then extruded and granulated to obtain the material.
10. The use of a fully degradable film material as claimed in any one of claims 1 to 8, wherein said material is used in the preparation of packaging films, mulching films, plastic wrap films, and film laminates.
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| CN113549309A (en) * | 2021-08-02 | 2021-10-26 | 安徽瑞鸿新材料科技有限公司 | Low-cost biodegradable film and preparation method thereof |
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