CN110791069B - Full-degradable high-barrier composite material for flexible package - Google Patents
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention relates to a fully-degradable high-barrier composite material for flexible packaging, which is prepared by blending the following components in parts by weight: 100 parts of biodegradable matrix resin; 0-30 parts of inorganic filler; 0.1-15 parts of an auxiliary agent. Preferably, the composite material is formed by double-layer co-extrusion compounding of inner-layer biodegradable matrix resin and outer-layer biodegradable matrix resin. The inner-layer biodegradable matrix resin comprises the following components in parts by weight: 10-90 parts of PBAT, 10-90 parts of PCL and 0.1-5 parts of auxiliary agent, wherein the total weight part of PBAT and PCL is 100 parts; the outer biodegradable matrix resin comprises: 10-90 parts of PBAT, 10-90 parts of PLA, 1-20 parts of inorganic filler and 0.1-8 parts of auxiliary agent; wherein the total weight of the PBAT and the PLA is 100 parts; the inorganic filler is nano calcium carbonate or talcum powder.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a fully-degradable high-barrier composite material for flexible packaging and a preparation method thereof.
Background
At present, plastic packaging materials are increasingly popularized, the plastic packaging materials are mainly made of materials such as polyethylene, polyester or polypropylene, plastic containers formed by blow molding, extrusion blowing or injection molding of plastic molds have the main advantages of corrosion resistance, low cost, light weight, easiness in carrying, diversified shapes and the like, and liquid packaging films belong to soft plastic packages and play an important role in packaging liquid foods such as soy sauce, vinegar, wine, non-carbonated beverages, milk and the like. Film materials for liquid food packaging should meet the requirements of packaging, printing, processing, storage and transportation, hygiene and the like. The liquid packaging film which is widely used in the market at present and can be used for an automatic packaging production line mainly adopts a Polyethylene (PE) co-extrusion film. Including transparent PE film, paper-aluminum-plastic composite film, etc.
However, most of the plastic packaging materials used in the market at present cannot be degraded in the natural environment, so that the plastic packaging materials bring convenience to human life and also bring an increasingly serious problem of environmental pollution. Because of its good corrosion resistance, some waste plastic packaging materials that cannot be reused are difficult to decompose and return to nature, resulting in the accumulation of waste plastic, which is often referred to as "white contamination". Such as: polypropylene, polyvinyl chloride and polyethylene can be remained in the field for decades without degradation, so that a series of soil problems are caused, the environmental protection negative effects caused by the degradation cause serious concerns and worries of various social circles, so that the development of degradable plastics becomes urgent and has very important significance for solving the problem of environmental pollution caused by plastic products.
Compared with the plastic, the biodegradable plastic has biodegradability, the completely biodegradable plastic comprises PLA, PBS, PBSA, PBAT, PCL, PHA, PHBV, starch and the like, and decomposed products and residues do not have any harm to the environment. The completely biodegradable plastic has important significance as a packaging material of a base material.
However, biodegradable plastics also have their drawbacks difficult to overcome, such as: poor processing thermal stability, strict requirements on processing conditions, low thermal deformation temperature and poor toughness，And poor barrier properties to oxygen, carbon dioxide and water vapor, as shown in the following:
polylactic acid (PLA), an aliphatic polyester obtained by dehydration polymerization of lactic acid produced by microbial fermentation as a monomer, has good biocompatibility and biodegradability. The renewable biomass materials such as corn, sugarcane, cassava and the like are used as raw materials, and the renewable biomass materials are wide in source and can be regenerated. The production process of the polylactic acid is low-carbon and environment-friendly, has less pollution, and the product can be composted and degraded after being used, thereby realizing the circulation in the nature. However, PLA has high modulus and strength, and PLA products are hard and brittle, so the main factors restricting the application of PLA are the problems of heat resistance and toughness, and blending other resins to modify PLA is a big way to improve the properties of PLA.
Poly (terephthalic acid) -succinic acid-1, 4-butanediol copolyester (PBAT) belongs to thermoplastic biodegradable plastics, is a copolymer of butanediol adipate and butanediol terephthalate, has the characteristics of PBA and PBT, and has better ductility and elongation at break as well as better heat resistance and impact performance because macromolecules have soft aliphatic chains and rigid aromatic groups; in addition, the PBAT also has excellent biodegradability, is one of the best degradable materials which are very active in the research of the current biodegradable plastics and applied in the market, but the PBAT has small tensile strength and low melt viscosity, and limits the processing performance and the practical application value of the PBAT.
Polycaprolactone (PCL) is an aliphatic polyester, has good biocompatibility and biodegradability, low melting point and good thermoplasticity and molding processability, and has wide research and application in food packaging materials and medical materials, but the PCL has low melting point and low mechanical strength, so that the application and development of the PCL are limited.
For single-component biodegradable matrix resins, such as PLA, PBAT or PCL, there are some performance deficiencies when used alone, and therefore, in order to improve the mechanical properties and performance of biodegradable plastics, blending modification is a common method, including:
the invention patent 201410733882.2 discloses a preparation method of high-toughness polycarbonate/polylactic acid-based alloy, the blending system of the two solves the problems of serious insufficient brittleness, poor heat resistance and the like of PLA, but the advantage that the PLA introduced is completely degradable is reduced, only partial degradation can be achieved, and the polycarbonate raw material source also causes certain consumption on petroleum resources and is not environment-friendly.
The invention patent CN109955555A discloses a biodegradable high-barrier liquid packaging film, which aims at the problem that the liquid food packaging film has higher requirements on heat sealability and barrier property (particularly barrier property to oxygen and aroma) and the biodegradable plastic packaging film which meets the requirements of liquid food packaging does not exist in the market at present. In particular, the present invention relates to a packaging film comprising, in order, a biodegradable heat-sealable layer, a barrier layer and a protective layer. The invention also relates to a method for producing said packaging film, to the use of said packaging film, and to a packaging article comprising said packaging film.
The invention patent CN106366588A provides a production method of a gas-barrier full-biodegradable beverage bottle, which comprises the following steps: raw material modification: adding a plastic auxiliary agent into a full-biodegradable material, mixing and granulating according to a certain proportion, wherein the auxiliary agent comprises at least one of a chain extender, a nucleating agent, a plasticizer and plastic expansion microspheres, and the full-biodegradable material comprises at least four of polycaprolactone PCL, polybutylene succinate PBS, polylactic acid PLA, polyhydroxyalkanoate PHA, polybutylene succinate adipate PBSA, polybutylene adipate PBAT and starch; processing the plastic master batch: uniformly mixing the mixture, processing plastic master batches, and blowing bottles: comprises extrusion bottle blowing, injection bottle blowing and finally surface treatment.
The invention patent CN109748381A discloses a biomass-based master batch and a preparation method thereof, which is prepared by the following steps: (1) grinding the crude plant fiber and calcium oxide by microwave, and then adding a coupling agent for high-mixing coating; (2) adding the blended powder and PCL into a continuous internal mixer, pre-dispersing for 2-3M in an internal mixing section, and then adding PCL-g-M H A and bio-based resin for internal mixing for 2-5 min; (3) and after banburying is finished, the mixture is transferred to a single screw section for extrusion granulation. The biomass-based master batch disclosed by the invention can be completely biodegraded, the plant fiber filling amount is high, the front-end plant fiber treatment step is simple, the cost is low, the process is simple, and the large-scale production can be realized. Compared with stone powder, the plant fiber powder has lower specific weight and better toughening and reinforcing effects.
However, the biodegradable biocomposites in the prior art are all single-layer composite structures, but have double-layer structures, and by endowing each layer with different functions, the fully biodegradable biocomposites which have excellent high barrier property, full biodegradability and low cost are not reported.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a fully-degradable biological composite material with a double-layer composite structure, each layer has different functions, so that the composite material has excellent high barrier property and good mechanical property, and simultaneously has full biodegradability, and in addition, the invention also provides a degradation regulation accelerator for promoting the degradation of PBAT.
The PBAT has flexible aliphatic chains and rigid aromatic bonds, has good tensile property and flexibility, excellent water resistance and high temperature resistance, and has biodegradability but low strength due to the existence of ester bonds. While PLA is relatively rigid, but hard and brittle. PCL, on the other hand, has excellent flexibility, biodegradability and good barrier properties, but its strength is low. Therefore, in order to fully exert the synergistic promotion effect of PBAT, PLA and PCL, the composite material has good full biodegradation performance, barrier property and mechanical property, and the method is realized by the following technical scheme:
the fully-degradable high-barrier composite material for the flexible package comprises biodegradable matrix resin, and is prepared by blending the following components in parts by weight: 100 parts of biodegradable matrix resin; 0-30 parts of inorganic filler; 0.1-15 parts of an auxiliary agent; the biodegradable matrix resin is one or a composition of more than two of PBAT, PCL, PLA, PBS, PBSA, PPC, PBST, PHB, PHA, PVA and PHBV.
In a preferred embodiment, the composite material is formed by at least multilayer coextrusion compounding of an inner layer biodegradable matrix resin and an outer layer biodegradable matrix resin.
In a further preferred embodiment, the composite material is formed by double-layer co-extrusion compounding of an inner-layer biodegradable matrix resin and an outer-layer biodegradable matrix resin. The inner-layer biodegradable matrix resin mainly comprises the following components in parts by weight: 10-90 parts of PBAT, 10-90 parts of PCL and 0.1-5 parts of auxiliary agent, wherein the total weight part of PBAT and PCL is 100 parts; the outer-layer biodegradable matrix resin mainly comprises the following components: 10-90 parts of PBAT, 10-90 parts of PLA, 1-20 parts of inorganic filler and 0.1-8 parts of auxiliary agent; wherein the total weight of the PBAT and the PLA is 100 parts; the inorganic filler is nano calcium carbonate or talcum powder. Wherein:
the inner layer biodegradable matrix resin plays a role in blocking, and the mass ratio of the inner layer biodegradable matrix resin to the outer layer biodegradable matrix resin is 0.8: 1-4:1.
As another preferred embodiment, the invention also comprises 1-10 parts of degradation regulation accelerant in the inner layer biodegradable matrix resin or/and the outer layer biodegradable matrix resin. The degradation regulation accelerant takes biochar as a carrier, forms a biochar composition by loading nano zinc oxide or/and nano titanium dioxide on the biochar, and carries out surface coating treatment on the biochar composition.
Wherein the preparation of the degradation regulating accelerant comprises the following steps:
step 1, preparing biochar into a solution with the mass concentration of 5% -15% by using deionized water, adding nano zinc oxide or/and nano titanium dioxide under stirring, performing ultrasonic dispersion treatment to form a biochar composition suspension, performing suction filtration and drying on the biochar composition suspension to obtain a biochar composition;
step 2, taking a silane coupling agent accounting for 1.0-2.5% of the mass of the biochar composition powder, and diluting the silane coupling agent by using absolute ethyl alcohol to ensure that the mass concentration of the silane coupling agent in the absolute ethyl alcohol is 5-10%;
3, putting the biochar composition powder into a high-speed stirrer for stirring, firstly stirring at a low speed, and adding a silane coupling agent/absolute ethyl alcohol mixed solution while stirring; after the mixed solution is poured into the container completely, stirring at high speed for 3-5min, and drying the composition in an oven at 80 deg.C for 6-12 h.
In other preferred embodiments, the preparation of the degradation regulating co-agent further comprises the steps of:
and 4, carrying out outer layer coating treatment by using polybutylene adipate terephthalate, polycaprolactone or polyvinyl alcohol solution, and drying to obtain the degradation regulation accelerant subjected to surface double-layer coating treatment. Wherein, the mass ratio of the outer coating layer to the degradation regulation accelerant is 2-10%, and the better preference is 3-6%.
The inventor of the invention intensively studies and discovers that: the surface of the biochar as a carrier is rich in nano pores
The porous structure has a larger specific surface area, so that on one hand, the nano zinc oxide or/and nano titanium dioxide can be loaded on the carbon skeleton of the biochar, on the other hand, the biochar can form a good interface bonding effect with a polymer matrix and has biodegradability. In addition, the biological carbon enhances the thermal stability of the biodegradable matrix resin system and relieves the thermal decomposition process of the biodegradable matrix resin system in the processing process.
As a further preferred embodiment, the inner biodegradable matrix resin is composed of the following components in parts by weight: 40-70 parts of PBAT, 30-60 parts of PCL, 5-8 parts of degradation regulation accelerator and 0.1-4 parts of auxiliary agent. The outer-layer biodegradable matrix resin comprises the following components in parts by weight: 40-80 parts of PBAT, 20-60 parts of PLA, 5-8 parts of degradation regulation accelerator, 5-15 parts of talcum powder and 0.1-5 parts of auxiliary agent.
The auxiliary agent is one or more of compatilizer, lubricant, chain extender, end capping agent and coupling agent.
Another object of the present invention is to provide a method for preparing a fully degradable high barrier composite for flexible packaging, comprising the steps of:
step 1, drying talcum powder, degradation regulation accelerant, PBAT and PCL respectively and testing the moisture content;
step 2, blending, stirring and mixing the PBAT, the PCL, the degradation regulation accelerant and the auxiliary agent to obtain an inner-layer biodegradable matrix resin mixture;
mixing PBAT parts, PLA, a degradation regulation accelerator, talcum powder and an auxiliary agent, and stirring and mixing the mixture to obtain an outer-layer biodegradable matrix resin mixture;
step 3, respectively putting the inner layer biodegradable matrix resin mixture and the outer layer biodegradable matrix resin mixture mixed in the step 2 into two twin-screw granulators, and respectively obtaining inner layer biodegradable matrix resin particles and outer layer biodegradable matrix resin particles with two different colors through heating, melting and extruding;
step 4, respectively placing the inner layer biodegradable matrix resin particles and the outer layer biodegradable matrix resin particles prepared in the step 3 in a dehumidifying dryer for drying, wherein the drying temperature is set to be 40-50 ℃, and the drying time is 8-12 hours;
step 5, respectively putting the inner layer biodegradable matrix resin particles and the outer layer biodegradable matrix resin particles prepared in the step 4 into feeding barrels of two screw extruders, controlling the flow of the biodegradable matrix resin melt by adopting a metering pump, and performing double-layer co-extrusion casting on the inner layer biodegradable matrix resin melt and the outer layer biodegradable matrix resin melt at a die head outlet under the action of a distributor;
and 6, carrying out double-layer co-extrusion casting on the biodegradable matrix resin composite melt obtained in the step 5 to form the fully-degradable high-barrier composite material for the flexible package under the action of a casting roller and a rubber compression roller.
In addition, the invention also provides application of the fully-degradable high-barrier composite material for the flexible package in the field of flexible packages. Among them, soft packages such as shampoo packages, cream packages, and the like.
The invention has the following beneficial effects:
firstly, a multilayer (preferably double-layer) co-extrusion compounding process is adopted, and the barrier property of the fully-degradable biological membrane is improved through a multilayer composite structure; the inner layer matrix resin is composed of PBAT and PCL, wherein the PCL is cooperated with the PBAT, the PBAT and the PCL play a role in realizing excellent barrier property, the outer layer matrix resin is composed of the PBAT and PLA, the flexibility of the PLA is enhanced through the PBAT, the PLA also enhances the strength of the PBAT, and the cooperation promotion function between the PBAT and the PLA is fully played.
Secondly, the degradation rate of PBAT is relatively slow due to the presence of aromatic PBT segments in the PBAT. The invention improves the degradation rate of the invention by the photocatalytic degradation synergistic biodegradation of the degradation regulation accelerant (nano titanium dioxide \ nano zinc oxide).
Finally, the invention takes the biochar which has biodegradability and good interface compatibility with matrix resin as a carrier framework of the degradation regulation accelerant, the surface of the biochar has rich nano-pore structures and larger specific surface area, and the pore structures and the specific surface area ensure that the ecotype biochar and a polymer matrix not only form good interface combination action, but also can obviously enhance the mechanical property of the composite material.
Detailed Description
The present invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the present invention, but the scope of the present invention is not limited to the following examples.
The auxiliary agent is one or more of compatilizer, lubricant, chain extender, end capping agent and coupling agent. These auxiliaries are all known to the person skilled in the art, such as: the compatilizer can adopt polycaprolactone grafted maleic anhydride (PCL-g-MHA); the lubricant is selected from stearic acid, calcium stearate, and epoxidized soybean oil; the chain extender can be selected from styrene-glycidyl methacrylate copolymer; the end-capping reagent can be maleic anhydride, and the end-capping reagent is added to ensure that the polyester does not undergo zipper type thermal decomposition in the processing process; the coupling agent can be selected from silane coupling agent KH 550/KH 570, titanate coupling agent and aluminate coupling agent.
The thickness or the square gram weight of the composite material is not limited by the invention, and the appropriate thickness can be selected by the skilled person according to the application requirements, for example, the thickness can be selected from 50 micrometers to 500 micrometers.
The invention is further illustrated by the following examples:
example 1
The fully-degradable high-barrier composite material is formed by compounding inner-layer biodegradable matrix resin and outer-layer biodegradable matrix resin through double-layer co-extrusion.
The inner biodegradable matrix resin of the embodiment plays a role in blocking, and the mass ratio of the inner biodegradable matrix resin to the outer biodegradable matrix resin is 1.5: 1. each layer is composed of the following components in parts by weight: PBAT 20 parts and PCL 80 parts, wherein the total weight part of PBAT and PCL is 100 parts; 0.5 part of compatilizer, 0.3 part of chain extender and 0.3 part of end capping agent.
The outer-layer biodegradable matrix resin mainly comprises the following components in parts by weight: 20 parts of PBAT and 80 parts of PLA, wherein the total weight part of PBAT and PLA is 100 parts; 5 parts of talcum powder, 0.5 part of compatilizer, 1 part of lubricant, 0.3 part of chain extender, 0.3 part of end-capping agent and 0.1 part of coupling agent.
The composite material of this example was prepared by the following steps:
step 1, respectively drying talcum powder, degradation regulation accelerant, PBAT and PCL (poly (butylene adipate/terephthalate)) at the temperature of 40-50 ℃ for 10-12h and testing the moisture content; then carrying out surface coupling treatment on the talcum powder, wherein the addition amount of the coupling agent is 1-3% of the weight percentage of the talcum powder.
Step 2, blending, stirring and mixing the PBAT, the PCL, the degradation regulation accelerant and the auxiliary agent to obtain an inner-layer biodegradable matrix resin mixture;
mixing the PBAT part, the PLA, the degradation regulation accelerant, the talcum powder and the auxiliary agent, and stirring and mixing the mixture to obtain the outer-layer biodegradable matrix resin mixture.
And 3, respectively putting the inner layer biodegradable matrix resin mixture and the outer layer biodegradable matrix resin mixture mixed in the step 2 into two twin-screw granulators, and heating, melting and extruding to respectively obtain inner layer biodegradable matrix resin particles and outer layer biodegradable matrix resin particles with two different colors.
And 4, respectively placing the inner-layer biodegradable matrix resin particles and the outer-layer biodegradable matrix resin particles prepared in the step 3 in a dehumidifying dryer for drying, wherein the drying temperature is set to be 40-50 ℃, and the drying time is 8-12 h.
And 5, respectively feeding the inner-layer biodegradable matrix resin particles and the outer-layer biodegradable matrix resin particles prepared in the step 4 into feeding barrels of two screw extruders, controlling the flow of the biodegradable matrix resin melt by adopting a metering pump, and performing double-layer co-extrusion casting on the inner-layer biodegradable matrix resin melt and the outer-layer biodegradable matrix resin melt at a die head outlet under the action of a distributor. In the step, the temperature of the screw extruder is set to be 160-190 ℃, and the temperature of the die head is set to be 180-195 ℃.
And 6, carrying out double-layer co-extrusion casting on the biodegradable matrix resin composite melt obtained in the step 5 to form the fully-degradable high-barrier composite material for the flexible package under the action of a casting roller and a rubber compression roller, wherein the thickness of the fully-degradable high-barrier composite material is 214 microns.
In the embodiment, a double-layer co-extrusion compounding process is adopted, and the barrier property of the fully-degradable biological film is improved through a multi-layer composite structure; the inner-layer matrix resin is composed of PBAT and PCL, wherein the PCL is cooperated with the PBAT, the PBAT and the PCL play a role in realizing excellent barrier property, the outer-layer matrix resin is composed of PBAT and PLA, the flexibility of the PLA is enhanced through the PBAT, the PLA also enhances the strength of the PBAT, the synergy promotion effect between the PBAT and the PBAT is fully exerted, the composite material has good full-biodegradation property and excellent barrier property, and is mainly applied to the flexible package application field of shampoo packages and skin cream packages.
Example 2
The composite material of this embodiment is formed by the double-deck coextrusion complex of inlayer biodegradable matrix resin, outer biodegradable matrix resin, wherein, inlayer biodegradable matrix resin plays the effect of separation, and the quality between inlayer biodegradable matrix resin, the outer biodegradable matrix resin than 0.8: 1. each layer is composed of the following components in parts by weight: 80 parts of PBAT and 20 parts of PCL, wherein the total weight part of PBAT and PCL is 100 parts; 1 part of compatilizer, 0.3 part of chain extender and 0.3 part of end capping agent.
The outer-layer biodegradable matrix resin mainly comprises the following components in parts by weight: 80 parts of PBAT and 20 parts of PLA, wherein the total weight part of PBAT and PLA is 100 parts; 15 parts of talcum powder, 1 part of compatilizer, 1.5 parts of lubricant, 0.3 part of chain extender, 0.3 part of end-capping agent and 0.2 part of coupling agent. Then, the double-layer co-extrusion compounding is carried out according to the steps of the embodiment 1 to form the fully degradable high-barrier composite material, and the thickness is 206 microns.
Example 3
Aiming at the problem that the PBAT has a slow degradation rate due to the existence of aromatic PBT chain segments, the degradation regulation accelerant is added into the inner layer biodegradable matrix resin and the outer layer biodegradable matrix resin. The degradation regulation accelerant takes biological carbon with the particle size of 150-200 meshes as a carrier, forms a biological carbon composition by loading nano zinc oxide or/and nano titanium dioxide on the biological carbon, and performs surface coupling coating treatment on the biological carbon composition.
The inner biodegradable matrix resin of the embodiment plays a role in blocking, and the mass ratio of the inner biodegradable matrix resin to the outer biodegradable matrix resin is 1: 1. each layer of the composite material of this example consisted of: the inner-layer biodegradable matrix resin comprises the following components in parts by weight: 40 parts of PBAT, 60 parts of PCL, 5 parts of degradation regulation accelerant and 0.5 part of compatilizer.
The outer-layer biodegradable matrix resin comprises the following components in parts by weight: 40 parts of PBAT, 60 parts of PLA, 5 parts of degradation regulation accelerator, 10 parts of talcum powder, 0.5 part of compatilizer, 1 part of lubricant and 0.2 part of coupling agent. Then, the two layers are co-extruded and compounded to form the fully degradable high barrier composite material with the thickness of 208 microns according to the steps of example 1.
The preparation process of the degradation regulation accelerant comprises the following steps:
step 1, preparing biochar into a solution with the mass concentration of 5% -15% by using deionized water, adding nano zinc oxide or/and nano titanium dioxide under stirring, performing ultrasonic dispersion treatment to form a biochar composition suspension, performing suction filtration on the biochar composition suspension, and drying to obtain the biochar composition.
And 2, taking a silane coupling agent accounting for 1.0-2.5% of the mass of the biochar composition powder, and diluting the silane coupling agent by using absolute ethyl alcohol to ensure that the mass concentration of the silane coupling agent in the absolute ethyl alcohol is 5-10%.
3, putting the biochar composition powder into a high-speed stirrer for stirring, firstly stirring at a low speed, and adding a silane coupling agent/absolute ethyl alcohol mixed solution while stirring; after the mixed solution is poured into the container completely, stirring at high speed for 3-5min, and drying the composition in an oven at 80 deg.C for 6-12 h.
In the embodiment, biochar which has biodegradability and good interface compatibility with matrix resin is used as a carrier framework of the degradation regulation accelerant, the surface of the biochar has rich nano-pore structures and a larger specific surface area, and the pore structures and the specific surface area enable the ecotype biochar and a polymer matrix to form good interface combination effect and obviously enhance the mechanical property of the composite material. The degradation rate of the composite material is improved by the photocatalytic degradation synergistic biodegradation of the degradation regulation accelerant (nano titanium dioxide \ nano zinc oxide).
The biochar of the embodiment enhances the mechanical property and the interface combination effect, also enhances the thermal stability of each layer of blending system, and avoids the thermal decomposition process of the blending system in the processing process.
Example 4
The inner biodegradable matrix resin of the embodiment plays a role in blocking, and the mass ratio of the inner biodegradable matrix resin to the outer biodegradable matrix resin is 1: 1. each layer of the composite material of this example consisted of: the inner-layer biodegradable matrix resin comprises the following components in parts by weight: 70 parts of PBAT, 30 parts of PCL, 8 parts of degradation regulation accelerant and 0.2 part of compatilizer.
The outer-layer biodegradable matrix resin consists of the following components in parts by weight: 80 parts of PBAT, 20 parts of PLA, 8 parts of degradation regulation accelerator, 10 parts of talcum powder, 0.2 part of compatilizer, 1 part of lubricant and 0.2 part of coupling agent. Then, the double-layer co-extrusion compounding is carried out according to the steps of the embodiment 1 to form the fully degradable high-barrier composite material, and the thickness is 210 microns.
The degradation regulation accelerator of the present example is different from example 3 in that the degradation regulation accelerator of the present example is subjected to surface double-layer coating treatment by the following steps: and carrying out outer layer coating treatment by using polybutylene adipate terephthalate, polycaprolactone or polyvinyl alcohol solution, and drying to obtain the degradation regulation accelerant subjected to surface double-layer coating treatment. Wherein the outer coating layer accounts for 6% of the degradation regulation accelerant by mass.
The PBAT solution or PCL solution of this example can be obtained by dissolving PBAT or PCL in a solvent, e.g., dissolving PBAT in dichloromethane under stirring to obtain a PBAT solution of a certain concentration.
After the degradation regulation accelerant is subjected to double-layer coating treatment, the interface binding force and the interface compatibility of each layer of blending system are improved, so that the mechanical property of the blending system is improved.
Comparative example
The fully-degradable composite material of the embodiment comprises the following components in parts by weight: 75 parts of PBAT, 15 parts of PCL, 10 parts of PLA, 5-15 parts of talcum powder and 0.5-10 parts of auxiliary agent. Then, the preparation is carried out according to the following steps:
putting PBAT, PLA and PCL into a vacuum oven, carrying out vacuum drying for 10-12h at 40-50 ℃, uniformly mixing talcum powder subjected to surface coupling treatment, PBAT, PLA, PCL and auxiliaries subjected to drying treatment, then carrying out melt blending by an internal mixer at the blending temperature of 180 ℃, the rotation speed of 40-60r/min and the blending time of 80-15min, and then transferring into a screw extruder to carry out extrusion granulation and drying to obtain the slice of the fully-degradable composite material. The section was cast to obtain a fully degradable film of a monolayer structure having a thickness of 202 μm.
Performance detection
The test method comprises the following steps:
tensile strength/elongation at break: testing according to GBT 1040.3-2006 standard.
Barrier properties: the oxygen transmission was tested in accordance with GB/T19789-.
And (3) testing the degradation performance:
(1) physical and chemical properties of soil: the pH value of the soil is 6.42, the organic matter content is 32.4g/kg, the total nitrogen content is 2.88g/kg, the total phosphorus content is 3.51 g/kg, the total potassium content is 7.83 g/kg, the alkaline hydrolysis nitrogen content is 98.65mg/kg, the quick-acting phosphorus content is 104.52mg/kg, and the quick-acting potassium content is 421.45 mg/kg. Collecting soil sample, air drying, and grinding with 5mm sieve.
(2) The method comprises the following steps: first, 3 samples of the sample to be tested in each example were weighed and then filled in 3 filling boxes, respectively, and taken out after 30 days. The test sample is naturally exposed for 20 days according to GB/T17603-1998, and then is buried in a landfill box again for 30 days and then taken out. The results were averaged over 3 samples.
(3) The degradation rate calculation method comprises the following steps: the weight loss rate of the sample is used for representing the degradation rate, and the calculation formula is as follows: degradation rate (%) = (initial weight before degradation-weight after degradation)/initial weight before degradation × 100.
Properties of fully degradable high-barrier composite material
| Test items | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Tensile strength, Mpa | 14.6 | 11.8 | 13.2 | 12.6 | 9.8 |
| Elongation at break,% | 156 | 178 | 164 | 170 | 126 |
| Oxygen transmission capacity, cm3 (m2.24h.0.1MPa) | 0.15 | 0.28 | 0.22 | 0.19 | 0.78 |
| Water vapor transmission amount, g (m)2.24h) | 0.33 | 0.42 | 0.32 | 0.36 | 1.04 |
| A degradation rate% | 57.45 | 36.97 | 68.72 | 63.22 | 51.24 |
As can be seen from the above table, the components of the fully-degradable composite material prepared by the invention can form good interface bonding effect, the mechanical property of the composite material is enhanced, the composite material has good barrier property, the biodegradation rate of the fully-degradable composite material can be effectively promoted through the photocatalysis effect of the degradation regulation accelerant (nano titanium dioxide \ nano zinc oxide), and the fully-degradable composite material can be widely applied to the field of flexible packages such as toothpaste packages, cosmetic packages and the like.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (1)
1. The utility model provides a flexible package is with high separation combined material of full degradation, combined material is formed by the double-deck coextrusion complex of inlayer biodegradable matrix resin, outer biodegradable matrix resin which characterized in that:
the inner-layer biodegradable matrix resin mainly comprises the following components in parts by weight: 40 parts of PBAT, 60 parts of PCL, 0.5 part of compatilizer and 5 parts of degradation regulation accelerator;
the outer-layer biodegradable matrix resin mainly comprises the following components: 40 parts of PBAT, 60 parts of PLA, 10 parts of talcum powder, 0.5 part of compatilizer, 1 part of lubricant, 0.2 part of coupling agent and 5 parts of degradation regulation accelerator;
the degradation regulation accelerant takes biochar as a carrier, forms a biochar composition by loading nano zinc oxide or/and nano titanium dioxide on the biochar, and carries out surface coating treatment on the biochar composition, and the preparation method comprises the following steps:
step 1, preparing biochar into a solution with the mass concentration of 5% -15% by using deionized water, adding nano zinc oxide or/and nano titanium dioxide under stirring, performing ultrasonic dispersion treatment to form a biochar composition suspension, performing suction filtration and drying on the biochar composition suspension to obtain a biochar composition;
step 2, taking a silane coupling agent accounting for 1.0-2.5% of the mass of the biochar composition powder, and diluting the silane coupling agent by using absolute ethyl alcohol to ensure that the mass concentration of the silane coupling agent in the absolute ethyl alcohol is 5-10%;
3, putting the biochar composition powder into a high-speed stirrer for stirring, firstly stirring at a low speed, and adding a silane coupling agent/absolute ethyl alcohol mixed solution while stirring; after the mixed solution is completely poured, stirring at a high speed for 3-5min, and then drying the composition in an oven at 80 ℃ for 6-12 h;
the tensile strength of the fully-degradable high-barrier composite material is 13.2Mpa, the elongation at break is 164 percent, and the oxygen transmission capacity is 0.22cm3/(m224h.0.1MPa) and a water vapor transmission of 0.32 g/(m)224h) and the degradation rate was 68.72%.
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