CN114957930A - Biodegradable material product and production process thereof - Google Patents
Biodegradable material product and production process thereof Download PDFInfo
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- CN114957930A CN114957930A CN202210511593.2A CN202210511593A CN114957930A CN 114957930 A CN114957930 A CN 114957930A CN 202210511593 A CN202210511593 A CN 202210511593A CN 114957930 A CN114957930 A CN 114957930A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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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 biodegradable material product and a production process thereof, and the biodegradable material comprises the following components of, by weight, 50-60 parts of PBAT, 15-25 parts of PLA, 1-10 parts of PPC, 1-10 parts of plant fiber, 0.5-2 parts of modified chitosan, 0.1-1 part of compatibilizer, 0.1-1 part of nucleating agent, 0.5-5 parts of modified hollow glass bead, 1-3 parts of organic modified montmorillonite, 0-10 parts of inorganic filler and 0.5-1 part of light stabilizer. The degradation material takes PBAT as a main raw material, PLA and plant fibers are added to increase the mechanical strength, an auxiliary agent is supplemented to improve the interface compatibility, the product uniformity is good, the hollow glass beads and the inorganic filler accelerate the material degradation, and chitosan provides short-term antibacterial performance. The material is produced by a multi-step method melt blending process, so that good compatibility among different plastics is ensured, and the product has stable specific functions. The degradable material has the advantages of excellent mechanical property, certain antibacterial property, capability of realizing rapid biodegradation and the like, and has wide application prospect in the field of packaging plastics.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a completely biodegradable high polymer material with excellent mechanical property and a production process thereof, and specifically relates to a biodegradable material which is prepared by compounding various biodegradable resins and additives and performing melt blending by a multi-step method and a production process thereof.
Background
Plastic packaging products are the most common packaging products in human social life, appear in various life scenes, such as plastic shopping bags, food packaging bags, beverage bottles, disposable tableware and the like, according to statistics, 5000 hundred million plastic bags are consumed all the year round at present, most of the plastic bags are made of Polyethylene (PE) serving as a raw material, and are difficult to decompose and recycle in a natural environment, so that huge environmental pollution is caused. In recent years, governments in China and various regions continue to take a series of measures such as 'plastic limit order', 'plastic limit order' and the like, biodegradable plastics are further popularized and applied, and the use of biodegradable plastic products to replace non-degradable plastics is one of the most effective ways for treating plastic pollution and protecting ecological environment at present.
The biodegradable plastic is a small molecule substance which can be decomposed into water, carbon dioxide or methane and the like under the action of microorganisms and is nontoxic and harmless. Biodegradable plastics can generally be divided into two main categories: 1 petroleum-based plastics such as polybutylene adipate/terephthalate (PBAT), polybutylene succinate (PBS), polyglycolic acid (PGA), polypropylene carbonate (PPC), and the like; 2 bio-based plastics such as polylactic acid (PLA), Polyhydroxyalkanoate (PHA), etc. The materials have different properties, such as PBAT, belong to thermoplastic plastics, have better ductility and elongation at break, better heat resistance and impact property, but have low tensile strength and easy tearing, and are main raw materials for manufacturing biodegradable plastic shopping bags; PLA and PBAT have the properties just opposite to each other, are obtained by polymerizing lactic acid serving as a raw material, have high tensile strength and transparency, but have poor toughness and crisp texture, and are mainly used for manufacturing straws, plastic knife forks, spoons and the like; PPC is synthesized by taking carbon dioxide and propylene oxide as raw materials, has better oxygen barrier property and can be used as a barrier layer for food packaging, however, the amorphous aggregation structure and the lower glass transition temperature of the PPC cause the PPC to have poor thermal property, mechanical property and dimensional stability, so that the PPC is difficult to be singly used as master batch to process and manufacture packaging products.
Although the biodegradable plastic is environment-friendly, the biodegradable plastic has some problems which need to be solved in the practical application of the packaging industry. For example, a plastic shopping bag produced by using PBAT as a main raw material is easy to puncture and deform according to the reflection of consumers, can be used for almost 1-2 times, and is expensive. Starch is added to a part of plastic bags, obvious peculiar smell can exist, enterprises can reduce cost, and more inorganic fillers are added, so that dust which is easy to fall off is arranged on the surfaces of the bags, and the bags cannot be in direct contact with food. In fact, the existing biodegradable plastic bag generally needs 60-180 days under the specific aerobic composting condition in a laboratory to realize complete degradation, and needs 1-2 years under the natural condition, if the biodegradable plastic bag is taken as a disposable tool, the biodegradable plastic bag runs counter to the original purpose of protecting the environment, and therefore, the key point is to research materials which have excellent mechanical properties, are durable, can be rapidly degraded and meet the market requirements.
Disclosure of Invention
The invention aims to provide a biodegradable material product and a production process thereof. The invention adopts various biodegradable resins and additives to compound, and adopts a multi-step method to melt and blend the produced biodegradable materials, and the products such as plastic shopping bags and the like prepared by the obtained high polymer materials have the advantages of firmness, durability, high strength, rapid degradation and the like.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a biodegradable material product which comprises the following components of (by weight parts) PBAT 50-60 parts, PLA 15-25 parts, PPC 1-10 parts, plant fiber 1-10 parts, modified chitosan 0.5-2 parts, a compatibilizer 0.1-1 part, a nucleating agent 0.1-1 part, modified hollow glass beads 0.5-5 parts, organic modified montmorillonite 1-3 parts, inorganic filler 0-10 parts and a light stabilizer 0.5-1 part.
Preferably, PBAT is poly adipic acid/butylene terephthalate with the number average molecular weight of 20000-150000, PLA is polylactic acid with the number average molecular weight of 30000-250000, and PPC is polypropylene carbonate with the number average molecular weight of 10000-50000.
Preferably, the plant fiber is coconut shell fiber, bamboo powder and rice hull, and the mass ratio of the coconut shell fiber to the bamboo powder to the rice hull is 1:1: 2.
Preferably, the modified chitosan is quaternized chitosan prepared by reacting chitosan with halogenated hydrocarbon, and the preparation method comprises the following steps:
s01, fully and uniformly mixing 50-150 g of chitosan, 100-200 mL of methanol and 100-200 mL of ethanol at normal temperature, pouring into a three-neck flask, heating to 40-55 ℃, and reacting at constant temperature for 1-2 h to obtain a solution a;
s02, adding 200-300 mLC of the solution A 4 H 9 Br and 100-250 mLC 3 H 7 And (3) carrying out Br reflux reaction for 6-24 h, washing and carrying out vacuum drying to obtain the modified chitosan.
Preferably, the compatibilizer is ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA) and tetrabutyl titanate (TBT) in a mass ratio of 1: 1.
Preferably, the nucleating agent is sebacic acid dibenzoyl hydrazine (TMC 300) or tert-butyl calixarene (TBC 8-d), and more preferably, the nucleating agent is sebacic acid dibenzoyl hydrazine.
Preferably, the modified hollow glass microspheres are prepared by etching common hollow glass microspheres by a sodium hydroxide solution and modifying by a silane coupling agent KH550, and the particle size is 10-100 μm, and the preparation method comprises the following steps:
s10, weighing 250-350 g of hollow glass microspheres in enough NaOH solution (0.5 mol/L), reacting for 4-6 hours under the conditions of constant temperature of 50-60 ℃ and magnetic stirring, washing with deionized water after the reaction is finished until the filtrate is neutral, and drying in vacuum for 1-2 hours at 100-120 ℃ for later use;
and S20, adding 5-8 gKH550 silane coupling agent into the treated hollow glass beads, placing the mixture into a high-speed mixer for dry mixing, and reacting for 0.5-1 h to obtain the modified hollow glass beads.
Preferably, the inorganic filler is micron calcium carbonate and talcum powder, and the mass ratio of the micron calcium carbonate to the talcum powder is 1: 1.
preferably, the light stabilizer is a hindered amine light stabilizer HS-944.
Optionally, the biodegradable material provided by the invention comprises the following components in percentage by mass: PBAT 50-60 parts, PLA 15-18 parts, PPC 6-10 parts, plant fiber 1-2 parts, modified chitosan 1.5-2 parts, compatibilizer 0.1-1 part, nucleating agent 0.1-1 part, modified hollow glass bead 0.5-1 part, organic modified montmorillonite 1-3 parts, inorganic filler 0-2 parts and light stabilizer 0.5-1 part.
Optionally, the biodegradable material provided by the invention comprises the following components in percentage by mass: PBAT56 parts, PLA18 parts, PPC4 parts, plant fiber 8 parts, modified chitosan 1 part, compatibilizer 0.5 part, nucleating agent 0.5 part, modified hollow glass bead 3 parts, organic modified montmorillonite 2 parts, inorganic filler 7 parts, and light stabilizer 0.5 part.
The invention also provides a production process of the biodegradable material, which comprises the following steps:
s1, preparing a first-grade material:
s11, taking the hollow glass beads and a NaOH solution (0.5 mol/L), and reacting for 4-6 hours at a constant temperature of 50-60 ℃ under the condition of magnetic stirring; after the washing, washing the mixture with deionized water to be neutral, and drying the mixture for 1 to 2 hours in vacuum at the temperature of between 100 and 120 ℃; adding a silane coupling agent KH550, and placing the mixture in a high-speed mixer for reaction for 0.5-1 h to obtain modified hollow glass microspheres for later use;
s12, uniformly mixing the PBAT and the modified hollow glass beads in a dry mode by using a high-speed mixer, and then adding the mixture into an internal mixer for melting and mixing, wherein the reaction temperature is 180-200 ℃, the rotation speed is 50-60 r/min, and the reaction time is 1-2 hours, so as to obtain a first-grade material;
s2, preparing a secondary material: preparing a first-grade material, organic modified montmorillonite, plant fiber, PPC and EMA-GMA, carrying out melting and banburying by adopting a multi-feed-port double-screw extruder, carrying out reaction at the temperature of 200-240 ℃ and at the screw rotation speed of 100-150 r/min, feeding the first-grade material, the organic modified montmorillonite and the plant fiber at a main port, feeding the PPC and the EMA-GMA at side ports, and carrying out granulation and cooling after the reaction is finished to obtain a second-grade material;
s3, preparing a third-grade material: preparing PLA, a nucleating agent, TBT and a secondary material, melting and banburying by adopting a multi-feed-port double-screw extruder, feeding the PLA and the nucleating agent at the reaction temperature of 160-190 ℃ and the screw rotation speed of 100-150 r/min, feeding the PLA and the nucleating agent at a main port, feeding the TBT and the secondary material at a side port, and granulating and cooling after the reaction is finished to obtain a tertiary material;
s4, preparing the biodegradable material:
s41, fully and uniformly mixing chitosan, methanol and ethanol at normal temperature, pouring into a three-neck flask, heating to 40-55 ℃, keeping the temperature constant, and adding C 4 H 9 Br and C 3 H 7 Performing Br reflux reaction for 6-24 h, washing and drying to obtain modified chitosan;
and S42, preparing the three-stage material, the modified chitosan, the inorganic filler and the light stabilizer, performing melt mixing by using a single-screw extruder, performing reaction at the temperature of 160-180 ℃, performing screw rotation at the speed of 500r/min, and performing granulation and cooling after the reaction is finished to obtain the biodegradable material.
In the production process provided by the invention, S1 adopts NaOH solution to etch the hollow glass beads, so that the smooth surfaces of the glass beads become rough and are easy to react with silane coupling agent, and the hollow glass beads and PBAT after two processes have good compatibility. The hollow glass beads are inorganic materials, the component is silicon dioxide, if unmodified glass beads are adopted, the hollow glass beads cannot form bonds with PBAT resin, the acting force is weak, the interface compatibility is poor, and the mechanical property of the resin is reduced after the hollow glass beads are mixed. In addition, the hollow glass beads are of hollow structures inside, the situation that the beads are broken in the subsequent processing process inevitably occurs, so that more micropores are reserved inside the material, microorganisms are favorably and quickly attached to the material, the degradation speed is accelerated, in the step S4, the inorganic filler is mixed, the purpose is also achieved, and along with the decomposition of the plastic bag, the inorganic filler falls off, and more attachment spaces are provided for the microorganisms. In S2, the blending of PPC and PBAT is to give the material a certain oxygen barrier property, and can be used for simple packaging of short-term food; in addition, under the action of affinity, the organic modified montmorillonite is more prone to be distributed in PLA and between phase interfaces of PLA and PBAT, the organic modified montmorillonite is blended with the PLA before the PBAT, and then the organic modified montmorillonite is migrated, so that the interface compatibility of the two plastics is improved. In S3, the main ports of the PLA and the nucleating agent are blanked firstly, so that the crystallization rate of the PLA is accelerated, the uneven crystallization condition is improved, and the heat resistance of the PLA is improved. S4, adding modified chitosan to provide certain antibacterial property for the material, the product can be used for food packaging, and meanwhile, in order not to influence the activity of later-stage degradation microorganisms, the process greatly accelerates the rotation speed of the screw, shortens the reaction time, limits the effective content and stability of chitosan, and meanwhile, enables the product to have antibacterial effect in a short period. In addition, under the condition of better degradation performance of the organic compost, a light stabilizer is added, so that the durability of the plastic bag can be effectively improved, and the aim of real environmental protection is fulfilled.
Preferably, the extruder adopted during preparation comprises a control machine table, an extruder body, a feeding hopper, a plurality of groups of heating rings, a plurality of groups of sliding blocks, a plurality of groups of locking blocks, a plurality of groups of sliding plates, a plurality of groups of top posts, a plurality of groups of second springs and a plurality of groups of pressing blocks, wherein the extruder body is arranged at the top end of the control machine table, the extruder body is electrically connected with the control machine table, the bottom end of the feeding hopper is communicated with the extruder body, the plurality of groups of heating rings are respectively sleeved on the extruder body, the front side of each group of heating rings is provided with a butt joint plate and a butt joint groove, the butt joint plate can be butted with the butt joint groove, the two ends of the butt joint plate are respectively provided with a hole cavity, each group of hole cavities is internally provided with a first spring, the sliding blocks are arranged in the hole cavities through the first springs, the left and right ends of the butt joint plate are respectively provided with first sliding holes communicated with the hole, the locking blocks are fixedly connected with the sliding blocks, two groups of locking holes are symmetrically arranged in the heating rings, and are respectively communicated with the butt joint grooves, two sets of slide plates are respectively slidably mounted in two sets of lock holes, second slide holes are formed in the left end and the right end of the heating ring, the two sets of second slide holes are respectively communicated with the two sets of lock holes, two sets of support posts respectively slide through the two sets of second slide holes and are fixedly connected with the two sets of slide plates, the second spring sleeves are sleeved on the support posts, the pressing blocks are fixedly connected with the support posts, and the two ends of the second spring are respectively fixedly connected with the heating ring and the pressing blocks.
In conclusion, the invention has the following beneficial effects:
1. PBAT is used as a main raw material, PLA, plant fiber and various auxiliaries are added, the mechanical property of the PBAT is comprehensively improved, and a light stabilizer is added, so that a plastic product produced by the PBAT is more firm and durable;
2. PPC is added to improve the oxygen barrier property of the material; the modified hollow glass beads are added, so that more attachment space is provided for microorganisms after the modified hollow glass beads are broken or fall off, the degradation process is accelerated, and the material performance is not influenced; the modified chitosan is added, so that short-term antibacterial property can be provided;
3. the product is produced by a multi-step method melt blending process, so that good compatibility among different plastics is ensured, the product has stable specific functions, and complete biodegradation can be realized;
4. when the heating ring is installed, firstly, the heating ring is sleeved on the extruder body, then one hand of a worker extrudes two groups of locking blocks inwards to enable the two groups of locking blocks to slide into the hole cavity, two groups of first springs contract, then the butt joint plate slides downwards into the butt joint groove, two groups of locking blocks are loosened, when the butt joint plate slides to the bottom of the butt joint groove, the two groups of locking blocks respectively penetrate through the two groups of first sliding holes to enter the two groups of locking holes under the action of the two groups of first springs and outwards push against the two groups of sliding plates to enable the two groups of top posts to move outwards to enable the second springs to stretch, thereby the butt joint plate and the heating ring are clamped and fixed, when the heating ring is disassembled, one hand of the worker extrudes the two groups of pressing blocks inwards to enable the two groups of top posts to push against the two groups of sliding plates inwards, the two groups of second springs contract to push the two groups of locking blocks back into the two groups of hole cavities to enable the locking blocks to leave the locking holes, the butt joint plate is pulled upwards at the moment, the butt joint plate can be separated from the butt joint groove, and therefore the heating ring can be detached.
Drawings
FIG. 1 is a graph comparing the relative biodegradation rates of materials in the presence of oxygen;
FIG. 2 is a schematic front view of the extruder for producing biodegradable material according to the present invention;
FIG. 3 is a schematic view of a front view of the connection of the docking plate and the heating collar;
FIG. 4 is a schematic cross-sectional front view of a heating ring;
FIG. 5 is a schematic diagram of a right side cross-sectional configuration of the heating coil;
in the drawings, the reference numbers: 1. controlling the machine; 2. an extruder body; 3. feeding a hopper; 4. heating a ring; 5. a butt plate; 6. a butt joint groove; 7. a bore; 8. a first spring; 9. a slider; 10. a first slide hole; 11. a locking block; 12. a lock hole; 13. a slide plate; 14. a second slide hole; 15. a top pillar; 16. a second spring; 17. briquetting; 18. a non-slip mat; 19. a fastening pad; 20. adjusting the ground feet; 21. a nut; 22. a sliding sleeve; 23. a rubber pad; 24. heat dissipation holes; 25. and (4) anti-skid lines.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
For avoiding redundancy, the following examples are provided by conventional methods unless otherwise indicated. Ethylene-methyl acrylate-glycidyl methacrylate, Lotader AX8900, arkema, france; sebacic acid dibenzoyl hydrazine, TMC300, chemical research institute of Shanxi province; chitosan, national drug group chemical agents limited; hollow glass beads, K20, 3M company, hindered amine light stabilizer HS-944, fertilizer-compounding Tianjian chemical company Limited.
Example 1
The embodiment provides a biodegradable material product and a production process thereof, and the material composition is as follows:
PBAT60 parts, PLA15 parts, PPC4 parts, plant fiber 8 parts, modified chitosan 1 part, compatibilizer 0.5 part, nucleating agent 0.5 part, modified hollow glass bead 3 parts, organic modified montmorillonite 2 parts, inorganic filler 7 parts, and light stabilizer 0.5 part.
Preparing a sample according to the material composition, which specifically comprises the following steps:
weighing 0.3kg of hollow glass microspheres, completely immersing in an excessive NaOH solution (0.5 mol/L), and reacting for 6 hours at a constant temperature of 55 ℃ under the condition of magnetic stirring; washing the mixture to be neutral by deionized water after the reaction is finished, and drying the mixture for 1 hour in vacuum at 120 ℃; placing the hollow glass beads and 6.1g of silane coupling agent KH550 in a high-speed mixer for reaction for 0.5h to obtain modified hollow glass microspheres for later use.
And (3) uniformly mixing 6.0kg of PBAT and the modified hollow glass beads in a dry way by using a high-speed mixer, and then adding the mixture into an internal mixer for melting and mixing, wherein the reaction temperature is 200 ℃, the rotating speed is 55r/min, and the reaction time is 1.5h, so as to obtain a first-grade material.
Preparing a first-grade material, 0.2kg of organic modified montmorillonite, 0.8kg of plant fiber, 0.4kg of PPC and 25g of EMA-GMA, carrying out melt banburying by adopting a multi-feed-port double-screw extruder, wherein the heating temperature of the extruder is as follows from a main material port to a machine head: feeding the primary material, the organic modified montmorillonite and the plant fiber at a main port and feeding the PPC and the EMA-GMA at a side port at 200 ℃, 240 ℃ and 220 ℃ at a screw rotating speed of 130r/min, and granulating and cooling after the reaction to obtain a secondary material;
0.15kg of PLA, 50g of TMC300, 25g of TBT and a secondary material are mixed and melted by a multi-feed-port double-screw extruder, and the heating temperature of the extruder is as follows from the temperature of a main material port to the temperature of a machine head: screw rotating speed of 130r/min at 160 ℃, 180 ℃, 190 ℃ and 180 ℃, feeding PLA and TMC300 through main ports, feeding TBT and secondary material through side ports, and granulating and cooling after reaction to obtain a tertiary material;
mixing 100g chitosan, 150mL methanol and 150mL ethanol at room temperature, pouring into three-neck flask, heating to 55 deg.C, maintaining constant temperature, adding 200mLC 4 H 9 Br and 150mLC 3 H 7 Br reflux reaction for 12h, washing and drying to obtain modified chitosan;
and (3) preparing the three-stage material, the modified chitosan, 0.7kg of inorganic filler and 50gHS-944, carrying out melt mixing by adopting a single-screw extruder, carrying out reaction at the temperature of 180 ℃ and at the screw rotation speed of 500r/min, and carrying out granulation cooling after the reaction is finished to obtain the biodegradable material.
As shown in fig. 2 to 5, the extruder for producing biodegradable material products comprises a control machine table 1, an extruder body 2, a feeding hopper 3, a plurality of groups of heating rings 4, a plurality of groups of sliding blocks 9, a plurality of groups of locking blocks 11, a plurality of groups of sliding plates 13, a plurality of groups of top pillars 15, a plurality of groups of second springs 16 and a plurality of groups of pressing blocks 17, wherein the extruder body 2 is installed at the top end of the control machine table 1, the extruder body 2 is electrically connected with the control machine table 1, the bottom end of the feeding hopper 3 is communicated with the extruder body 2, the plurality of groups of heating rings 4 are respectively sleeved on the extruder body 2, the front side of each group of heating rings 4 is provided with a butt joint plate 5 and a butt joint groove 6, the butt joint plate 5 can be in butt joint with the butt joint groove 6, both ends of the butt joint plate 5 are provided with a cavity 7, a first spring 8 is arranged in each group of cavity 7, the sliding blocks 9 are slidably installed in the cavity 7 through the first springs 8, both left and right ends of the butt joint plate 5 are provided with first sliding holes 10 communicated with the cavity 7, the locking block 11 is fixedly connected with the sliding block 9, two groups of locking holes 12 are symmetrically arranged in the heating ring 4, the two groups of locking holes 12 are respectively communicated with the butt joint groove 6, two groups of sliding plates 13 are respectively and slidably arranged in the two groups of locking holes 12, the left end and the right end of the heating ring 4 are respectively provided with a second sliding hole 14, the two groups of second sliding holes 14 are respectively communicated with the two groups of locking holes 12, two groups of top posts 15 respectively slide through the two groups of second sliding holes 14 and are fixedly connected with the two groups of sliding plates 13, a second spring 16 is sleeved on the top posts 15, a pressing block 17 is fixedly connected with the top posts 15, and two ends of the second spring 16 are respectively and fixedly connected with the heating ring 4 and the pressing block 17; when the heating ring 4 is installed, firstly, the heating ring 4 is sleeved on the extruder body 2, then one hand of a worker extrudes two groups of locking blocks 11 inwards to enable the two groups of locking blocks 11 to slide into the hole cavity 7, two groups of first springs 8 are contracted, then the butt joint plate 5 slides downwards into the butt joint groove 6, at the moment, the two groups of locking blocks 11 are loosened, when the butt joint plate 5 slides to the bottom of the butt joint groove 6, the two groups of locking blocks 11 respectively penetrate through the two groups of first sliding holes 10 to enter the two groups of lock holes 12 under the action of the two groups of first springs 8, and outwards push the two groups of sliding plates 13 to enable the two groups of top posts 15 to move outwards, the second springs 16 are stretched to enable the butt joint plate 5 and the heating ring 4 to be clamped and fixed, when the heating ring 4 is disassembled, one hand of the worker extrudes two groups of pressing blocks 17 inwards to enable the two groups of top posts 15 to push the two groups of sliding plates 13 inwards, and the two groups of second springs 16 are contracted, two sets of locking pieces 11 are pushed back to two sets of pore cavities 7, so that the locking pieces 11 leave the lock holes 12, the butt joint plate 5 is pulled upwards at the moment, the butt joint plate 5 and the butt joint groove 6 can be separated, and the heating ring 4 is detached, so that the convenience is improved, and the heating ring 4 is convenient to disassemble and assemble.
A plurality of groups of anti-skid pads 18 are arranged on the inner wall of each group of heating rings 4; through setting up slipmat 18, can increase the friction of heating collar 4, prevent that heating collar 4 from rotating on extruder body 2, promote stability. The extruder also comprises a plurality of groups of fastening pads 19, and the plurality of groups of fastening pads 19 are respectively and fixedly arranged on the plurality of groups of heating rings 4; by providing the fastening pad 19, the fastening of the installation of the heating ring 4 can be enhanced. The extruder further comprises four groups of adjusting feet 20 and four groups of nuts 21, the four groups of adjusting feet 20 are respectively screwed at the bottom end of the control machine table 1, the four groups of nuts 21 are respectively screwed on the four groups of adjusting feet 20, and the four groups of adjusting feet 20 are tightly attached to the bottom end of the control machine table 1; not hard up nut 21 rotates regulation lower margin 20, is convenient for adjust the height and the level of control board 1, screws nut 21, can prevent to adjust lower margin 20 and rotate again, improves stability.
The extruder further comprises a plurality of groups of sliding sleeves 22, and the plurality of groups of sliding sleeves 22 are respectively and fixedly installed in the plurality of groups of first sliding holes 10 and the plurality of groups of second sliding holes 14; through setting up sliding sleeve 22, can strengthen the gliding smoothness nature of locking piece 11 and fore-set 15 respectively, prevent the bite. Four groups of rubber pads 23 are respectively and fixedly arranged at the bottom ends of the four groups of adjusting feet 20; through setting up rubber pad 23, can increase the friction of adjusting lower margin 20, prevent to adjust lower margin 20 and slide, improve the stability of control board 1. The front end of the control machine table 1 is provided with a plurality of groups of heat dissipation holes 24; through setting up louvre 24, be convenient for control the inside operation heat dissipation of board 1, improve stability. The circumferential surface of each group of nuts 21 is provided with anti-skid grains 25; by providing the anti-slip threads 25, the friction of the nut 21 can be increased, facilitating the rotation of the nut 21.
The invention relates to an extruder for producing biodegradable material products, which works, when a heating ring 4 is installed, firstly the heating ring 4 is sleeved on an extruder body 2, then one hand of a worker presses two groups of locking blocks 11 inwards to enable the two groups of locking blocks 11 to slide into a hole cavity 7 to enable two groups of first springs 8 to contract, then a butt joint plate 5 slides downwards into a butt joint groove 6 to loosen the two groups of locking blocks 11, when the butt joint plate 5 slides to the bottom of the butt joint groove 6, the two groups of locking blocks 11 respectively pass through two groups of first sliding holes 10 to enter two groups of locking holes 12 under the action of the two groups of first springs 8 and push outwards two groups of sliding plates 13 to enable two groups of ejection columns 15 to move outwards to enable a second spring 16 to stretch, so that the butt joint plate 5 and the heating ring 4 are tightly clamped and fixed, when the heating ring 4 is disassembled, one hand of the worker presses two groups of pressing blocks 17 inwards, two groups of jack posts 15 push two groups of sliding plates 13 inwards, two groups of second springs 16 contract to push two groups of locking blocks 11 back to two groups of hole cavities 7, the locking blocks 11 leave the lock holes 12, the butt joint plate 5 is pulled upwards at the moment, the butt joint plate 5 and the butt joint groove 6 can be separated, so that the heating ring 4 can be disassembled, the anti-slip pad 18 can increase the friction of the heating ring 4, the heating ring 4 is prevented from rotating on the extruder body 2, the stability is improved, the fastening pad 19 can enhance the installation tightness of the heating ring 4, the nuts 21 are loosened, the anchor feet 20 are rotatably adjusted, the height and the level of the machine table 1 can be conveniently adjusted, the nuts 21 are screwed to prevent the anchor feet 20 from rotating again, the stability is improved, the sliding sleeve 22 can respectively enhance the sliding performance of the locking blocks 11 and the jack posts 15 and prevent jamming, the rubber pad 23 can increase the friction of the anchor feet 20 and prevent the anchor feet 20 from sliding, and improve the stability of the machine table 1, the heat dissipation holes 24 are convenient for controlling the heat dissipation of the internal operation of the machine table 1, the stability is improved, the anti-slip threads 25 can increase the friction of the nut 21, and the nut 21 is convenient to rotate.
Example 2
The embodiment provides a biodegradable material product and a production process thereof, and the material composition is as follows:
PBAT56 parts, PLA18 parts, PPC4 parts, plant fiber 8 parts, modified chitosan 1 part, compatibilizer 0.5 part, nucleating agent 0.5 part, modified hollow glass bead 3 parts, organic modified montmorillonite 2 parts, inorganic filler 7 parts, and light stabilizer 0.5 part.
The production process of the degradable material in this example was the same as in example 1.
Example 3
The embodiment provides a biodegradable material product and a production process thereof, and the material composition is as follows:
PBAT50 parts, PLA25 parts, PPC4 parts, plant fiber 10 parts, modified chitosan 1 part, compatibilizer 0.5 part, nucleating agent 0.5 part, modified hollow glass bead 3 parts, organic modified montmorillonite 2 parts, inorganic filler 7 parts, and light stabilizer 0.5 part.
The production process of the degradable material in this example was the same as in example 1.
Example 4
The embodiment provides a biodegradable material product and a production process thereof, and the material composition is as follows:
PBAT56 parts, PLA18 parts, PPC10 parts, plant fiber 1 part, modified chitosan 2 parts, compatibilizer 0.5 part, nucleating agent 0.5 part, modified hollow glass bead 0.5 part, organic modified montmorillonite 2 parts, inorganic filler 0 part, and light stabilizer 0.5 part.
The production process of the degradable material in this example was the same as in example 1.
Example 5
In this example, the material ratio and production process of the degradable material were the same as those of example 1, and TBC8-d was used as the nucleating agent.
Example 6
The embodiment provides a biodegradable material product and a production process thereof, wherein the product comprises the following materials:
PBAT56 parts, PLA18 parts, PPC4 parts, 8 parts of plant fibers, 0.5 part of modified chitosan, 0.5 part of compatibilizer, 0.5 part of nucleating agent, 0.5 part of modified hollow glass beads, 1 part of organic modified montmorillonite, 0 part of inorganic filler and 1.0 part of light stabilizer.
The production process of the degradable material in this example was the same as in example 1.
Example 7
The embodiment provides a biodegradable material product and a production process thereof, and the material composition is as follows:
PBAT56 parts, PLA18 parts, PPC4 parts, plant fiber 8 parts, modified chitosan 1.0 part, compatibilizer 0.5 part, nucleating agent 0.5 part, modified hollow glass bead 3 parts, organic modified montmorillonite 3 parts, inorganic filler 7 parts, and light stabilizer 0.8 part.
In the production process of the degradable material in this embodiment, the chitosan modification process is as follows: mixing 50g chitosan, 200mL methanol and 200mL ethanol at room temperature, pouring into three-neck flask, heating to 40 deg.C, maintaining the temperature, adding 200mLC 4 H 9 Br and 150mLC 3 H 7 Br is refluxed and reacted for 6h, and the modified chitosan is obtained after washing and drying, and the rest steps are the same as the example 1.
Example 8
The embodiment provides a biodegradable material product and a production process thereof, and the material composition is as follows:
PBAT56 parts, PLA18 parts, PPC4 parts, plant fiber 8 parts, modified chitosan 1.0 part, compatibilizer 0.5 part, nucleating agent 0.5 part, modified hollow glass bead 3 parts, organic modified montmorillonite 2 parts, inorganic filler 7 parts, and light stabilizer 0.8 part.
In the production process of the degradable material in this embodiment, the chitosan modification process is as follows: mixing 150g chitosan, 100mL methanol and 100mL ethanol at room temperature, pouring into three-neck flask, heating to 55 deg.C, keeping constant temperature, adding 300mLC 4 H 9 Br and 100mLC 3 H 7 Br is refluxed and reacted for 24 hours, and the modified chitosan is obtained after washing and drying, and the rest steps are the same as the example 1.
Comparative example 1
The comparative example had the following composition:
PBAT56 parts, PLA18 parts, PPC4 parts, plant fiber 0 part, modified chitosan 1 part, compatibilizer 0.5 part, nucleating agent 0.5 part, modified hollow glass bead 3 parts, organic modified montmorillonite 2 parts, inorganic filler 7 parts, and light stabilizer 0.5 part.
The production process of the degradable material in this comparative example was the same as in example 1.
Comparative example 2
The comparative example had the following composition:
PBAT56 parts, PLA18 parts, PPC4 parts, plant fiber 8 parts, modified chitosan 1 part, compatibilizer 0.5 part, nucleating agent 0.5 part, modified hollow glass bead 0 part, organic modified montmorillonite 2 parts, inorganic filler 0 part, and light stabilizer 0.5 part.
The production process of the degradable material in this example was the same as in example 1.
Comparative example 3
In the comparative example, the material ratio of the degradable material is the same as that in example 2, the modification process of the hollow glass beads and the chitosan is the same as that in example 1, all the materials are melted and blended by adopting a one-pot method to prepare the degradable material, and an internal mixer process is adopted, wherein the reaction temperature is 240 ℃, the rotation speed is 100r/min, and the reaction time is 2 h.
Comparative example 4
The production process of the degradable material in this comparative example was the same as in example 1. The material proportion adopts common chitosan, and the rest components are the same as the components in the embodiment 1.
(1) Degradation performance test under aerobic conditions
The degradation performance tests in aerobic conditions were carried out on the degraded materials obtained in example 2 and in comparative examples 2 to 3, with reference to the standard GB/T19277.1-2011 "determination of the final aerobic biological decomposition capacity of materials in controlled composting conditions, using method part 1 of the determination of the carbon dioxide released: the general method is carried out, the degraded material is pre-crushed and screened by a 100-mesh sieve, the culture temperature is 58 +/-2 ℃, the composting period is not more than 6 months and is more than 45 days, the relative biodegradation rate is calculated according to the experimental result, and the material can be considered to be completely degraded when the relative biodegradation rate is more than 90 percent. The experimental results are shown in fig. 1, and the results show that the sample prepared in example 2 has better degradation rate and final degradation rate than other samples, and achieves complete biodegradation; the sample prepared by the one-pot method has the conditions of nonuniform master batch, impurities and the like, and can not be completely biodegraded; the sample without the modified hollow glass beads and the inorganic filler is slow in degradation rate, and the two substances are broken and fall off to provide more attachment spaces for microorganisms, so that the degradation rate can be accelerated in the early and middle stages of degradation.
(2) Comprehensive mechanical property test
The samples prepared in examples 1 to 5 and comparative examples 1 to 3 were blown into plastic shopping bags and tested for comprehensive mechanical properties. The lifting test, the falling test and the falling dart impact test are carried out according to the standard GB/T38082-. Lifting test: a bag lifting fatigue testing machine has the amplitude of 30mm +/-2 mm, the vibration frequency of 2 Hz-3 Hz and 3 samples. Drop test: height 0.5m, 5kg of sand, number 3 samples. Dart impact: the dart had a mass of 25g and a sample number of 10 chips. The tensile force and elongation at break were carried out according to the standard GB/T1040.3-2006, the tensile rate 250mm/min and the strip width 15 mm. The results are shown in Table 1. As can be seen from Table 1, the tensile strength of the material increases with the increase of the content of PLA and plant fiber, but when 25 parts of PLA and 10 parts of plant fiber are added, the elongation at break is obviously reduced, and the prepared plastic product is easy to brittle fracture; the plastic bag made of the degradable material provided by the invention has better mechanical property and is more durable.
TABLE 1 comprehensive mechanical Properties test results
Note: and recording the number of the damaged samples in a lifting test, a falling test and a dart impact test.
(3) Antibacterial property test
The shopping bags newly prepared from the degradable material in the example 2 and the used shopping bags are cut into pieces, the same mass is weighed, the pieces are respectively mixed with 100mL of low-concentration bacterial suspension, the mixture is cultured for 10 days in an air bath constant temperature oscillator at 37 ℃ and 150r/min, the bacterial concentration is measured by adopting a viable count method, and the bacterial concentration is compared with the initial concentration of the suspension to calculate the antibacterial rate. The results are shown in table 2, and the newly prepared shopping bag has certain antibacterial property and can be used for containing food in a short period, and the used shopping bag has no obvious antibacterial property, so that the degradation process is not influenced.
TABLE 2 results of the antibacterial property test before and after use
The shopping bags newly prepared from the degradable materials of examples 1-4, 6-8 and 4 are cut into pieces, weighed to the same mass, respectively mixed with 100mL of low-concentration bacterial suspension, cultured for 10 days in an air bath constant temperature oscillator at 37 ℃ and 150r/min, the bacterial concentration is determined by adopting a viable count method, and compared with the initial concentration of the suspension, the antibacterial rate is calculated. The results are shown in table 3, and the test results of the samples of comparative examples 1-4 and comparative example 4 show that the antibacterial property of the quaternized chitosan is obviously increased, and the shopping bags prepared by adding the modified chitosan in the formula are more suitable for containing food; with the increase of the content of the modified chitosan, the antibacterial property of the material is improved, but when the proportion of the modified chitosan is increased from 1 part to 2 parts, the antibacterial property is not obviously increased, so that the addition of 1 part of the modified chitosan is considered comprehensively to be better; by comparing the antibacterial property of samples prepared under different chitosan modification process conditions, the antibacterial property of the material is basically unaffected, the reaction temperature is 55 ℃, the reflux time is 12 hours, the reaction temperature is reduced to 40 ℃, the reaction time is shortened to 6 hours, the antibacterial property of the material is obviously reduced, and the reflux time is increased to 24 hours.
TABLE 3 results of antibacterial property test of different samples
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. An article of biodegradable material, characterized in that: the material comprises the following components of PBAT 50-60 parts, PLA 15-25 parts, PPC 1-10 parts, plant fiber 1-10 parts, modified chitosan 0.5-2 parts, compatibilizer 0.1-1 part, nucleating agent 0.1-1 part, modified hollow glass bead 0.5-5 parts, organic modified montmorillonite 1-3 parts, inorganic filler 0-10 parts, and light stabilizer 0.5-1 part.
2. The biodegradable material according to claim 1, wherein said PBAT is polybutylene adipate/terephthalate with number average molecular weight of 20000-150000, said PLA is polylactic acid with number average molecular weight of 30000-250000, and said PPC is polypropylene carbonate with number average molecular weight of 10000-50000.
3. The biodegradable material according to claim 1, wherein the plant fiber is coconut fiber, bamboo powder and rice hull, and the mass ratio of the coconut fiber, the bamboo powder and the rice hull is 1:1: 2.
4. The biodegradable material according to claim 1, wherein said modified chitosan is a quaternized chitosan obtained by reacting chitosan with a halogenated hydrocarbon, and the preparation method comprises the following steps:
s01, fully and uniformly mixing 50-150 g of chitosan, 100-200 mL of methanol and 100-200 mL of ethanol at normal temperature, pouring into a three-neck flask, heating to 40-55 ℃, and reacting at constant temperature for 1-2 h to obtain a solution a;
s02, adding 200-300 mLC of the solution A 4 H 9 Br and 100-250 mLC 3 H 7 And (3) carrying out Br reflux reaction for 6-24 h, washing and carrying out vacuum drying to obtain the modified chitosan.
5. The biodegradable material according to claim 1, wherein said compatibilizer is ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA) and tetrabutyl titanate (TBT) in a mass ratio of 1: 1.
6. The biodegradable material according to claim 1, wherein said nucleating agent is dibenzoylhydrazide sebacate (TMC 300) or tert-butylcalixarene (TBC 8-d); preferably, the nucleating agent is sebacic acid dibenzoylhydrazine.
7. The biodegradable material according to claim 1, wherein the modified hollow glass microspheres are prepared by etching common hollow glass microspheres with a sodium hydroxide solution and modifying with a silane coupling agent KH550, and the particle size is 10-100 μm, and the preparation method comprises the following steps:
s10, weighing 250-350 g of hollow glass microspheres in enough NaOH solution (0.5 mol/L), reacting for 4-6 h under the conditions of constant temperature of 50-60 ℃ and magnetic stirring, washing with deionized water after the reaction is finished until the filtrate is neutral, and drying in vacuum for 1-2 h at 100-120 ℃ for later use;
and S20, adding 5-8 gKH550 silane coupling agents into the treated hollow glass beads, placing the mixture into a high-speed mixer for dry mixing, and reacting for 0.5-1 hour to obtain the modified hollow glass beads.
8. The biodegradable material according to claim 1, wherein said inorganic filler is micron-sized calcium carbonate and talc powder, and the mass ratio of said inorganic filler is 1: 1.
9. biodegradable material according to claim 1, characterized in that it has the following composition by mass: PBAT 50-60 parts, PLA 15-18 parts, PPC 6-10 parts, plant fiber 1-2 parts, modified chitosan 1.5-2 parts, compatibilizer 0.1-1 part, nucleating agent 0.1-1 part, modified hollow glass bead 0.5-1 part, organic modified montmorillonite 1-3 parts, inorganic filler 0-2 parts and light stabilizer 0.5-1 part.
10. Process for the production of a biodegradable material according to any one of claims 1 to 9, characterized in that it comprises the following steps:
s1, preparing a first-grade material:
s11, taking the hollow glass beads and a NaOH solution (0.5 mol/L), and reacting for 4-6 hours at a constant temperature of 50-60 ℃ under the condition of magnetic stirring; washing the product to be neutral by using deionized water after the reaction is finished, and drying the product in vacuum for 1 to 2 hours at the temperature of 100 to 120 ℃; adding a silane coupling agent KH550, and placing the mixture in a high-speed mixer for reaction for 0.5-1 h to obtain modified hollow glass microspheres for later use;
s12, uniformly mixing the PBAT and the modified hollow glass beads in a dry mode by using a high-speed mixer, and then adding the mixture into an internal mixer for melting and mixing, wherein the reaction temperature is 180-200 ℃, the rotation speed is 50-60 r/min, and the reaction time is 1-2 hours, so as to obtain a first-grade material;
s2, preparing a secondary material: preparing a primary material, organic modified montmorillonite, plant fiber, PPC and EMA-GMA, carrying out melt banburying by adopting a multi-feed-port double-screw extruder, feeding the primary material, the organic modified montmorillonite and the plant fiber at the main port and the PPC and EMA-GMA side ports at the reaction temperature of 200-240 ℃ and the screw rotation speed of 100-150 r/min, and granulating and cooling to obtain a secondary material after the reaction is finished;
s3, preparing a third-grade material: preparing PLA, a nucleating agent, TBT and a secondary material, melting and banburying by adopting a multi-feed-port double-screw extruder, feeding the PLA and the nucleating agent at the reaction temperature of 160-190 ℃ and the screw rotation speed of 100-150 r/min, feeding the PLA and the nucleating agent at a main port, feeding the TBT and the secondary material at a side port, and granulating and cooling after the reaction is finished to obtain a tertiary material;
s4, preparing a biodegradable material:
s41, fully and uniformly mixing chitosan, methanol and ethanol at normal temperature, pouring into a three-neck flask, heating to 40-55 ℃, keeping the temperature, adding C 4 H 9 Br and C 3 H 7 Performing Br reflux reaction for 6-24 h, washing and drying to obtain modified chitosan;
and S42, preparing the three-stage material, the modified chitosan, the inorganic filler and the light stabilizer, carrying out melt mixing by adopting a single-screw extruder, carrying out reaction at the temperature of 160-180 ℃ and the screw rotation speed of 500r/min, and carrying out granulation and cooling after the reaction is finished to obtain the biodegradable material.
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