CN113773559A

CN113773559A - Biodegradable composite modified film bag particle material and preparation method thereof

Info

Publication number: CN113773559A
Application number: CN202111048211.9A
Authority: CN
Inventors: 黄炜岚; 谭卓华; 谭晓露
Original assignee: Guangzhou Lvhui New Material Research Institute Co ltd
Current assignee: Guangzhou Lvhui New Material Research Institute Co ltd
Priority date: 2021-09-08
Filing date: 2021-09-08
Publication date: 2021-12-10

Abstract

The invention relates to a biodegradable composite modified film/bag particle material and a preparation method thereof, which is prepared from a biodegradable polyester composite, a natural organic plant fiber material, oxidized modified high amylose starch, a composite plasticizer, a combined modifier, a functional assistant, a modifier, modified nano carbon fibers and an inorganic filler; the granular material is obtained by melt reaction extrusion at 55-170 ℃ through a two-stage series screw granulator set, and mixing → reaction → extrusion → cooling → cutting → drying → sterilization → packaging. Various films, bags, disposable gloves, table cloth, aprons, raincoats and other products are produced by adopting a film blowing machine, a casting machine set and other universal equipment. The adopted raw materials have rich sources, low cost, simple process and low production cost.

Description

Biodegradable composite modified film bag particle material and preparation method thereof

Technical Field

The invention belongs to the technical field of preparation of biodegradable materials, and particularly relates to a biodegradable composite modified film/bag particle material and a preparation method thereof.

Background

The active prevention and deterrence of the flooding of disposable plastic articles has become a consensus in china and in most countries of the world. The industry of degradable plastics has keenly captured this trend. According to the statistics of the Huaan securities, 36 companies build or plan degradable plastic projects, and the newly increased capacity is 440.5 ten thousand tons in total. Many large companies in the food and beverage industry have promised to eliminate the use of plastic tableware over the past year as they are adapted to consumer expectations and legislative changes;

therefore, the method is oriented to recycling, easy recovery and degradability, develops and popularizes plastic products and substitute products with standard popularization performance, environmental protection, economy and applicability, and cultivates a new mode in a new state which is beneficial to standard recovery and recycling and reduces plastic pollution.

At present, the degradable plastic film material or particle material is expected to solve the pollution problem caused by plastics, and a certain amount of degradable plastic film or particle material is also disclosed in the prior art, but the degradable plastic material disclosed in the prior art generally has the problems of low strength, poor weather resistance, hydrophobicity, antibacterial property and the like, and cannot generally treat common plastic materials in the prior art, so that the application range of the degradable plastic material is small.

Chinese patent CN113004607A discloses a degradable environment-friendly plastic film, which is prepared from the following raw materials in parts by weight: 45 parts of thermoplastic starch, 6 parts of a compatible modification component, 15 parts of polylactic acid, 10 parts of calcium stearate, 25 parts of a plastic base material, 15 parts of polycaprolactone, 7 parts of an antibacterial agent, 3 parts of a degradation promoter, 3 parts of a filler, 4 parts of a cross-linking agent, 26 parts of plant fiber, 1 part of an auxiliary agent, 50 parts of linear low-density polyethylene, 20 parts of polypropylene, 10 parts of disulfide carbamate, 10 parts of ethyl cellulose, 10 parts of bamboo charcoal powder, 3 parts of a plasticizer, 5 parts of sodium alginate, 10 parts of zein, 5 parts of tartrate, 3 parts of 2-hydroxypropyl-beta-cyclodextrin, 3 parts of ASA high-rubber powder, 2 parts of a photodegradation agent, 1 part of a light stabilizer and 2 parts of cedar wood oil. Although the degradable film material has certain strength and certain antibacterial performance, the strength of the degradable film material cannot meet the strength requirement of common plastic materials, and the degradable film material has insufficient weather resistance, hydrophobicity and antibacterial performance.

Chinese patent CN112159580A discloses a preparation method of a completely degradable agricultural plastic film, belonging to the technical field of plastic films. The invention takes polylactic acid and polyvinyl alcohol as raw materials, and adds corn stalk, tea stalk, polyethylene glycol, high amylose starch, nano titanium dioxide and kaolin to prepare the completely degradable agricultural plastic film. The strength of the film material is improved by adding the plant fiber, but the strength is improved to a limited extent, and the antibacterial property and the hydrophobic property are insufficient, so that the application range is narrow.

Chinese patent CN111690264A discloses a degradable packaging bag, which particularly relates to the field of packaging and comprises, by mass, 10-30 parts of polyurethane, 1-15 parts of a cross-linking agent, 5-15 parts of a cosolvent, 30-50 parts of plant fibers, 1-8 parts of kaolin, 1-6 parts of polyvinyl alcohol and 10-20 parts of corn starch. The material has low strength and does not have weather resistance, hydrophobicity or antibacterial performance.

Chinese patent CN01114513A discloses a completely biodegradable plant material product and its manufacturing method. The product comprises 40-90% of plant fiber powder, 0.5-35% of natural gum, 0.05-20% of biodegradable chemical synthetic gum, 0.01-1% of catalyst, 0-10% of colorant, 0.01-5% of lubricant and 0-2% of foaming agent (all the above are weight percentages). The manufacturing method comprises the following process flows of plant fiber smashing → raw material formula mixing → pretreatment → glue adding and mixing → shaping → decoration → film spraying → packaging, and the manufactured products comprise tableware, film materials, sectional materials, pots and bowls for planting flowers, cultivation cups, various daily necessities and the like. The material has low strength and does not have weather resistance, hydrophobicity and antibacterial performance.

In summary, most of the environmental protection materials on the market are considered to be different from each other, and cannot simultaneously meet the defects of safety, sanitation, convenience, environmental protection, low cost and the like. Because of poor performance, insufficient mechanical strength, poor water resistance, poor antibacterial property, easy cracking, difficult long-term packaging, storage and use, high cost, poor experience, serious operation pollution or high raw material cost and the like. Or other reasons, which restricts the further large-scale industrial production and popularization and application. Along with the higher living standard of people, the quality of various living goods is required to be higher and higher, so that the adopted degradable plastic material has the advantages of high strength, safety, durability, good hydrophobic property and antibacterial property, cleanness, sanitation, difficult dirtiness and elegant appearance. None of the various degradable film materials or particle materials developed in the prior art can simultaneously satisfy the above properties. Through long-term research, the company develops a naturally degradable composite modified film/bag particle material which has excellent antibacterial property, ageing resistance and hydrophobic property and has the strength reaching the strength of common plastic materials.

Disclosure of Invention

A biodegradable composite modified film/bag particle material is characterized in that: the feed is prepared from the following raw materials in parts by weight: 60-80 parts of oxidation modified high amylose starch, 6-10 parts of composite plasticizer, 3-8 parts of natural organic plant fiber material, 1-3 parts of combined modifier, 20-30 parts of biodegradable polyester compound, 1 part of functional assistant, 1-1.5 parts of modifier, 4.5-8 parts of modified carbon nanofibers and 10-30 parts of inorganic filler;

the preparation method of the modified carbon nanofiber comprises the following steps:

1) preparing the hydroxylated modified porous carbon nanofiber: weighing a certain amount of ammonium bicarbonate and polyvinyl alcohol, adding the ammonium bicarbonate and the polyvinyl alcohol into a certain amount of deionized water, and uniformly stirring by magnetic force to obtain a mixed aqueous solution, wherein the mass concentration of the polyvinyl alcohol in the mixed aqueous solution is 15%, and the mass concentration of the ammonium bicarbonate is 0.1-1%; according to the weight ratio of polyvinyl alcohol: adding thermosetting phenolic resin into the mixed aqueous solution according to the mass ratio of 2.5:1, and carrying out ultrasonic treatment for 3 hours at the temperature of 50 ℃ in a water bath to obtain a uniform and transparent solution; adding the uniform transparent solution serving as electrostatic spinning solution into a micro-injection pump, applying a voltage of 22-28kV to a needle head of the micro-injection pump, enabling a negative electrode receiving electrode to be a grounded stainless steel net, controlling the flow rate of the micro-injection pump, enabling liquid drops to move towards the negative electrode under the action of an electric field, performing electrostatic spinning, and obtaining polyvinyl alcohol/thermosetting phenolic resin composite nano fibers on the stainless steel net; heating and curing the composite nanofiber at the temperature of 100-160 ℃, and then carbonizing the composite nanofiber at the temperature of 850-950 ℃ in a nitrogen atmosphere to obtain porous carbon nanofiber; adding the porous carbon nanofibers into a sodium hydroxide aqueous solution, and magnetically stirring for 1-2 hours under the water bath condition to obtain porous carbon nanofibers with hydroxylated surfaces;

2) preparing a citric acid modified silver quantum dot dispersion: under the condition of 20-30 ℃, adding 10-20ml of silver nitrate aqueous solution with the concentration of 0.1-0.2mol/L and 30-50mg of hydrazine hydrate into 1L of deionized water, magnetically stirring for 0.5-1h, adding 5-15ml of citric acid solution with the concentration of 0.05-0.15mol/L, continuously stirring for reaction for 0.5-1h, centrifugally collecting a solid product, repeatedly washing with deionized water and absolute ethyl alcohol, dispersing in a proper amount of deionized water, and performing ultrasonic treatment to obtain a silver quantum dot dispersion liquid modified by citric acid;

3) dispersing the porous carbon nanofibers with hydroxylated surfaces obtained in the step 1) into the silver quantum dot dispersion liquid modified by citric acid obtained in the step 2) according to a certain solid-to-liquid ratio, magnetically stirring for 1-2h, and filtering and separating to obtain the porous carbon nanofibers loaded with silver quantum dots, namely the modified carbon nanofibers.

The high amylose starch is one or a mixture of two of corn starch, wheat starch, potato starch, barley starch, mung bean starch, pea starch, sweet potato starch and cassava starch. The amylose content of the high amylose starch is 40-90%.

The preparation method of the oxidation modified high amylose starch comprises the following steps: dispersing the high amylose starch into deionized water to obtain starch emulsion with the mass concentration of 40-50%, adding a certain amount of hydrogen peroxide, reacting at room temperature for 1-2h, finally washing, drying and crushing to obtain the oxidized modified high amylose starch; the amylose content of the high amylose starch is 40-90%.

The composite plasticizer is a mixture of two or more of polyethylene glycol stearate, 1-ethyl-3-methylimidazole acetate, poloxamer, lecithin, acetyl tributyl citrate, propylene glycol, glycerol, xylitol and epoxidized soybean oil. The molecular weight of the plasticizer is 76-2000.

The natural organic plant fiber material is a mixture of two or more than two of corn vinasse concentrated dry powder, wheat vinasse concentrated dry powder, sugarcane vinasse concentrated dry powder, sorghum vinasse concentrated dry powder, green naked vinasse concentrated dry powder, coconut shell powder, betel nut shell powder, olive kernel powder, coffee residue dry powder, cocoa extract dry powder, bamboo powder, reed powder, sunflower seed shell powder, durian peel fiber powder and kapok fiber powder. The particle size of the natural organic plant fiber material is 800-2000 meshes.

The combined modifier is a mixture of dodecenyl succinic anhydride, octenyl succinic anhydride, absolute ethyl alcohol and sodium hydroxide; the mixture ratio was 1:1:4: 0.7.

The biodegradable polyester compound is a blend of Polyhydroxyalkanoates (PHAs) and polybutylene adipate terephthalate (PBAT); the blend ratio was 4: 6.

The Polyhydroxyalkanoates (PHAs) are a mixture of two or more than two of poly-3-hydroxybutyrate (PHB), poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34 HB.

The functional auxiliary agent is an epoxy functionalized ADR chain extender of BASF company; the modifier is a mixture of Polyoxyethylene (PEO) and maleic anhydride.

The inorganic filler is one or a mixture of two of graphene, nano zinc oxide, nano calcium carbonate, octadecyl quaternary ammonium salt modified nano montmorillonite and multi-walled carbon nano tube.

A preparation method of a biodegradable composite modified film/bag particle material comprises the following steps:

weighing the following components in parts by weight: adding 60-80 parts of high amylose starch and 6-10 parts of composite plasticizer into a high-speed mixer, sealing a top cover, stirring for 5-12 minutes, oscillating for 30 minutes at room temperature by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

weighing the following components in parts by weight: 3-8 parts of natural organic plant fiber material and 1-3 parts of combined modifier are slowly added into the mixture at a high speed

Stirring at high speed (2000r/min) in a stirrer for 5 minutes, then oscillating at room temperature for 30 minutes by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

before the natural organic plant fiber material is used, drying treatment is carried out; the drying temperature is 90-100 ℃, and the drying time is 6-8 hours;

weighing the following components in parts by weight: 20-30 parts of biodegradable polyester compound, 1 part of functional assistant, 1-1.5 parts of modifier, 4.5-8 parts of modified carbon nanofibers and 10-30 parts of inorganic filler are added into a mixer, a top cover is sealed, and the mixture is stirred at low speed (500r/min) for 10 minutes for later use;

adding the raw materials obtained in the step I into a first material inlet of a first temperature zone of a double-order series screw granulator set with the length-diameter ratio of 48:1 through a vacuum feeding machine conveying device, fully mixing → reacting until a second material inlet of a third temperature zone, adding the raw materials obtained in the step II, and fully mixing → reacting until a third material inlet of a fifth temperature zone, and adding the raw materials obtained in the step III; beginning from the first feeding port, the temperature of the temperature zone of each section of the screw cylinder of the extruder set to be 75-80 ℃, 80-85 ℃, 85-90 ℃, 95-100 ℃, 110-120 ℃, 120-130 ℃, 130-140 ℃, 140-150 ℃, 155-170 ℃, 135-140 ℃, 105-110 ℃, 75-80 ℃, 55-60 ℃ and the rotation speed of the screw is 150-200 r/min, and the biodegradable composite modified film/bag particle material is obtained by melt reaction extrusion → cooling → cutting → drying → packaging → from 55-170 ℃. The two-stage series screw granulator has 13 heating temperature zones.

Various films, bags, disposable gloves, table cloth, aprons, raincoats and other products are processed and produced in large scale by adopting a film blowing machine, a casting machine set and other universal equipment.

The invention has the beneficial effects that:

(1) in the invention, high amylose starch is subjected to oxidation modification treatment, and hydroxyl of a molecular chain of the starch is partially oxidized into hydrophobic carbonyl, so that the hydrophobic property of the starch is improved.

The invention adopts high amylose starch, breaks through the limitation that the prior biodegradable plastic is only prepared by adopting common starch, and the traditional starch has high amylopectin content, and the prepared packaging material has poor strength and can be immediately dissolved in water. The experimental research of the patent application finds and verifies that the high amylose starch adopted by the invention has swelling resistance, poor water solubility and insolubility in fat; the higher the amylose content is, the higher the tensile strength of the film is and the lower the water absorption rate is, because the higher the amylose content of linear macromolecules is, the higher the consistent degree of molecular orientation is, and the intermolecular bonding is tighter, so the film has the performance similar to fiber if the strength is higher, and has unique application value compared with common starch; the biodegradable food packaging material is tasteless, odorless, nontoxic and pollution-free, has water resistance and oil resistance, and is a good biodegradable food packaging material; can be applied to the production of sealing materials, packaging materials and water-resistant and pressure-resistant materials.

Compared with multiple properties, the potato starch has better anti-retrogradation property and transparency, and the best mildew resistance, mechanical property and water resistance;

(2) the invention adopts the plasticizer with high relative molecular mass containing hydroxyl and the composite plasticizer with low relative molecular mass to plasticize high amylose starch

The plasticizing principle is that polar groups of the plasticizer interact with starch intramolecular and intermolecular hydroxyl groups to reduce intramolecular acting force, so that the processing temperature is reduced.

The application synthesizes the efficient plasticizer, prepares the plasticizer with various functional groups simultaneously by an organic synthesis method, has the advantages of avoiding the defects and is one of the possible development directions.

The invention adopts the hydroxyl-containing plasticizer with high relative molecular mass and the plasticizer with low relative molecular mass to compound and plasticize

The experimental research of the patent application finds and verifies that: the advantages of some plasticizers can be optimized by compounding and combining different plasticizers, the defects existing when a certain plasticizer is used independently can be eliminated, and the purposes of reducing the cost and improving the plasticizing effect are achieved. The results show that:

1-ethyl-3-methylimidazolyl acetate changes the entanglement mode of amylose, and the starch-based film is more uniform, has no gel, is lower in molecular level, better in plasticizing effect and remarkably improved in flexibility.

Lecithin is a substance which can improve the affinity between water and oil, has excellent wettability, can maintain an ideal wetting effect for a long time, and also contributes to the extension of the shelf life of the product. Adhesion and coking are prevented, and starch retrogradation can be delayed by combining the fat and the starch, so that an anti-aging effect is achieved. Under the condition of Cu, Fe, Mn and other ions, the antioxidant effect is high. Can promote the stirring and mixing of the raw materials, greatly reduce the mixing time of the raw materials, obviously reduce dust and assist the granulation and extrusion of the feed.

The glycerol with small molecular weight is easier to move and can more effectively permeate into chains of starch molecules than xylitol molecules with slightly larger molecular weight, the destructive power to the acting force among the starch molecules is larger, the xylitol with more carbon atoms also contains more hydroxyl groups per molecule, the acting force with the starch molecules is also strong, and the permeation effect is far inferior to that of the glycerol with smaller molecular weight. The size of molecular chain flexibility was identified by calculating the viscous flow activation energy Δ e η of the different blends, and it was found that Δ e η =225.1kg/mol for xylitol blends, and Δ e η =122.5kg/mol for glycerol blends, the activation energy indicating a large increase in the rigidity of the molecular chains. Can effectively reduce the melt viscosity of the system and reduce the moisture absorption phenomenon of the thermoplastic starch.

One end of the polyethylene glycol stearate is hydrophilic medium-high molecular weight polyethylene glycol, and the other end of the polyethylene glycol stearate is oleophylic stearic acid, so that the polyethylene glycol stearate can be respectively adsorbed on two mutually exclusive phase surfaces of oil and water to form a thin molecular layer, and the interfacial tension of the two phases is reduced, so that the original mutually insoluble substances are uniformly mixed to form a uniform dispersion system, and the physical state of the raw materials is changed.

The citrate (ATBC) is used as a water-resistant plasticizer, has better plasticity for the biodegradable polyester compound adopted by the application, so that the addition of the citrate better ensures the common plasticization of the whole system, and the elongation at break of the citrate is better than that of polyethylene glycol according to the elongation at break.

Poloxamers have very low toxicity and can be used for shaping, emulsifying, wetting, lubricating, dispersing, dedusting and viscosity regulating.

The epoxidized soybean oil can be used as an auxiliary plasticizer and a heat stabilizer, and has almost no toxicity.

According to the invention, in the research on plasticization of the mixed compound plasticizer of corn starch and cassava starch, the mechanical property of the product can be improved under the condition that the thermoplastic starch matrix is plasticized by mixing two or more plasticizers:

high amylose starch has good plasticity and is easy to implement because of its low crystallinity.

Secondly, the data shows that the characterization of the composite film after the polyethylene glycol stearate is added is excellent, and the film is more flexible, which is probably caused by the fact that the plasticizing effect of the glycerin on the composite film is obviously improved due to the addition of the polyethylene glycol stearate. And thus can function as both a plasticizer and a surfactant. The plasticizing effect is reflected in: the polyethylene glycol stearate with medium and high molecular weight can reduce intermolecular acting force of starch or the biodegradable polyester compound adopted by the application, improve the processing performance and avoid pyrolysis and carbonization of the starch. The function of the surfactant is represented by: stearic acid has good compatibility with the biodegradable polyester compound adopted by the application, and forms an insoluble compound with amylose to generate anti-aging effect. The polyethylene glycol and the starch have good compatibility, namely the biodegradable polyester compound and the starch adopted by the application are mutually lapped by the polyethylene glycol stearate, so that the interfacial interaction force is increased. In addition, the molecular chain of the selected high molecular weight polyethylene glycol is longer, so that the polyethylene glycol can form more entanglement with the biodegradable polyester compound or starch adopted by the application, and the intermolecular force is increased.

The addition of the polyethylene glycol stearate and the citric acid ester (ATBC) improves the tensile strength of the composite film, and shows that the addition of the two second plasticizers and the composite system interact to form a strong hydrogen bond, so that the compatibility of the starch, the biodegradable polyester compound and the inorganic filler adopted by the application and the formation of an intercalation structure are promoted.

And the epoxidized soybean oil is used as an auxiliary plasticizer and a heat stabilizer, has excellent heat processing and flexibility, and can improve the performance of the biopolymer so that the biopolymer is more flexible and/or the flow characteristic is changed.

Under the test conditions, the larger the molecular weight of the plasticizer is and the weaker the water absorption capacity is, the better the water vapor barrier property of the film is, and on the contrary, the worse the water vapor barrier property is.

Sixthly, the mechanical properties of the thermoplastic starch material show regular changes due to different plasticizer contents, and generally, the tensile strength is reduced and the elongation is increased along with the increase of the plasticizer content.

The crystallization rate of the starch is increased along with the increase of the moisture content, the mobility of starch chains and the stability of bound water are reduced due to the strong hydrogen bond interaction between the plasticizer and the starch, and the crystallization rate is reduced due to the increase of the plasticizer content. However, if the plasticizer has a high hygroscopicity, the moisture content of the material increases accordingly, and the crystallization rate of the starch increases conversely.

The stronger the capability of forming hydrogen bonds between the plasticizer and the starch, the better the anti-retrogradation performance of the thermoplastic starch.

Experimental research on the composite plasticizer system of the invention finds and verifies that:

the starch plasticizer has strong and stable hydrogen bond with starch, difficult recovery of starch conformation, key effect in starch plasticization, better durability than the traditional plasticizer, good surface activity when being used as the plasticizer, emulsification, dispersion, starch aging resistance and other effects, can play a role of an emulsifier, enables starch particles to be dispersed more uniformly, and can obviously inhibit starch from returning back to the starch

The starch retrogradation phenomenon is effectively prevented, and the gelatinization temperature is reduced.

Secondly, the plasticizer has stronger interaction with starch and the molecules of the biodegradable polyester compound adopted by the application, and the plasticizing effect is better than that of single plasticizing.

According to the ultrasonic oscillation principle, due to the fact that mass points of the substance have extremely high motion acceleration in ultrasonic waves, intense and rapidly-changing mechanical motion is generated, solid molecules are degraded in a medium along with fluctuating high-speed vibration and shearing force, starch particles are thinned, the particle size is reduced, the specific surface area is increased, and coating of other hydrophobic components is facilitated.

(3) The composite modifier is used for carrying out composite esterification modification on natural organic plant fiber materials and is used as a reinforcing agent to prepare the thermoplastic starch composite material

Although thermoplastic starch has the advantages of low cost, complete degradation and the like, the wide application of the thermoplastic starch is limited by the problems of large change of water resistance and mechanical property of the thermoplastic starch along with the environmental humidity and the like. The plant fiber is used as a reinforcing agent and is one of methods for improving the performance of the thermoplastic starch. The starch and the natural organic plant fiber material have the same polysaccharide structure, and the starch and the natural organic plant fiber material can be combined together well by compounding. The mechanical property of the starch can be obviously improved by blending the fiber and the starch. And the natural organic plant fiber material is hydrophobic, the starch is hydrophilic, the water resistance of the starch can be obviously improved after the natural organic plant fiber material is added, and the thermal stability is also obviously improved. However, the surface of the natural organic plant fiber material has a large number of hydrophilic hydroxyl groups, so that the natural organic plant fiber material is easy to agglomerate through hydrogen bond interaction, and the improvement of the mechanical property, hydrophilicity/hydrophobicity and moisture permeability of the reinforced thermoplastic starch composite material of the natural organic plant fiber material is not facilitated.

The invention utilizes the combined modifier to carry out composite esterification modification on the natural organic plant fiber material, combines ultrasonic oscillation, takes the natural organic plant fiber material as a reinforcing agent to prepare the thermoplastic starch composite material, utilizes a single-factor test to examine the influence of surface esterification treatment process parameters from the aspects of the sensitivity of the material to environmental humidity, the hydrophilicity of the surface of the material and the like, and utilizes the single-factor test and the mixed orthogonal test design to analyze a plurality of factors influencing the surface esterification modification degree of the material on the basis, thereby obtaining the following main conclusions:

the composite esterification modification that the ware is gone on natural organic plant fiber material is not destroyed natural organic plant fiber material's crystal structure to the ware that has received, and esterification reaction only takes place on natural organic plant fiber material surface, at natural organic plant fiber material's the modified in-process of composite esterification, and preparation thermoplasticity starch complex film can not destroyed.

The addition of the composite esterified modified natural organic plant fiber material in the wall component increases the mechanical strength by 300%, and the tensile strength of the composite membrane is increased and then reduced along with the increase of the addition amount, so that the elastic modulus is increased continuously, the elongation at break is reduced continuously, and the tensile strength and the elastic modulus of the thermoplastic starch composite membrane can be increased. Within the range of the addition amount to be examined, the size of the natural organic plant fiber material particles only has a significant influence on the elastic modulus of the thermoplastic starch composite film.

⒊ the water vapor transmission rate of the thermoplastic starch composite film can be reduced after the composite esterified modified natural organic plant fiber material is added, and the water vapor transmission rate of the composite film is continuously reduced along with the increase of the addition amount, so that the water can be better prevented from penetrating through the thermoplastic starch composite film, and the water vapor transmission rate is greatly reduced by 59.81 percent. Within the range of the addition amount to be examined, the smaller the particle size of the natural organic plant fiber material, the lower the water vapor transmission rate of the thermoplastic starch composite.

⒋ the moisture absorption rate of the thermoplastic starch composite film can be reduced after the composite esterified modified natural organic plant fiber material is added, but the influence of the addition amount on the moisture absorption rate of the thermoplastic starch composite film is not obvious, and the service life of the product is prolonged. Because they are completely compatible with the amylose molecules, these polymers form a compact structure between them, thereby reducing the water absorption capacity of the thermoplastic starch. Within the range of the addition amount to be examined, the influence of the particle size of the natural organic plant fiber material on the hygroscopicity of the thermoplastic starch composite film is not obvious.

⒌ the contact angle between the surface of the thermoplastic starch composite film and water can be improved and the water resistance can be improved by 75.46% after the composite esterified modified natural organic plant fiber material is added. And the contact angle is gradually increased along with the increase of the addition amount, so that the contact angle between the surface of the thermoplastic composite film and water can be more effectively improved.

⒍ A small amount of composite esterified modified natural organic plant fiber material can be added to improve the thermal stability of the material.

⒎ the natural organic plant fiber material adopted by the invention has a particle size of 800-2000 meshes, and the finer the particles, the smaller the particle size and the larger the specific surface area, thereby being beneficial to coating of other hydrophobic components.

⒏ the invention has certain progress in the modification of natural organic plant fiber material and the application research thereof in starch-based packaging material, and provides some new ideas for the application of natural organic plant fiber material in starch-based composite packaging material.

In addition, a composite plasticizing system is adopted to chemically modify the surface of the natural organic plant fiber material, so that the performance of the natural organic plant fiber material/biodegradable polymer can be effectively improved, and the researches provide a new research idea for the research of the natural organic plant fiber material/biodegradable polymer composite material.

(4) Biodegradable polyester compound

Preparation method of polyhydroxy alkanoate (PHAs)

Polyhydroxyalkanoates (PHAs) are biodegradable materials with good biocompatibility, high degradation rate in natural environment and bioabsorbability, have melting point and strength higher than PE, have very excellent strength and gas barrier property, and have application potential in the field of high-performance plastics. But the product has large brittleness, narrow processing window, difficult processing and forming, slow crystallization rate and high price, and the tensile toughness is lower than that of PE, so that the Polyhydroxyalkanoates (PHAs) are necessary to be compounded and blended:

the structural diversification and the performance variability of Polyhydroxyalkanoates (PHAs) make the PHAs an important member of biological materials, have excellent material thermal processing performance, gas separation, hydrophobicity, biocompatibility, optical activity, gas barrier property, ultraviolet stability, high-temperature liquid bearing performance and other excellent performances, and have product stability, thermal forming performance and moisture resistance equivalent to polyolefin. Since it is a family of materials with a wide range of properties, from rigid to highly elastic, it can be adapted to different application needs. The PHA material has various varieties and structures, so that the PHA material has the performance from rigid materials to elastomers, the application range can almost cover all the fields of general plastics, and the PHA material has incomparable advantages of other materials in the aspects of environmental protection performance and biocompatibility.

The obvious advantage of Polyhydroxyalkanoates (PHAs) is the possibility of adapting the end product to different fields of application by structural adjustment, which supports the diversity of the monomers

The poly-3-hydroxybutyrate (PHB) is similar to the traditional plastic in certain performances, and has similar mechanical properties to polypropylene (PP), but the poly-3-hydroxybutyrate (PHB) has simple and regular chemical structure and high crystallinity of 60-80 percent, so the poly-3-hydroxybutyrate (PHB) has strong brittleness, small toughness, low fracture elongation, poor ductility, easy aging, low thermal stability and narrow processing window, and greatly limits the application range of the poly-3-hydroxybutyrate (PHB).

The poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) has higher hardness, certain ductility and toughness improvement, higher biocompatibility, hydrophobicity and better physical property; but still has serious low crystallization rate and post-crystallization phenomenon, and the brittleness is still larger;

the poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) has the advantages that the flexibility is greatly improved compared with that of PHB, the hardness of the material is reduced, the ductility is improved, the crystallinity is reduced, the crystallization rate is not changed greatly, the mechanical property is improved, and the processing and the forming are facilitated; the biocompatibility is much better than that of other high polymer materials, and the surface property is more excellent;

poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (P34HB) has high strength and ductility, remarkably improves thermal stability, improves processability and can adjust material performance (between glass state and rubber state); the material has excellent physical and chemical properties and application range, the melting point can be reduced from 178 ℃ to 130 ℃, the glass transition temperature can be reduced from 4 ℃ to 48 ℃, and the crystallinity can be reduced from 60% to 14%, so that the material can be used as a biodegradable hard plastic product, a film and a fiber product, an elastomer, an adhesive and a modifier of other materials; however, P34HB is sensitive to shearing and temperature during processing, and the performance and the shape of the product are difficult to guarantee; therefore, P34HB also needs to be modified to improve its performance and expand its application field.

The experimental result of preparing PHBV/P3HB4HB blend with different proportions by adopting a solvent casting method shows that the highest breaking strength of the PHBV/P3HB4HB blend can reach 25MPa, the elastic modulus is reduced by 3 times and is 460MPa compared with pure PHBV, and the breaking elongation is improved to 670 percent from 2.3 percent of the pure PHBV and is improved by nearly 290 times. From the SEM picture of the cross section of the blend, it can be observed that the fracture behavior of the PHBV/P3HB4HB blend changes from brittle to ductile. Therefore, the blend overcomes the rigidity and brittleness of pure PHBV and the low modulus of P3HB4HB, can improve the defects of high crystallinity and brittleness by compounding and blending Polyhydroxyalkanoates (PHAs), improves the mechanical property, heat resistance and water resistance of the Polyhydroxyalkanoates (PHAs), and expands the industrial application of Polyhydroxyalkanoates (PHAs) materials.

Di-adipic acid-butylene terephthalate copolymer (PBAT)

The adipic acid-terephthalic acid-butylene terephthalate copolymer (PBAT) 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. PBAT combines the excellent degradation performance of aliphatic polyester and the good mechanical and thermal properties of aromatic polyester. The PBAT fiber is a biodegradable material with excellent toughness, low strength and high elongation at break (+/-600%), the glass transition temperature of PBAT is-30 ℃, and the PBAT fiber is lower than room temperature, so that the PBAT fiber has soft hand feeling at normal temperature. The crystallization temperature is 110 ℃, the melting temperature is 130 ℃, the decomposition temperature is 375 ℃, the flexible aliphatic chain segment enables the polyester to have good degradation performance, and the rigid aromatic polyester enables the polyester to have excellent mechanical property, heat resistance and impact resistance.

Research shows that PBAT can be almost completely biodegraded under certain conditions, and PBAT does not cause harm to the environment in composting experiments.

The good mechanical property and biodegradability of the PBAT make the PBAT suitable for film products, such as agricultural mulching films, environment-friendly garbage bags, food packaging bags and other products.

The melting point and mechanical properties of PBAT are comparable to those of PE, suggesting that it may essentially cover the application of PE in the disposable article industry.

But the tensile strength and the gas barrier property of the PBAT are not good, compared with common plastics, the PBAT has the problems of poor crystallinity, low melt strength, high price and the like, and the application of the PBAT in the fields of fibers and membrane materials is limited.

In summary, starch, PBAT, Polyhydroxyalkanoates (PHAs) are all biodegradable materials with great development prospects. However, when the three materials are used independently, the requirements of the market on the comprehensive performance of the three materials are difficult to meet, and the three materials need to be modified. The melt blending modification is the simplest and most simple and efficient modification method:

(5) based on the blending technical principle, the Coleman-PainterF hydrogen bond theory and the molecular assembly theory, the modified thermoplastic starch is used as a matrix, the natural organic plant fiber material is modified by composite esterification, the reinforcement is used, the biodegradable polyester and the related auxiliary agents are subjected to a blending and copolymerization measure, a new intermolecular assembly structure is formed by a melt reaction of a two-stage series screw granulator set at 55-180 ℃, and the defects of the modified thermoplastic starch in the use performance can be effectively overcome by virtue of the excellent mechanical property, water resistance and moisture resistance of the biodegradable polyester; the water resistance and the mechanical strength of the modified thermoplastic starch are improved by modifying the natural organic plant fiber material through composite esterification, and the application range of the modified thermoplastic starch is enlarged.

The interaction between two components in the blend, the aggregation structure of the blended polymer, the crystallization dynamics, the mechanical property, the moisture resistance and the mechanical property stability are researched and analyzed by adopting FTR Fourier infrared spectrum test, SEM and PLM morphological structure observation, DSC isothermal crystallization characterization, mechanical property tensile test, moisture resistance and time stability characterization and other methods for extruded particles. The results reveal that:

the glass transition temperature of the composite material is changed by adding the driving plasticizer, so that the crystallinity of the composite material is changed, and the composite material has good performance.

The mixing of Polyhydroxyalkanoates (PHAs) and PBAT by the wall-through component can not only keep a certain degradation rate, but also obtain the mechanical property of rigidity and toughness balance, and the toughness of the wall-through component is improved while the degradation property of the material is kept.

The viscous flow activation energy of the PHBV/PBAT blend is lower than that of pure PHBV and pure PBAT, the sensitivity of the PHBV to temperature is reduced, the thermal stability is improved, and the processing temperature range is expanded.

The PHBV/PBAT blend film is prepared by melt blending PHBV and PBAT and extruding and blowing the film, and the co-extrusion of the PHBV and the PBAT achieves better effects on the aspects of tearing resistance and sealing property of the food packaging film; the mechanical properties (breaking strain and tear resistance) of the double-layer film are equivalent to those of a PBAT (poly (butylene adipate-co-terephthalate)) blown film for commercial food packaging, and reach about 750 percent.

Thirdly, when the mass ratio of the PBAT to the PHBV is 50: 50, the impact strength of the composite material is improved to 63.9kJ/m2 from 6.5kJ/m2 of the pure PHBV; the elongation at break is 55%, the notch impact strength is 542J/m, which is respectively 19 times and 22.6 times of that of the PHBV material before modification, and the toughness of the PHBV is obviously improved; meanwhile, the PBAT can also inhibit the crystallization of the PHBV, so that the crystallization temperature of the PHBV is reduced by 20-40 ℃;

SEM pictures show that the PBAT content exceeds 50%, and the PBAT begins to change from dispersed phase to continuous phase; differential Scanning Calorimetry (DSC) research shows that the crystallization of PHBV is inhibited by adding PBAT, so that the crystallization temperature is reduced by more than 20 ℃.

Blending PBAT and PHB, adding a small amount of coconut shell powder, and preparing a biodegradable film by adopting a melt extrusion method; the rheology, thermal properties and mechanical properties show that the addition of coconut shell powder reduces the crystallization rate of the blend, which is beneficial to the processing of PBAT/PHB blends; the PBAT/PHB composite material containing 3 parts of coconut shell powder (the mass ratio is 50: 50) has lower degradation rate in the processing process and simultaneously keeps good mechanical property.

⒊ blending PBAT with modified starch

The addition of the biodegradable polyester obviously improves the performance of the starch. When the starch matrix is in a glass state, the addition of the biodegradable polyester reduces the Young modulus of the material, but improves the impact strength; the addition of the biodegradable polyester increases the Young's modulus when the starch matrix is in a rubbery state (the state of the starch matrix is related to the degree of starch plasticization). Even if the addition amount is 20%, the dimensional stability of the system and the water resistance of the material are obviously improved no matter what state the starch matrix is; the hydrophobic property of the material is obviously improved by carrying out oxidation modification treatment on the starch. The film made of the TPS/PBAT composite material has good mechanical properties, such as: high tensile strength and elongation at break, antistatic properties, oxygen and water permeability are printed and sealed, the handfeel is very soft, and meanwhile, the cost can be greatly reduced, the degradation rate of PBAT can be accelerated, the cost can be reduced, and the problems of resource shortage and environmental pollution can be solved. Therefore, the application range of the material is very wide.

⒋ the mechanical property of the composite material is enhanced significantly with the addition of the modified nanometer carbon fiber, the nanometer carbon fiber has higher strength compared with the composite esterification modified natural organic plant fiber material, and can play a complementary role when being added with the composite esterification modified natural organic plant fiber material, thereby significantly improving the tensile strength, the flexural strength and the compressive strength of the material. The purpose of improving the mechanical property and the like is achieved, and the cost is reduced.

And with the increase of the addition amount of the biodegradable polyester, the composite material provided by the invention has better mechanical property, water resistance and light transmittance. The composite material added with 20-30% of biodegradable polyester has better performance.

⒌ for the blending system, the compatibility of the multi-component substance is an important factor influencing the mechanical property of the material, in order to solve the phase separation of the starch and the biodegradable polyester blending system, the research of the invention finds and verifies that:

firstly, the amphiphilic composite esterified modified natural organic plant fiber material plays a bridge connection role between the modified thermoplastic starch and the biodegradable polyester, the hydrophobic end of the amphiphilic composite esterified modified natural organic plant fiber material is combined with the biodegradable polyester, and the hydrophilic end of the amphiphilic composite esterified modified natural organic plant fiber material is combined with the modified thermoplastic starch, so that the interface combination of the composite material is enhanced, and the mechanical property of the composite material is improved.

Secondly, the combination of the starch granules and the biodegradable polyester can be improved by Polyoxyethylene (PEO), and the dosage of the starch can reach 50 percent (far more than 25 percent of the proper dosage of the traditional method) in the presence of a small amount of the PEO.

The research on the aspect of improving the compatibility is carried out through experiments, and the compatibility of the biodegradable polyester and the starch can be improved by adding maleic anhydride as a compatibilizer; fourier transform infrared spectroscopy shows that the addition of the maleic anhydride can enhance the interaction among molecules, and the tensile strength and the elongation at break of the composite material are improved.

According to the test result, the addition of the maleic anhydride promotes the transesterification reaction of the starch and the PBAT, improves the compatibility of the composite material, improves the mechanical property of the composite material and improves the hydrophobicity of the film. The glass transition temperature of the PBAT is increased, the crystallinity of the TPS/PBAT is reduced, and the interface action between two phases in the composite material is improved. Meanwhile, the composite viscosity of the TPS/PBAT blending system has obvious shear thinning behavior compared with that of pure PBAT, which is beneficial to blow molding film formation, and the mechanical property of the film is also improved due to the compatibilization of maleic anhydride.

⒍ the inorganic filler is added into the composite material system of the invention to achieve the purpose of improving the mechanical property and the like, and the cost is reduced. The results discovered and verified by the inventor through a series of experimental researches show that:

the octadecyl quaternary ammonium salt modified nano-montmorillonite and multi-wall carbon nanotube mixture are added into the composite material system, so that the hardness and the water-blocking performance of the material can be improved.

The results found and verified by experimental studies show that: the addition of the octadecyl quaternary ammonium salt modified nano montmorillonite obviously reduces the water vapor transmission rate of PBAT, and the main reason for the reduction is that the added filler plays a role of a physical barrier; when the octadecyl quaternary ammonium salt modified nano montmorillonite in the composite material system is increased to be more than 3 percent, the tensile strength, the bending strength, the impact strength and the tensile elastic modulus of the composite material of the blending system can be obviously improved, the nano intercalation structure of the octadecyl quaternary ammonium salt modified nano montmorillonite effectively blocks oxygen and other combustible gases, and the thermal stability, the mechanical property and the water resistance of the composite material blend are obviously improved; research shows that the tensile property, the air permeability and the biodegradability of the composite film are related to the content of octadecyl quaternary ammonium salt modified nano montmorillonite, and the ultraviolet aging influences the permeability of oxygen and carbon dioxide.

When the mass fraction of the multi-walled carbon nanotubes in the composite material system exceeds 0.5%, the tensile strength and the tensile elasticity can be obviously improved, and the tensile strength, the tensile elastic modulus and the elongation at break of the system are improved by adding the multi-walled carbon nanotubes. Researches show that the carbon nano tube has heterogeneous nucleation effect, reduces the phase transition temperature of the TPS, enables the composite material to have higher critical temperature and promotes the crystallization of the composite material.

Adding graphene

The graphene is doped into the PBAT to prepare the high-gas-barrier polymer film, and the high-gas-barrier polymer film can be applied to food packaging sensitive to oxygen and water vapor so as to prolong the shelf life of food.

Firstly, preparing a graphene/PBAT nano composite film, and finding that graphene is completely peeled off in a PBAT substrate and is well dispersed; the low-concentration graphene has obvious influence on the thermal stability and the mechanical property of the PBAT film, the tensile strength of the graphene/PBAT nano composite material is improved from 24.6MPa of pure PBAT to 58.5MPa, and the mechanical property is obviously improved compared with that of the pure PBAT; the addition of the graphene also enables the PBAT matrix to have good thermal stability; the impermeability, complete stripping and good dispersibility of the graphene and the strong interface bonding force between the graphene and the PBAT substrate enhance the air resistance performance of the composite membrane.

The blending result of the PHBV, the PBAT and the graphene shows that the toughness of the composite material is increased and the processing performance of the composite material is improved when the PHBV, the PBAT and the graphene are blended, when 5 percent (w) of graphene is added, the biodegradation performance of the composite material is good, and the tensile modulus is increased from 509MPa of pure PHBV to 664 MPa.

The PBAT is filled with the nano calcium carbonate CaCO3 and the nano calcium carbonate CaCO3 inorganic particles, and researches on mechanical properties show that when the content of the nano calcium carbonate CaCO3 inorganic particles is 10%, the tensile strength, the elongation at break and the tear strength of the PBAT/nano calcium carbonate CaCO3 composite material are greatly improved, and even when the content of the nano calcium carbonate CaCO3 inorganic particles is more than 20%, the material can still keep better properties:

increasing air permeability.

Secondly, the film stiffness is obviously increased, and the film is beneficial to flattening and curling.

And improving the electroplating property, the coating property and the printing property of the composite material.

And fourthly, the heat resistance of the composite material is improved, and the tear resistance of the film is obviously improved.

The film has good openness, and can not generate adhesion during curling, thereby playing the effect of the opening agent.

Fourth, nano zinc oxide is added into the composite material system of the invention

The strong interaction between the nano zinc oxide and the PBAT is found to cause the ZnO nano particles to be uniformly dispersed in the PBAT matrix; when the ZnO mass fraction is 10%, the tensile strength of the composite film is 45MPa and is higher than that of a pure PBAT film (37.9 MPa); the result of the prepared PBAT/nano zinc oxide film shows that the addition of ZnO has good antibacterial activity on escherichia coli and staphylococcus aureus. The antibacterial performance of the composite membrane on staphylococcus aureus, pseudomonas aeruginosa and bacillus subtilis can be obviously improved.

⒎ the results of experimental research finding and verification show that:

the epoxy functionalized ADR chain extender can improve the thermal stability of an esterified modified natural organic plant fiber material, effectively improves the strength of a melt, has the maximum shear strength, the maximum tensile strength and the optimal heat resistance, has little influence on the crystal structure of biodegradable polyester, can reduce the crystallization speed and improve the maximum crystallization temperature, and obviously improves the mechanical property.

The chain extender can act through the dispersed CaCO3 particles and improve the dispersity of CaCO 3; the addition of the chain extender does not affect the form of the PBAT, and the Young modulus and the elongation at break of the pure PBAT are improved; the addition of the chain extender has no influence on the thermal behavior of the pure PBAT and the PBAT/CaCO3 composite material; the addition of CaCO3 reduced the crystallinity of the pure PBAT and the composite because CaCO3 hindered the movement of the polymer molecular chains.

⒏ the results of experimental research finding and verification show that: the coffee grounds, the olive kernel powder and the cocoa extract have synergistic antioxidation, so that the catalytic oxidation effect of water and light can be effectively avoided, the service life of the bioplastic can be prolonged, and meanwhile, the materials can be composted into fertilizers within one year.

The composite material has the advantages of high tensile strength, high light transmittance, high water resistance, high thermal stability and high compatibility, and has a smooth and uniform microstructure.

The naturally degradable composite modified film/bag particle material prepared by the invention has good biodegradability and use stability, can realize the improvement of material performance on the basis of not influencing the degradation of the material, can greatly reduce the cost, and can replace various (more than 50 percent) plastic materials. The adopted raw materials have rich sources, low cost, simple process and low production cost. Has good theoretical and practical significance and is expected to become a general biodegradable material.

The strength of the plastic tableware can be obviously improved by adding the modified nano carbon fiber, so that the plastic tableware has the strength of wood or common ceramic tableware, has good toughness, and is less prone to being broken compared with common ceramic tableware; the preparation method comprises the steps of preparing the porous carbon nanofibers, hydroxylating the porous carbon nanofibers to enable a large number of hydroxyl groups to exist on the surfaces of the porous carbon fibers, then placing the porous carbon fibers in a citric acid modified silver quantum dot dispersion liquid to enable the silver quantum dots to enter pore structures of the nanofibers, enabling carboxyl groups existing on the surfaces of the citric acid modified silver quantum dots to be capable of being in a hydroxyl structure on the surfaces of the carbon nanofibers, enabling the silver quantum dots to be firmly attached to the porous carbon fibers, and compared with the method of directly adding a small amount of nano silver into plastic raw materials, the preparation method has the advantages that the silver quantum dots with smaller particle sizes are loaded in the nanofiber fibers with more added amounts, the silver quantum dots can be fully and uniformly dispersed in the plastic, the antibacterial performance of the plastic is improved, and local mildew of plastic tableware is avoided; simultaneously, through filling of nanometer silver particle and load at the pore structure and the surface of nanometer carbon fiber, can further improve nanometer carbon fiber's intensity to further improve the intensity of plastics tableware, through because silver quantum dot evenly distributed can improve the antibacterial property of plastics tableware on the one hand, on the other hand can make the plastics tableware have certain metallic luster, can satisfy the tableware demand in high-end place.

Detailed Description

The present invention is further illustrated in detail by the following examples, which are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.

Example 1

A biodegradable composite modified film/bag particle material is prepared from the following raw materials in parts by weight: 80 parts of oxidation modified high-amylose corn starch, 6.5 parts of 1-ethyl-3-methylimidazolium acetate, 3.5 parts of poloxamer, 4 parts of concentrated dried corn vinasse powder, 4 parts of coconut shell powder, 3 parts of a combined modifier, 2.4 parts of poly-3-hydroxybutyrate (PHB), 5.6 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 12 parts of polybutylene adipate-terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender from Pasteur, 0.7 part of maleic anhydride, 0.8 part of Polyoxyethylene (PEO), 4.5 parts of modified carbon nanofiber, 20 parts of nano calcium carbonate and 10 parts of nano zinc oxide; the preparation method comprises the following steps:

weighing the following components in parts by weight: adding 80 parts of oxidized modified high-amylose corn starch, 6.5 parts of 1-ethyl-3-methylimidazolyl acetate and 3.5 parts of poloxamer into a high-speed mixer, sealing a top cover, stirring for 5-12 minutes, oscillating for 30min at room temperature by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

weighing the following components in parts by weight: slowly adding 4 parts of corn vinasse concentrated dry powder, 4 parts of coconut shell powder and 3 parts of combined modifier into a high-speed stirrer, stirring at a high speed (2000r/min) for 5 minutes, then oscillating at room temperature for 30 minutes by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use; before the natural organic plant fiber material is used, drying treatment is carried out; the drying temperature is 100 ℃, and the drying time is 6 hours;

weighing the following components in parts by weight: adding 2.4 parts of poly 3-hydroxybutyrate (PHB), 5.6 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 12 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of Pasteur company, 0.7 part of maleic anhydride, 0.8 part of Polyoxyethylene (PEO), 4.5 parts of modified nano carbon fiber, 20 parts of nano calcium carbonate and 10 parts of nano zinc oxide into a mixer, sealing a top cover, stirring at a low speed (500 r/min)) for 10 minutes, and then keeping for later use;

adding the raw materials obtained in the step I into a first material inlet of a first temperature zone of a double-order series screw granulator set with the length-diameter ratio of 48:1 through a vacuum feeding machine conveying device, fully mixing → reacting until a second material inlet of a third temperature zone, adding the raw materials obtained in the step II, and fully mixing → reacting until a third material inlet of a fifth temperature zone, and adding the raw materials obtained in the step III; beginning from the first feeding port, the temperature of the temperature zone of each section of the screw cylinder of the extruder set to be 75-80 ℃, 80-85 ℃, 85-90 ℃, 95-100 ℃, 110-120 ℃, 120-130 ℃, 130-140 ℃, 140-150 ℃, 155-170 ℃, 135-140 ℃, 105-110 ℃, 75-80 ℃, 55-60 ℃ and the rotation speed of the screw is 150-200 r/min, and the biodegradable composite modified film/bag particle material is obtained by melt reaction extrusion → cooling → cutting → drying → packaging → from 55-170 ℃.

Various products such as films, bags, disposable gloves, table cloth, aprons, raincoats and the like are processed and produced in large scale by adopting general equipment such as a film blowing machine, a casting machine set and the like.

Example 2

A biodegradable composite modified film/bag particle material is prepared from the following raw materials in parts by weight: 80 parts of oxidation modified high-amylose wheat starch, 5 parts of 1-ethyl-3-methylimidazolyl acetate, 5 parts of epoxidized soybean oil, 5 parts of betel nut shell powder, 3 parts of wheat vinasse concentrated dry powder, 3 parts of a combined modifier, 2.4 parts of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, 5.6 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 5.6, 12 parts of polybutylene adipate-terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender from Pasteur company, 0.7 part of maleic anhydride, 0.8 part of Polyoxyethylene (PEO), 5 parts of modified nano carbon fiber, 18 parts of nano calcium carbonate and 12 parts of nano zinc oxide; the preparation method comprises the following steps:

weighing the following components in parts by weight: adding 80 parts of oxidized modified high-amylose wheat starch, 5 parts of 1-ethyl-3-methylimidazolyl acetate and 5 parts of epoxidized soybean oil into a high-speed mixer, sealing a top cover, stirring for 5-12 minutes, carrying out ultrasonic oscillation for 30min at room temperature, wherein the ultrasonic power is 480W, and sealing and placing the obtained material for 24h for later use;

weighing the following components in parts by weight: slowly adding 5 parts of betel nut shell powder, 3 parts of wheat vinasse concentrated dry powder and 3 parts of combined modifier into a high-speed stirrer, stirring at a high speed (2000 r/min)) for 5 minutes, oscillating at room temperature for 30 minutes by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

before the natural organic plant fiber material is used, drying treatment is carried out; the drying temperature is 90 ℃, and the drying time is 7 hours;

weighing the following components in parts by weight: adding 2.4 parts of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, 5.6 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 5.6, 12 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of Pasteur company, 0.7 part of maleic anhydride, 0.8 part of Polyoxyethylene (PEO), 5 parts of modified nano carbon fiber, 18 parts of nano calcium carbonate and 12 parts of nano zinc oxide into a mixer, sealing a top cover, stirring at a low speed (500 r/min)) for 10 minutes, and then standby;

Example 3

A biodegradable composite modified film/bag particle material is prepared from the following raw materials in parts by weight: 80 parts of oxidation modified high-amylose potato starch, 6 parts of lecithin, 4 parts of poloxamer, 4 parts of concentrated dried sugarcane vinasse powder, 4 parts of olive kernel powder, 3 parts of a combined modifier, 2.4 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 2.4, 5.6 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 12 parts of polybutylene adipate-terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender from Pasteur, 0.6 part of maleic anhydride, 0.9 part of Polyoxyethylene (PEO), 6 parts of modified carbon nanofiber, 19.5 parts of nano calcium carbonate, 10 parts of nano zinc oxide and 0.5 part of multi-walled carbon nanotube; the preparation method comprises the following steps:

weighing the following components in parts by weight: adding 80 parts of oxidized modified high-amylose potato starch, 6 parts of lecithin and 4 parts of poloxamer into a high-speed mixer, sealing a top cover, stirring for 5-12 minutes, oscillating for 30min at room temperature by ultrasonic waves with the ultrasonic wave power of 480W, and sealing and placing the obtained material for 24 hours for later use;

weighing the following components in parts by weight: slowly adding 4 parts of concentrated and dried sugarcane wine lees powder, 4 parts of olive pit powder and 3 parts of combined modifier into a high-speed stirrer, stirring at a high speed (2000 r/min)) for 5 minutes, then oscillating at room temperature for 30 minutes by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

before the natural organic plant fiber material is used, drying treatment is carried out; the drying temperature is 95 ℃, and the drying time is 7 hours;

weighing the following components in parts by weight: adding 2.4 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 2.4, 5.6 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 12 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of Pasteur company, 0.6 part of maleic anhydride, 0.9 part of Polyoxyethylene (PEO), 6 parts of modified nano carbon fiber, 19.5 parts of nano calcium carbonate, 10 parts of nano zinc oxide and 0.5 part of multi-walled carbon nanotube into a mixer, sealing a top cover, stirring at low speed (500 r/min)) for 10 minutes, and then reserving for later use;

Example 4

A biodegradable composite modified film/bag particle material is prepared from the following raw materials in parts by weight: 60 parts of oxidation modified high-amylose barley starch, 5 parts of lecithin, 3 parts of epoxidized soybean oil, 4 parts of sorghum vinasse concentrated dry powder, 4 parts of coffee grounds dry powder, 2 parts of a combined modifier, 6 parts of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, 6 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 18 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR (ADR) chain extender from Pasteur company, 0.6 part of maleic anhydride, 0.6 part of Polyoxyethylene (PEO), 7 parts of modified carbon nanofibers and 10 parts of nano zinc oxide; the preparation method comprises the following steps:

weighing the following components in parts by weight: adding 60 parts of oxidized modified high-amylose barley starch, 5 parts of lecithin and 3 parts of epoxidized soybean oil into a high-speed mixer together, sealing a top cover, stirring for 5-12 minutes, oscillating for 30min at room temperature by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

weighing the following components in parts by weight: slowly adding 4 parts of sorghum vinasse concentrated dry powder, 4 parts of coffee grounds dry powder and 2 parts of combined modifier into a high-speed stirrer, stirring at a high speed (2000 r/min)) for 5 minutes, then carrying out ultrasonic oscillation for 30 minutes at room temperature, wherein the ultrasonic power is 480W, and sealing and placing the obtained material for 24 hours for later use; before the natural organic plant fiber material is used, drying treatment is carried out; the drying temperature is 90 ℃, and the drying time is 7 hours;

weighing the following components in parts by weight: adding 6 parts of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, 6 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 18 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of Pasteur company, 0.6 part of maleic anhydride, 0.6 part of Polyoxyethylene (PEO), 7 parts of modified nano carbon fiber and 10 parts of nano zinc oxide into a mixer, sealing a top cover, and stirring at a low speed (500r/min) for 10 minutes for later use;

Example 5

A biodegradable composite modified film/bag particle material is prepared from the following raw materials in parts by weight: 60 parts of oxidation modified high-amylose mung bean starch, 3 parts of propylene glycol, 3 parts of polyethylene glycol stearate, 4 parts of green naked lees concentrated dry powder, 4 parts of cocoa extract dry powder, 2 parts of a combined modifier, 4.8 parts of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, 7.2 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 7.2, 18 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender from Pasteur company, 0.5 part of maleic anhydride, 0.5 part of Polyoxyethylene (PEO), 6.5 parts of modified nano carbon fiber and 10 parts of nano zinc oxide; the preparation method comprises the following steps:

weighing the following components in parts by weight: adding 60 parts of oxidized modified high-amylose mung bean starch, 3 parts of propylene glycol and 3 parts of polyethylene glycol stearate into a high-speed mixer, sealing a top cover, stirring for 5-12 minutes, oscillating for 30min at room temperature by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

weighing the following components in parts by weight: slowly adding 4 parts of green naked vinasse concentrated dry powder, 4 parts of cocoa extract dry powder and 2 parts of combined modifier into a high-speed stirrer, stirring at a high speed (2000 r/min)) for 5 minutes, then carrying out ultrasonic oscillation at room temperature for 30 minutes with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

before the natural organic plant fiber material is used, drying treatment is carried out; the drying temperature is 90 ℃, and the drying time is 8 hours;

weighing the following components in parts by weight: adding 4.8 parts of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, 7.2 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 7.2, 18 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of BASF company, 0.5 part of maleic anhydride, 0.5 part of Polyoxyethylene (PEO), 6.5 parts of modified nano carbon fiber and 10 parts of nano zinc oxide into a mixer, sealing a top cover, and stirring at a low speed (500 r/min)) for 10 minutes for later use;

Example 6

A biodegradable composite modified film/bag particle material is prepared from the following raw materials in parts by weight: 60 parts of oxidation modified high-amylose pea starch, 4 parts of propylene glycol, 3 parts of acetyl tributyl citrate, 3 parts of bamboo powder, 1 part of a combined modifier, 7.2 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 7.2, 4.8 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 18 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of Passion company, 0.5 part of maleic anhydride, 0.5 part of Polyoxyethylene (PEO), 5 parts of modified carbon nanofibers, 3 parts of octadecyl quaternary ammonium salt modified nano montmorillonite and 10 parts of nano zinc oxide; the preparation method comprises the following steps:

weighing the following components in parts by weight: adding 60 parts of oxidized modified high-amylose pea starch, 4 parts of propylene glycol and 3 parts of acetyl tributyl citrate into a high-speed mixer together, sealing a top cover, stirring for 5-12 minutes, oscillating for 30min at room temperature by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

weighing the following components in parts by weight: slowly adding 3 parts of bamboo powder and 1 part of combined modifier into a high-speed stirrer, stirring at high speed (2000 r/min)) for 5 minutes, oscillating at room temperature for 30 minutes by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use; before the natural organic plant fiber material is used, drying treatment is carried out; the drying temperature is 90 ℃, and the drying time is 8 hours;

weighing the following components in parts by weight: adding 7.2 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 7.2, 4.8 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 18 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of Pasteur company, 0.5 part of maleic anhydride, 0.5 part of Polyoxyethylene (PEO), 5 parts of modified nano carbon fiber, 3 parts of octadecyl quaternary ammonium salt modified nano montmorillonite and 10 parts of nano zinc oxide into a mixer, sealing a top cover, and stirring at a low speed (500 r/min)) for 10 minutes for later use;

Example 7

A biodegradable composite modified film/bag particle material is prepared from the following raw materials in parts by weight: 70 parts of oxidation modified high-amylose sweet potato starch, 4 parts of glycerol, 5 parts of polyethylene glycol stearate, 4 parts of reed powder, 4 parts of kapok fiber powder, 2 parts of a combined modifier, 6 parts of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, 5.2 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 16.8 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of BASF company, 0.7 part of maleic anhydride, 0.7 part of Polyoxyethylene (PEO), 8 parts of modified carbon nanofibers, 5 parts of nano calcium carbonate, 5 parts of graphene and 10 parts of nano zinc oxide; the preparation method comprises the following steps:

weighing the following components in parts by weight: adding 70 parts of oxidized modified high-amylose sweet potato starch, 4 parts of glycerol and 5 parts of polyethylene glycol stearate into a high-speed mixer together, sealing a top cover, stirring for 5-12 minutes, oscillating for 30min at room temperature by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

weighing the following components in parts by weight: slowly adding 4 parts of reed powder, 4 parts of wood wool fiber powder and 2 parts of combined modifier into a high-speed stirrer, stirring at a high speed (2000 r/min)) for 5 minutes, then oscillating at room temperature for 30 minutes by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

before the natural organic plant fiber material is used, drying treatment is carried out; the drying temperature is 100 ℃, and the drying time is 6 hours;

weighing the following components in parts by weight: adding 6 parts of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, 5.2 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 16.8 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of Pasteur company, 0.7 part of maleic anhydride, 0.7 part of Polyoxyethylene (PEO), 8 parts of modified nano carbon fiber, 5 parts of nano calcium carbonate, 5 parts of graphene and 10 parts of nano zinc oxide into a mixer, sealing a top cover, stirring at a low speed (500 r/min)) for 10 minutes, and then reserving for later use;

Example 8

A biodegradable composite modified film/bag particle material is prepared from the following raw materials in parts by weight: 70 parts of high amylose tapioca starch, 5 parts of glycerol, 3.5 parts of acetyl tributyl citrate, 3 parts of sunflower seed shell powder, 4 parts of durian peel fiber powder, 2 parts of a combined modifier, 4 parts of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, 7.2 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 7.2, 16.8 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of BASF company, 0.5 part of maleic anhydride, 0.7 part of Polyoxyethylene (PEO), 7 parts of modified carbon nanofiber, 1.5 parts of nano calcium carbonate, 3 parts of octadecyl quaternary ammonium salt modified nano montmorillonite, 5 parts of graphene, 10 parts of nano zinc oxide and 0.5 part of multi-walled carbon nanotube; the preparation method comprises the following steps:

weighing the following components in parts by weight: adding 70 parts of oxidation modified high amylose tapioca starch, 5 parts of glycerol and 3.5 parts of acetyl tributyl citrate into a high-speed mixer together, sealing a top cover, stirring for 5-12 minutes, carrying out ultrasonic oscillation for 30min at room temperature, wherein the ultrasonic power is 480W, and sealing and placing the obtained material for 24h for later use;

weighing the following components in parts by weight: slowly adding 3 parts of sunflower seed shell powder, 4 parts of durian peel fiber powder and 2 parts of combined modifier into a high-speed stirrer, stirring at a high speed (2000 r/min)) for 5 minutes, then oscillating at room temperature for 30 minutes by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use;

weighing the following components in parts by weight: adding 4 parts of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, 7.2 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 7.2, 16.8 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of Pasteur company, 0.5 part of maleic anhydride, 0.7 part of Polyoxyethylene (PEO), 7 parts of modified nano carbon fiber, 1.5 parts of nano calcium carbonate, 3 parts of octadecyl quaternary ammonium salt modified nano montmorillonite, 5 parts of graphene, 10 parts of nano zinc oxide and 0.5 part of multi-walled carbon nanotube into a mixer, sealing a top cover, and stirring at a low speed (500 r/min)) for 10 minutes for later use;

adding the raw materials obtained in the step I into a first material inlet of a first temperature zone of a double-order series screw granulator set with the length-diameter ratio of 48:1 through a vacuum feeding machine conveying device, fully mixing → reacting until a second material inlet of a third temperature zone, adding the raw materials obtained in the step II, and fully mixing → reacting until a third material inlet of a fifth temperature zone, and adding the raw materials obtained in the step III; beginning from the first feeding port, the temperature of the temperature zone of each section of the screw cylinder of the extruder set to be 75-80 ℃, 80-85 ℃, 85-90 ℃, 95-100 ℃, 110-120 ℃, 120-130 ℃, 130-140 ℃, 140-150 ℃, 155-170 ℃, 135-140 ℃, 105-110 ℃, 75-80 ℃, 55-60 ℃ and the rotation speed of the screw is 150-200 r/min, and the materials are subjected to melt reaction extrusion at 55-170 ℃, cooling → cutting → drying → sterilizing → packaging → obtaining the naturally biodegradable composite modified film/bag particle material.

Example 9

A composite modified film/bag particle material capable of being biodegraded naturally is prepared from the following raw materials in parts by weight: 35 parts of oxidation modified high amylose corn starch, 35 parts of cassava starch, 5 parts of xylitol, 3.5 parts of polyethylene glycol stearate, 3 parts of bamboo powder, 4 parts of concentrated dried sugarcane vinasse powder, 2 parts of a combined modifier, 5.6 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 5.6, 5.6 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 16.8 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of Pasteur, 0.7 part of maleic anhydride, 0.7 part of Polyoxyethylene (PEO), 5.5 parts of modified nano carbon fiber, 10 parts of nano calcium carbonate and 10 parts of nano zinc oxide; the preparation method comprises the following steps:

weighing the following components in parts by weight: adding 35 parts of oxidation modified high amylose corn starch, 35 parts of cassava starch, 5 parts of xylitol and 3.5 parts of polyethylene glycol stearate into a high-speed mixer, sealing a top cover, stirring for 5-12 minutes, carrying out ultrasonic oscillation for 30min at room temperature with the ultrasonic power of 480W, and sealing and placing the obtained material for 24h for later use;

weighing the following components in parts by weight: slowly adding 3 parts of bamboo powder, 4 parts of concentrated and dried sugarcane wine lees powder and 2 parts of combined modifier into a high-speed stirrer, stirring at a high speed (2000 r/min)) for 5 minutes, then oscillating at room temperature for 30 minutes by ultrasonic waves with the ultrasonic power of 480W, and sealing and placing the obtained material for 24 hours for later use; before the natural organic plant fiber material is used, drying treatment is carried out; the drying temperature is 90 ℃, and the drying time is 8 hours;

weighing the following components in parts by weight: adding 5.6 parts of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P34HB 5.6, 5.6 parts of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHx, 16.8 parts of polybutylene adipate terephthalate (PBAT), 1 part of epoxy functionalized ADR chain extender of Pasteur company, 0.7 part of maleic anhydride, 0.7 part of Polyoxyethylene (PEO), 5.5 parts of modified nano carbon fiber, 10 parts of nano calcium carbonate and 10 parts of nano zinc oxide into a mixer, sealing a top cover, stirring at a low speed (500 r/min)) for 10 minutes, and then reserving for later use;

Example 10

The only difference compared to example 1 is that the modified filamentous nanocarbon was not added.

Example 11

Compared with the embodiment 1, the difference is only that the common nano carbon fiber is added, and 0.1-0.3 part of nano silver is additionally added.

Example 12, compared to example 1, differs only in that: the added starch is ordinary starch which is not subjected to oxidation modification.

The following table 1 shows the corresponding performance data of the biodegradable composite modified film/bag particle material obtained in examples 1 and 10-12.

All foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. Or the equivalent substitution is made for some technical characteristics; the modifications, substitutions and other conceivable alternative means are within the scope of the present invention, and do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A biodegradable composite modified film/bag particle material is characterized in that: the feed is prepared from the following raw materials in parts by weight: 60-80 parts of oxidation modified high amylose starch, 6-10 parts of composite plasticizer, 3-8 parts of natural organic plant fiber material, 1-3 parts of combined modifier, 20-30 parts of biodegradable polyester compound, 1 part of functional assistant, 1-1.5 parts of modifier, 4.5-8 parts of modified carbon nanofibers and 10-30 parts of inorganic filler;

2. The biodegradable composite modified film/bag particle material as claimed in claim 1, wherein: the high amylose starch is one or a mixture of two of corn starch, wheat starch, potato starch, barley starch, mung bean starch, pea starch, sweet potato starch and cassava starch. The amylose content of the high amylose starch is 40-90%.

3. The biodegradable composite modified tableware particle material according to claim 1, wherein the oxidative modified high amylose starch is prepared by the following method: dispersing the high amylose starch into deionized water to obtain starch emulsion with the mass concentration of 40-50%, adding a certain amount of hydrogen peroxide, reacting at room temperature for 1-2h, finally washing, drying and crushing to obtain the oxidized modified high amylose starch; the amylose content of the high amylose starch is 40-90%.

4. The biodegradable composite modified film/bag particle material as claimed in claim 1, wherein the composite plasticizer is a mixture of two or more of polyethylene glycol stearate, 1-ethyl-3-methylimidazolium acetate, poloxamer, lecithin, tributyl acetylcitrate, propylene glycol, glycerol, xylitol, and epoxidized soybean oil; the molecular weight of the plasticizer is 76-2000.

5. The biodegradable composite modified film/bag particle material as claimed in claim 1, wherein: the natural organic plant fiber material is a mixture of two or more than two of corn vinasse concentrated dry powder, wheat vinasse concentrated dry powder, sugarcane vinasse concentrated dry powder, sorghum vinasse concentrated dry powder, green naked vinasse concentrated dry powder, coconut shell powder, betel nut shell powder, olive kernel powder, coffee residue dry powder, cocoa extract dry powder, bamboo powder, reed powder, sunflower seed shell powder, durian peel fiber powder and kapok fiber powder. The particle size of the natural organic plant fiber material is 800-2000 meshes.

6. The biodegradable composite modified film/bag particle material as claimed in claim 1, wherein said combination modifier is dodecenyl succinic anhydride, octenyl succinic anhydride, anhydrous ethanol and sodium hydroxide mixture; the mixture ratio was 1:1:4: 0.7.

7. The biodegradable composite modified film/bag particle material as claimed in claim 1, wherein: the biodegradable polyester compound is a blend of Polyhydroxyalkanoates (PHAs) and polybutylene adipate terephthalate (PBAT); the blend ratio was 4: 6.

8. The biodegradable composite modified film/bag particle material as claimed in claim 1, wherein the functional adjuvant is epoxy functionalized ADR chain extender from basf corporation; the modifier is a mixture of Polyoxyethylene (PEO) and maleic anhydride.

9. The biodegradable composite modified film/bag particle material as claimed in claim 1, wherein the inorganic filler is one or a mixture of two of graphene, nano zinc oxide, nano calcium carbonate, octadecyl quaternary ammonium salt modified nano montmorillonite and multi-wall carbon nanotube.

10. The preparation method of the naturally biodegradable composite modified film/bag particle material as claimed in claims 1-9, which is characterized by comprising the following steps: