CN111286164B - Biodegradable plastic and preparation method thereof - Google Patents
Biodegradable plastic and preparation method thereof Download PDFInfo
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- CN111286164B CN111286164B CN202010096454.9A CN202010096454A CN111286164B CN 111286164 B CN111286164 B CN 111286164B CN 202010096454 A CN202010096454 A CN 202010096454A CN 111286164 B CN111286164 B CN 111286164B
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- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Abstract
Discloses a biodegradable plastic, the raw materials of the plastic comprise modified thermoplastic starch and polybutylene terephthalate-co-adipate; and further comprises nano-hydroxyapatite. In addition, a preparation method of the biodegradable plastic is also disclosed. The compatibility of the biodegradable plastic is greatly improved, so that the mechanical property of the plastic is improved; the nano-hydroxyapatite accelerates the degradation of the biodegradable plastic, thereby improving the degradation performance.
Description
Technical Field
The invention belongs to the technical field of bio-based materials; relates to a degradable material and a preparation method thereof; more particularly, it relates to a biodegradable plastic and a preparation method thereof.
Background
The biodegradable plastic is an environment-friendly plastic which is developed rapidly in recent years and has excellent application performance. It is a type of plastic caused by the action of microorganisms (bacteria, molds, fungi, etc.) and algae. The material can be widely applied to the fields of catering, packaging, films and the like. After being used, the water-soluble organic fertilizer is degraded into non-toxic and harmless micromolecules in nature through proper conditions, thereby not only avoiding the waste of plastic products, but also realizing the recycling of energy.
According to the different types of the high polymer materials used in the biodegradable plastics, the biodegradable plastics can be divided into three types, namely natural high polymers, chemically synthesized high polymers and microorganism synthesized high polymers. Wherein, the natural polymer has rich sources and short regeneration period, but has poor thermal stability and poor melt fluidity, is difficult to form and process and cannot be used independently; the chemically synthesized polymer has excellent mechanical property and processing property, is widely applied, but has poor biodegradation property; the microbe synthesized high polymer has good biocompatibility, but the production cost of the material is higher.
Therefore, in most cases, a chemical synthetic polymer and a natural polymer are blended, and the obtained blended biodegradable plastic can be completely degraded in a natural environment. Carbon dioxide and water are generated during degradation, the carbon dioxide and the water can participate in carbon circulation in the nature, and the environment is not polluted. Therefore, the development of blended biodegradable plastics with good service performance is a research target for researchers.
Among natural polymer materials, starch is the most widely used degradation material, but natural starch has hydrogen bonds among molecules, is poor in solubility and thermoplasticity, good in hydrophilicity but not easy to dissolve in water, and cannot be subjected to melt extrusion thermal processing because the melting temperature is higher than the decomposition temperature. It is generally necessary to modify it by heat plastification to obtain heat plastified starch TPS, using plasticizers including, but not limited to, water, glycerol, urea, sorbitol, low molecular polysaccharides, etc. TPS has low cost and excellent degradation performance, but the mechanical property and the processing performance are still unsatisfactory; meanwhile, the storage performance is insufficient, the regeneration is easy to occur, the application range is greatly limited, and the blend with synthetic polymer is still needed.
Among chemically synthesized polymers, polybutylene terephthalate-co-adipate (PBAT) is a widely used material. PBAT is a ternary copolyester polymerized from terephthalic acid, adipic acid and 1, 4-butanediol by a direct esterification or transesterification process. The molar content of the terephthalic acid can reach 35 percent, so the PBAT has excellent thermal stability and mechanical property, and the tensile strength of Ecoflex commercial product of Germany BASF company can reach 36M Nm-2. However, the biodegradability of such materials is limited by the chemical structure and crystallinity of butylene terephthalate, and it is difficult to obtain the desired biodegradability.
Chinese patent application CN103881145A discloses a thermoplastic starch/poly (adipic acid)/butylene terephthalate composite material, which is prepared from the following components in parts by weight: 100 parts of thermoplastic starch and 100 parts of PBAT40-100 parts. The composite material has the advantages of excellent water resistance, good flexibility, easy molding and processing and the like. The processing fluidity, the mechanical property and the water resistance of the starch-based material can be obviously improved by blending the PBAT and the TPS; however, the mechanical properties and the degradation properties of the composite are still unsatisfactory.
Chinese patent application CN109504042A discloses a PHA-modified TPS/PBAT biodegradable resin, which is prepared from the following raw materials in parts by weight: TPS 1030%; PBAT 2050%; 130% of PHA. When TPS and PBAT are blended and granulated, a certain amount of PHA is added for modification, the PHA and starch in the TPS and esters in the PBAT have good compatibility, and the degradation resin can be uniformly combined with the TPS and the PBAT under the shearing action of a double screw. After PHA is added, the mechanical property of TPS/PBAT biodegradable resin can be greatly improved by more than 20%. However, the patent application does not describe the degradation properties of the biodegradable resin.
Zhang Hei et al (plastics industry, 2016, 44(2), P14-22) synthesized compatibilizer poly (butylene adipate-terephthalate) grafted maleic anhydride by melt grafting method using maleic anhydride and poly (butylene adipate-terephthalate) as raw materials, and prepared thermoplastic starch/poly (adipate-butylene terephthalate) blended alloy by melt extrusion blending method. The mechanical property of the blend alloy is improved by grafting the polybutylene adipate-terephthalate with the maleic anhydride, the tensile strength of the material is improved by 92.1 percent compared with the blend material without the compatibilizer, and the elongation at break of the material is improved by 83.7 percent compared with the blend material without the compatibilizer. However, the mechanical properties and the degradation properties of the composite are still unsatisfactory.
In view of the above-mentioned defects in the prior art, a biodegradable plastic with improved mechanical properties and degradation properties and a preparation method thereof are needed.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a biodegradable plastic having both good mechanical properties and good degradability, and a preparation method thereof.
In order to achieve the purpose, on one hand, the invention adopts the following technical scheme: a biodegradable plastic, the raw materials of the plastic comprise modified thermoplastic starch and polybutylene terephthalate-co-adipate; characterized in that the raw material further comprises nano hydroxyapatite.
The biodegradable plastic according to the invention, wherein the modified thermoplasticized starch is selected from maleic anhydride grafted thermoplasticized starches.
The biodegradable plastic is prepared from corn starch and glycerol through preplasticizing and extruding and granulating by a double-screw extruder.
The biodegradable plastic provided by the invention is characterized in that the mass ratio of the corn starch to the glycerol is 100 (20-40).
Preferably, the mass ratio of the corn starch to the glycerol is 100 (25-35).
In a specific embodiment, the mass ratio of corn starch to glycerol is 100: 30.
The biodegradable plastic provided by the invention is characterized in that the process parameters of the pre-plasticizing step are as follows: the temperature is 80-100 ℃ and the time is 4-8 h.
Preferably, the temperature is 85-95 ℃ and the time is 5-7 h.
In a specific embodiment, the temperature is 90 ℃ and the time is 6 h.
The biodegradable plastic is characterized in that each temperature zone of the double-screw machine is set as follows: a first zone 90 ℃; a second area is 110 ℃; a three-zone is 120 ℃; four areas are 130 ℃; a fifth area is 130 ℃; a six area is 130 ℃; seven areas are 135 ℃; eight regions are 135 ℃; nine areas are 135 ℃; the screw speed was 200 rpm.
The biodegradable plastic is prepared by extruding and granulating the modified thermoplastic starch by a double-screw extruder according to the mass ratio of 100 (4-8) and maleic anhydride.
Preferably, the mass ratio of the thermoplastic starch to the maleic anhydride is 100 (5-7).
In a particular embodiment, the mass ratio of the thermoplasticized starch and the maleic anhydride is 100: 6.
The biodegradable plastic is characterized in that each temperature zone of the double-screw machine is set as follows: a first zone is 135 ℃; a second zone is 140 ℃; a three region of 145 ℃; 155 ℃ in four areas; a fifth area is 160 ℃; a sixth zone 165 ℃; seven regions are 165 ℃; an eight zone 165 ℃; a nine-zone 160 ℃; the screw speed was 200 rpm.
The biodegradable plastic provided by the invention is characterized in that the mass ratio of the modified thermoplastic starch to the polybutylene terephthalate-co-adipate is (30-50) to (70-50).
Preferably, the mass ratio of the modified thermoplastic starch to the polybutylene terephthalate-co-adipate is (35-45) to (65-55).
In a specific embodiment, the mass ratio of the modified thermoplasticized starch to the polybutylene terephthalate-co-adipate is 40: 60.
The biodegradable plastic provided by the invention is characterized in that the average molecular weight Mn of polybutylene terephthalate-co-adipate is 9000-15000 dalton; the density is 1.22-1.28g/cm3。
Preferably, the polybutylene terephthalate-co-adipate has an average molecular weight Mn of 10000-14000 daltons; the density is 1.23-1.27g/cm3。
In a specific embodiment, polybutylene terephthalate-co-adipate has an average molecular weight Mn of 12000 daltons; the density was 1.26g/cm3。
The biodegradable plastic is characterized in that the nano hydroxyapatite is selected from nano hydroxyapatite with the length-diameter ratio of more than 4: 1.
Preferably, the nano hydroxyapatite is selected from nano hydroxyapatite with the length-diameter ratio of more than 6: 1.
In a specific embodiment, the nano-hydroxyapatite is selected from nano-hydroxyapatite having an aspect ratio of 7.5: 1. More specifically, the length of the nano hydroxyapatite is 150nm, and the diameter of the nano hydroxyapatite is 20 nm.
The biodegradable plastic provided by the invention is characterized in that the nano hydroxyapatite is further subjected to surface modification through reaction with a silane coupling agent KH 550.
The biodegradable plastic provided by the invention is characterized in that the mass ratio of the nano hydroxyapatite to the KH550 is 100 (15-25).
Preferably, the mass ratio of the nano hydroxyapatite to the KH550 is 100 (18-22).
In a specific embodiment, the mass ratio of the nano hydroxyapatite to the KH550 is 100: 20.
The biodegradable plastic provided by the invention is characterized in that the addition amount of the nano hydroxyapatite is 5-9wt% based on the mass sum of the modified thermoplastic starch and the polybutylene terephthalate-co-adipate.
Preferably, the nano hydroxyapatite is added in an amount of 6 to 8 wt% based on the sum of the mass of the modified thermoplastic starch and the mass of polybutylene terephthalate-co-adipate.
In a specific embodiment, the nano-hydroxyapatite is added in an amount of 7 wt% based on the sum of the mass of the modified thermoplasticized starch and the mass of polybutylene terephthalate-co-adipate.
In another aspect, the present invention further provides a preparation method of the biodegradable plastic, wherein the method comprises: and uniformly mixing the modified thermoplastic starch, the polybutylene terephthalate-co-adipate and the nano-hydroxyapatite, and extruding and granulating by a double-screw extruder to obtain the biodegradable plastic.
The preparation method comprises the following steps of: a first zone 130 ℃; a second area is 135 ℃; a third area is 140 ℃; the fourth zone is 145 ℃; a fifth area is 150 ℃; a sixth area is 150 ℃; a seventh area is 155 ℃; 155 ℃ in eight areas; a nine-zone 160 ℃; the screw speed was 200 rpm.
Compared with the prior art, the biodegradable plastic obtained by the invention greatly improves the compatibility between different components of the thermoplastic starch and the polybutylene terephthalate-co-adipate due to the use of the modified thermoplastic starch and the nano-hydroxyapatite, and simultaneously, the mechanical property of the biodegradable plastic is improved by the maleic anhydride grafted on the thermoplastic starch and the amino on the surface of the nano-hydroxyapatite. On the other hand, during degradation, the nano-hydroxyapatite is more easily corroded and broken, and the degradation of the biodegradable plastic is accelerated by combining the surface effect of the nano-material, so that the degradation performance is improved.
The materials, compounds, compositions, and components described herein can be used in, or in combination with, the methods and compositions described herein, or can be used in the practice of the methods and in the preparation of the compositions, or as products from the methods. It is to be understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each and every collective combination and permutation of these compounds may not be explicitly made, each is specifically contemplated and described herein. For example, if an extraction aid component is disclosed and discussed, and a number of alternative solid state forms of that component are discussed, each and every combination and permutation of the possible reference aid components and solid state forms is specifically contemplated unless specifically indicated to the contrary. This concept applies to all aspects of the invention, including but not limited to steps in methods of making and using the disclosed compositions. Thus, if there are a plurality of additional steps that can be performed it is understood that each of these additional steps can be performed by any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.
In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings:
it must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include both one and more than one (i.e., two, including two) unless the context clearly dictates otherwise.
Unless otherwise indicated, the numerical ranges in this disclosure are approximate and thus may include values outside of the stated ranges. The numerical ranges may be stated herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the numerical ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
Reference in the specification and concluding claims to parts by weight of a particular element or component in a composition or article refers to the weight relationship between that element or component and any other elements or components in the composition or article, expressed as parts by weight.
Unless specifically indicated to the contrary, or implied by the context or customary practice in the art, all parts and percentages referred to herein are by weight and the weight percentages of a component are based on the total weight of the composition or product in which it is included.
References to "comprising," "including," "having," and similar terms in this specification are not intended to exclude the presence of any optional components, steps or procedures, whether or not any optional components, steps or procedures are specifically disclosed. In order to avoid any doubt, all methods claimed through use of the term "comprising" may include one or more additional steps, apparatus parts or components and/or materials unless stated to the contrary. In contrast, the term "consisting of … …" excludes any component, step, or procedure not specifically recited or recited. Unless otherwise specified, the term "or" refers to the listed members individually as well as in any combination.
In the present invention, the nanometer means a scale range of 1 to 1000 nm; more preferably in the range of 1-500 nm; and, most preferably, in the scale range of 1-200 nm.
Furthermore, the contents of any referenced patent or non-patent document in this application are incorporated by reference in their entirety, especially with respect to definitions disclosed in the pertinent art (to the extent not inconsistent with any definitions specifically provided herein) and general knowledge.
Detailed Description
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and/or methods described and claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for.
Unless otherwise indicated, parts are parts by weight, temperatures are in degrees celsius or at ambient temperature, and pressures are at or near atmospheric. There are many variations and combinations of reaction conditions (e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
Modified heat plastified starch
The thermoplastic starch is obtained by pre-plasticizing corn starch and glycerol and extruding and granulating by a double-screw extruder. Wherein the mass ratio of the corn starch to the glycerol is 100: 30. The technological parameters of the preplasticizing step are as follows: the temperature is 90 ℃ and the time is 6 h. Each temperature zone of the double-screw machine is set as follows: a first zone 90 ℃; a second area is 110 ℃; a three-zone is 120 ℃; four areas are 130 ℃; a fifth area is 130 ℃; a six area is 130 ℃; seven areas are 135 ℃; eight regions are 135 ℃; nine areas are 135 ℃; the screw speed was 200 rpm.
The modified thermal plasticizing starch is obtained by extruding and granulating thermal plasticizing starch and maleic anhydride by a double-screw machine according to the mass ratio of 100: 6. Wherein, each temperature zone of the double-screw machine is set as follows: a first zone is 135 ℃; a second zone is 140 ℃; the three region is 145 ℃; 155 ℃ in four areas; a fifth area is 160 ℃; a sixth zone 165 ℃; seven regions 165 ℃; an eight zone 165 ℃; a nine area is 160 ℃; the screw speed was 200 rpm.
Surface modified nano-hydroxyapatite
Dissolving KH550 in ethanol/water solution with volume ratio of 9:1, and adding nano-hydroxyapatite after complete hydrolysis. Wherein, the length of the nano hydroxyapatite is 150nm, and the diameter is 20 nm. Reacting for 3 hours under the condition of stirring at room temperature, then adjusting the pH value to about 10.0 by using ammonia water, and continuing to react for 3 hours; filtering, drying, and drying at 130 deg.C for 1.5 h. Washing with anhydrous ethanol for 3 times, and freeze drying to obtain surface modified nano-hydroxyapatite. SEM observation results show that the length and the diameter of the nano-hydroxyapatite have no obvious change before and after surface modification.
Example 1
Modified heat plastified starch and polybutylene terephthalate-co-adipate (average molecular weight Mn 12000 dalton; density 1.26 g/cm) in a mass ratio of 40:603) Mixing uniformly; then based on the total mass of the modified thermoplastic starch and the polybutylene terephthalate-co-adipate, 7 wt% of surface modified nano-hydroxyapatite is added and the mixture is continuously and uniformly mixed. And then extruding and granulating by a double-screw extruder to obtain the biodegradable plastic. Wherein, each temperature zone of the double-screw machine is set as follows: a first zone 130 ℃; a second area is 135 ℃; a third area is 140 ℃; the fourth zone is 145 ℃; a fifth area is 150 ℃; a sixth area is 150 ℃; seven areas are 155 ℃; 155 ℃ in eight areas; a nine-zone 160 ℃; the screw speed was 200 rpm.
Example 2
Modified heat plastified starch and polybutylene terephthalate-co-adipate (average molecular weight Mn 12000 dalton; density 1.26 g/cm) in a mass ratio of 45:553) Mixing uniformly; then based on the total mass of the modified thermoplastic starch and the polybutylene terephthalate-co-adipate, 8 wt% of surface modified nano-hydroxyapatite is added and the mixture is continuously and uniformly mixed. And then extruding and granulating by a double-screw extruder to obtain the biodegradable plastic. Wherein, each temperature zone of the double-screw machine is set as follows: a first zone 130 ℃; a second area is 135 ℃; a third area is 140 ℃; the fourth zone is 145 ℃; a fifth area is 150 ℃; a sixth area is 150 ℃; a seventh area is 155 ℃; 155 ℃ in eight areas; a nine-zone 160 ℃; the screw speed was 200 rpm.
Example 3
Modified heat plastified starch and polybutylene terephthalate-co-adipate (average molecular weight Mn 12000 dalton; density 1.26 g/cm) in a mass ratio of 35:653) Mixing uniformly; then based on the total mass of the modified thermoplastic starch and the polybutylene terephthalate-co-adipate, 6 wt% of surface modified nano-hydroxyapatite is added and the mixture is continuously and uniformly mixed. Then extruded by a twin-screw extruderThe granules are made into biodegradable plastic. Wherein, each temperature zone of the double-screw machine is set as follows: a first zone 130 ℃; a second area is 135 ℃; a third area is 140 ℃; the fourth zone is 145 ℃; a fifth area is 150 ℃; a sixth area is 150 ℃; seven areas are 155 ℃; 155 ℃ in eight areas; a nine-zone 160 ℃; the screw speed was 200 rpm.
Comparative example 1
The other conditions were the same as in example 1, except that nano-hydroxyapatite which was not surface-modified was used.
Comparative example 2
The other conditions were the same as in example 1, except that spherical hydroxyapatite having an average particle diameter of 12 μm was used.
Comparative example 3
The other conditions were the same as in example 1, except that nano-hydroxyapatite having a length of 100nm and a diameter of 30nm was used.
Comparative example 4
The other conditions were the same as in example 1, but using a heat-plasticized starch.
Performance testing
The biodegradable plastics of examples 1-3 and comparative examples 1-4 were made into standard test specimens of a dumbbell type by an injection molding machine in accordance with the relevant national standard GB/T1040-2018, and the respective tensile strengths (MPa) were measured at a tensile speed of 50 mm/min. The final release amount of carbon dioxide after the biodegradable plastics of examples 1-3 and comparative examples 1-4 are degraded for 45 days is tested according to the relevant national standard GB/T19277-2011, and the biodegradation rate (%) of the material is expressed by the ratio of the actual release amount of carbon dioxide to the theoretical maximum release amount of carbon dioxide.
The results are shown in Table 1.
TABLE 1
| Sample (I) | Tensile Strength (MPa) | Biodegradation Rate (%) |
| Example 1 | 19.3 | 91 |
| Example 2 | 18.5 | 87 |
| Example 3 | 21.4 | 84 |
| Comparative example 1 | 15.7 | 85 |
| Comparative example 2 | 12.9 | 49 |
| Comparative example 3 | 17.8 | 73 |
| Comparative example 4 | 9.6 | 82 |
The results show that compared with comparative examples 1-4, the biodegradable plastic obtained in examples 1-3 of the present invention uses the modified thermoplastic starch and the nano-hydroxyapatite, so that the compatibility between different components of the thermoplastic starch and the polybutylene terephthalate-co-adipate is greatly improved, and the mechanical properties of the biodegradable plastic are improved by the maleic anhydride grafted on the thermoplastic starch and the amino group on the surface of the nano-hydroxyapatite. On the other hand, during degradation, the nano-hydroxyapatite is more easily corroded and broken, and the degradation of the biodegradable plastic is accelerated by combining the surface effect of the nano-material, so that the degradation performance is improved.
It should be understood that the detailed description of the invention is intended to illustrate the spirit and principles of the invention, and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
Claims (4)
1. A biodegradable plastic, the raw materials of the plastic comprise modified thermoplastic starch and polybutylene terephthalate-co-adipate; characterized in that the raw material further comprises nano hydroxyapatite;
wherein the modified heat plastified starch is selected from the group consisting of maleic anhydride grafted heat plastified starch; the modified thermoplastic starch is obtained by extruding and granulating the thermoplastic starch and maleic anhydride by a double-screw extruder according to the mass ratio of 100 (4-8);
the mass ratio of the modified thermoplastic starch to the polybutylene terephthalate-co-adipate is (30-50) to (70-50);
the nano hydroxyapatite is selected from nano hydroxyapatite with the length-diameter ratio of more than 4: 1; the nano hydroxyapatite is further subjected to surface modification through reaction with a silane coupling agent KH 550;
the nano hydroxyapatite is added in an amount of 5-9wt% based on the total mass of the modified thermoplastic starch and the polybutylene terephthalate-co-adipate.
2. The biodegradable plastic according to claim 1, wherein each temperature zone of the twin-screw machine is set as follows: a first zone is 135 ℃; a second zone is 140 ℃; a three region of 145 ℃; 155 ℃ in four areas; a fifth area is 160 ℃; a sixth zone 165 ℃; seven regions are 165 ℃; an eight zone 165 ℃; a nine-zone 160 ℃; the screw speed was 200 rpm.
3. A method for preparing the biodegradable plastic according to claim 1 or 2, the method comprising: the biodegradable plastic according to claim 1 or 2 is obtained by uniformly mixing the modified thermoplastic starch, the polybutylene terephthalate-co-adipate and the nano-hydroxyapatite and performing extrusion granulation by a twin-screw extruder.
4. The production method according to claim 3, wherein each temperature zone of the twin-screw machine is set as follows: a first zone 130 ℃; a second area is 135 ℃; a third area is 140 ℃; the fourth zone is 145 ℃; a fifth area is 150 ℃; a sixth area is 150 ℃; seven areas are 155 ℃; 155 ℃ in eight areas; a nine-zone 160 ℃; the screw speed was 200 rpm.
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