CN113354843B - Preparation method and application of high-molecular degradable master batch - Google Patents
Preparation method and application of high-molecular degradable master batch Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a high-molecular degradable master batch, wherein the ratio t1/t2 of 60 ℃ aerobic degradation time t1 to 60 ℃ anaerobic degradation time t2 of the degradable master batch is 5-10, and the total content of metal ions with atomic numbers larger than 30 in the degradable master batch is less than 100ppm. The high-molecular degradable master batch has strong processing adaptability and high biodegradation activity, can assist the beginning degradation of polyolefin, polyester and polyamide, improves the biodegradation rate, and meets the requirement of meeting the biodegradation.
Description
Technical Field
The invention relates to the technical field of composite material production, in particular to a preparation method and application of a high-molecular degradable master batch.
Background
The plastic is a safe, durable and low-cost product, and is widely applied to daily life in industries such as daily necessities, packaging, buildings and the like. The use of general plastics such as PE and PP, synthetic fibers such as PA and the like, and synthetic polyesters such as PBT and PET and the like facilitates the physical life of people, and the produced waste can not be decomposed under natural conditions, thereby causing serious environmental pollution.
In response to the above problems, the search for environmentally friendly materials has become a common goal of many researchers. Therefore, biodegradable polymer materials such as PBAT and PGA have been the focus of research.
For example, PBAT has better molecular flexibility and biodegradability, is a biodegradable polymer which is most widely applied at present, and is harmless to the environment when the PBAT is subjected to composting test; PGA is a synthetic polymer material having good biodegradability and biocompatibility, and PGA as a material is gradually degraded after use for a certain period of time, and finally becomes water and carbon dioxide harmless to the human body, animals and plants, and natural environments. The two are added with part of additives according to a certain proportion to obtain the degradable material which is environment-friendly and can be applied to the fields of packaging, medical treatment, films and the like.
Chinese patent (ZL 201310067471. X) discloses a controllable oxidation biodegradable plastic masterbatch, which comprises: inorganic filler, carrier, oxidative degradation promoter, biodegradation promoter and degradation control agent; wherein the degradation control agent is an antioxidant.
Chinese patent (CN 200410043710.9) relates to a degradable master batch made of plant fiber and a process for manufacturing films, sheets and tableware by using the master batch, wherein the master batch comprises the following components in percentage by weight: 5-75% of plant fiber, 5-50% of carbon dioxide polymer, 5-30% of polyvinyl alcohol, 1-10% of compatilizer and 1-15% of plasticizer, wherein the components are fully stirred by a mixer and then are fed into a plastic granulator to be prepared into master batch; sending the master batch into a plastic blow molding extruder or a casting machine to be processed into a film or a sheet; and (3) performing injection molding on the film or the sheet by using a plastic injection molding machine to obtain tableware.
Chinese patent (ZL 201410029614.2) discloses a biodegradable plastic master batch, which mainly comprises the following components: 20 to 65 percent of modified compatilizer, 20 to 35 percent of biological catalyst, 20 to 35 percent of nutritional agent, 10 to 15 percent of catalyst, 0.5 to 6 percent of surfactant and 1 to 3 percent of glycerol; firstly, heating the catalyst to 200-300 ℃ for high-temperature dehydration, drying for 1-2 hours, and grinding to more than 5000 meshes; then adding the nutrient, the surfactant and the glycerol into a catalyst for adsorption, stirring at a low speed for 3-5 minutes by using a high-speed stirrer at the temperature of 35-50 ℃ until all liquid is fully absorbed, and then presenting the flowing state of powder; directly putting the modified compatilizer, the biocatalyst and the stirred catalyst into a kneader for processing; the biodegradable master batch is prepared, and the sum of the components of the master batch is not more than 100%.
Chinese patent ZL 201110214966.1 discloses a non-petroleum base complete degradable color master batch, which comprises the following formula components in percentage by weight: 30-50% of carrier, 20-70% of pigment and 0-60% of filler, wherein the carrier is a bio-based completely degradable polymer, and the bio-based completely degradable polymer comprises one or two of polyhydroxyalkanoate PHA series, polylactic acid PLA and polybutylene succinate PBS.
At present, the degradation of macromolecules mainly comprises modes such as aerobic degradation, photodegradation, anaerobic degradation and the like, and the conventional degradation process mainly breaks macromolecule chains into small molecular fragments which are disordered and uncontrollable; the existing biodegradation process is usually to accelerate the degradation of molecules by utilizing the degradation of enzymes through microbial enzyme interaction.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method and application of a high-molecular degradable master batch.
The purpose of the invention is realized by the following technical scheme:
the high-molecular degradable master batch is characterized in that the melting index of the high-molecular degradable master batch is 3-30 g/min under the condition of 2.16kg and the temperature of 190 ℃, and the melting range is 90-165 ℃; the ratio t1/t2 of the 60 ℃ aerobic degradation time t1 to the 60 ℃ anaerobic degradation time t2 of the degradable master batch is 5-10, and the total content of metal ions with atomic numbers larger than 30 in the degradable master batch is less than 100ppm.
The macromolecular degradable master batch comprises the following main components in percentage by weight:
a preparation method of high-molecular degradable master batch comprises the following steps:
the method comprises the following steps: preparation of modified polyglycolic acid
Using glycolic acid as a raw material, adopting a titanium modified catalyst, firstly carrying out esterification reaction on the glycolic acid at the temperature of 190-210 ℃, adopting nitrogen as protective gas in the esterification reaction process, carrying out normal pressure reaction, carrying out polycondensation reaction at the temperature of 230-250 ℃ when the esterification water yield is more than 90%, controlling the polycondensation vacuum degree to be 30-500 Pa, and finishing the reaction when the molecular weight is increased to 8000-12000 to prepare the modified polyglycolic acid; the content of the titanium modified catalyst in the modified polyglycolic acid is 50-200 ppm;
step two: preparation of master batch with degradation function
And (2) taking the modified polyglycolic acid, calcium lactate, calcium stearate, ferric stearate and manganese stearate prepared in the step one as raw materials, dispersing and mixing the raw materials according to a proportion, and then carrying out melt extrusion granulation by adopting a double-screw extruder to prepare the master batch with the degradation function.
Step three: preparing bioactive functional master batch
The preparation method comprises the following steps of taking PBAT, an auxin promoter, bacillus and an auxiliary agent as raw materials, firstly dispersing and melting the auxiliary agent, the auxin promoter and the bacillus at a high speed at a temperature of 80-90 ℃, then adding the PBAT into a dispersion system, and then extruding and granulating by adopting a low-temperature high-pressure extrusion method to prepare the bioactive functional master batch;
step four: preparing high molecular degradable master batch
And (3) taking the degraded functional master batch prepared in the second step and the bioactive functional master batch prepared in the third step as raw materials, adopting a melt blending method, taking the degraded functional master batch prepared in the second step as a main melt, taking the bioactive functional master batch prepared in the third step as a side material, and carrying out melt extrusion granulation, wherein the retention time of the side material in an extruder is controlled to be 5-30 s, and the melt granulation processing temperature is 110-180 ℃.
The preparation method of the titanium modified catalyst comprises the steps of taking tetrabutyl titanate and glycollic acid as raw materials, taking nitrogen as protective gas, carrying out ester exchange reaction at 120 ℃ for 1-1.5 h, then adopting a vacuum extraction method, controlling the vacuum degree at 120 ℃ to be 1000-5000 Pa, carrying out vacuum extraction on unreacted tetrabutyl titanate and butanol products, and carrying out vacuum extraction for 30min to obtain the titanium modified catalyst; the molar ratio of the tetrabutyl titanate to the glycollic acid is 1: 4.15-1: 4.55.
Wherein the PBAT is powder of PBAT, and the particle size of the powder is 0.1-2.0 mm; the auxin promoter is cow milk extract with nitrogen content more than 5%, bacillus is alcaligenes, preferably lactobacillus bulgaricus, and the auxiliary agent is polypropylene glycol 600.
Wherein the processing temperature of the double-screw extruder in the step two is 130-180 ℃.
Wherein the melt ratio of the degradation functional master batch prepared in the second step and the bioactive functional master batch prepared in the third step is 1: 0.5-1: 3.
The application of the high-molecular degradable master batch obtained by the preparation method in high-molecular composite materials. Wherein the mass fraction of the high molecular degradable master batch in the high molecular composite material is 3-15%.
Polyglycolic acid has excellent biodegradation characteristics, repeating units in the molecular structure of the polyglycolic acid are similar to the structure of polypropylene, and during reprocessing and degradation, the degradation of the polyglycolic acid can aggregate the production of microorganisms similar to the degraded molecular structure of the polyglycolic acid, and the degradation of the structure of the polypropylene and the like can be accelerated by utilizing the mutual attraction effect among molecules and the degradation of the structure of the polyvinylalcohol; in order to further optimize the biodegradation characteristic, a polyglycolic acid structure with the molecular weight of 8000-12000 is adopted, the molecular structure is closer to the base chain segment of polypropylene and the like after photodegradation, the microbial degradation activity and the biological similarity of degradation are more similar, and the degradation of materials such as high polymer material polypropylene and the like is more facilitated.
In the growth process of microorganisms, the bacteria content is high and the bacteria are mixed, the lactic acid bacteria, the alcaligenes and the like can effectively decompose polyester and a high molecular chain segment structure containing ester bonds, the decomposition of biological materials is rapidly accelerated by utilizing materials such as lactic acid, ammonium salt and the like generated by the metabolism of the microorganisms, and meanwhile, the moisture absorption effect of stearate is utilized to maintain the humidity balance in the degradation environment and improve the biological activity; the optical degradation activity of stearate is utilized to endow the stearate with excellent optical degradation characteristics, and meanwhile, the high polymer material is rapidly degraded to the required molecular weight and molecular chain segment through the synergistic effect of ferric stearate and manganese stearate.
Conventional auxin accelerators, bacilli and the like have poor heat-resistant stability, and in order to avoid the influence of long-time high temperature on the performance of the auxin, active materials such as polypropylene glycol and the like are adopted for melting and dispersing and then are extruded and granulated at low temperature, so that the failure of bioactive materials is avoided; meanwhile, the polypropylene glycol is a grease-like material, has the purposes of lubricating and protecting bioactive materials, further ensures that the materials are subjected to high temperature, and also achieves the purpose of plasticizing and granulating.
Compared with the prior art, the invention has the following positive effects:
this application is through introducing the material that has photodegradation, realize the preliminary degradation to macromolecular material, make macromolecular material fracture into the micromolecule fragment, then the reuse has bioactive material, through promoting biological growth, in the short time, decompose a large amount of enzymes, and combine microbial growth hormone, a large amount of microorganisms are cultivateed to short time class, do benefit to the degradation process of microorganism, realize behind the preliminary molecular fracture, then carry out the biodegradation process again. In order to guarantee the failure of the high-temperature microbial active material in the reprocessing process, the uniform addition of the material is realized by adopting the processes of low-temperature high-pressure extrusion and lateral material, the problem of rapid degradation of the material is avoided, the excellent biodegradation activity is achieved, and the material is widely applied to polyolefin, polyester and polyamide.
Drawings
Fig. 1 is a schematic diagram of a preparation method and an application preparation process of a high-molecular degradable master batch.
Detailed Description
The following provides specific embodiments of the preparation method and the application of the high-molecular degradable master batch.
Example 1
The melt index of the high-molecular degradable master batch is 3g/min (2.16kg, 190 ℃) and the melting range is 90 ℃; the ratio t1/t2 of the 60 ℃ aerobic degradation time t1 to the 60 ℃ anaerobic degradation time t2 of the degradable master batch is 5, and the total content of metal ions with atomic numbers larger than 30 in the degradable master batch is less than 100ppm.
A preparation method of high-molecular degradable master batches comprises the following specific steps:
the macromolecular degradable master batch comprises the following main components in percentage by weight:
the preparation method of the high-molecular degradable master batch comprises the following steps:
preparation of modified polyglycolic acid
Using glycolic acid as a raw material, adopting a titanium modified catalyst, firstly carrying out esterification reaction on the glycolic acid at 190-210 ℃, adopting nitrogen as protective gas in the esterification reaction process, carrying out normal pressure reaction, carrying out polycondensation reaction at 230-250 ℃ when the esterification water yield is more than 90%, controlling the polycondensation vacuum degree to be 30-500 Pa, and finishing the reaction when the molecular weight is increased to 8000 to prepare the modified polyglycolic acid; the content of the titanium modified catalyst in the modified polyglycolic acid is 50ppm;
the preparation method of the titanium modified catalyst comprises the steps of taking tetrabutyl titanate and glycollic acid as raw materials, taking nitrogen as protective gas, carrying out ester exchange reaction at 120 ℃ for 1-1.5 h, then adopting a vacuum extraction method, controlling the vacuum degree at 120 ℃ to be 1000-5000 Pa, carrying out vacuum extraction on unreacted tetrabutyl titanate and butanol products, and carrying out vacuum extraction for 30min to obtain the titanium modified catalyst; the molar ratio of tetrabutyl titanate to glycolic acid is 1: 4.15.
(II) preparation of master batch with degradation function
Taking the modified polyglycolic acid, calcium lactate, calcium stearate, ferric stearate and manganese stearate prepared in the step (one) as raw materials, dispersing and mixing the raw materials according to a proportion, and then carrying out melt extrusion granulation by adopting a double-screw extruder to prepare the master batch with the degradation function;
the processing temperature of the double-screw extruder is 130-180 ℃.
Preparation of (III) bioactive functional master batch
The preparation method comprises the following steps of taking PBAT, an auxin promoter, bacillus and an auxiliary agent as raw materials, firstly dispersing and melting the auxiliary agent, the auxin promoter and the bacillus at a high speed at a temperature of 80-90 ℃, then adding the PBAT into a dispersion system, and then extruding and granulating by adopting a low-temperature high-pressure extrusion method to prepare the bioactive functional master batch;
the PBAT is PBAT powder, and the particle size of the PBAT powder is 0.1mm; the auxin promoter is cow milk extract with nitrogen content more than 5%, bacillus is alcaligenes, preferably lactobacillus bulgaricus, and the auxiliary agent is polypropylene glycol 600.
(IV) preparation of high molecular degradable master batch
And (3) taking the degraded functional master batch prepared in the step (II) and the bioactive functional master batch prepared in the step (III) as raw materials, adopting a melt blending method, taking the degraded functional master batch prepared in the step (II) as a main melt, taking the bioactive functional master batch prepared in the step (III) as a side material, and carrying out melt extrusion granulation, wherein the retention time of the side material in an extruder is controlled to be 5s, and the melt granulation processing temperature is 110-180 ℃.
The melt ratio of the degradation functional master batch prepared in the step (II) to the biological activity functional master batch prepared in the step (III) is 1: 0.5.
The application method of the high-molecular degradable master batch adopts a melt extrusion method, the high-molecular degradable master batch is used as a functional component, the high-molecular resin and an additive are used as main raw materials, and the high-molecular composite material such as a plate, a sheet, a film and the like is prepared by melt processing, wherein the high-molecular resin is one of polyolefin, polyester and polyamide polymer, and the mass fraction of the high-molecular degradable master batch in the high-molecular composite material is 3%.
Example 2
The melt index of the high-molecular degradable master batch is 30g/min (2.16kg, 190 ℃), and the melting range is 165 ℃; the ratio t1/t2 of 60 ℃ aerobic degradation time t1 to 60 ℃ anaerobic degradation time t2 of the degradable master batch is 10, and the total content of metal ions with atomic numbers larger than 30 in the degradable master batch is less than 100ppm.
A preparation method of a high-molecular degradable master batch comprises the following specific steps:
the macromolecular degradable master batch comprises the following main components in percentage by weight:
the preparation method of the high-molecular degradable master batch comprises the following steps:
preparation of modified polyglycolic acid
Using glycolic acid as a raw material, adopting a titanium modified catalyst, firstly carrying out esterification reaction on the glycolic acid at 190-210 ℃, adopting nitrogen as protective gas in the esterification reaction process, carrying out normal pressure reaction, carrying out polycondensation reaction at 230-250 ℃ when the esterification water yield is more than 90%, controlling the polycondensation vacuum degree to be 30-500 Pa, and finishing the reaction when the molecular weight is increased to 12000 to prepare the modified polyglycolic acid; the content of the titanium modified catalyst in the modified polyglycolic acid is 200ppm;
the preparation method of the titanium modified catalyst comprises the steps of taking tetrabutyl titanate and glycollic acid as raw materials, taking nitrogen as protective gas, carrying out ester exchange reaction at 120 ℃ for 1-1.5 h, then adopting a vacuum extraction method, controlling the vacuum degree at 120 ℃ to be 1000-5000 Pa, carrying out vacuum extraction on unreacted tetrabutyl titanate and butanol products, and carrying out vacuum extraction for 30min to obtain the titanium modified catalyst; the molar ratio of tetrabutyl titanate to glycolic acid is 1: 4.55.
(II) preparation of master batch with degradation function
Taking the modified polyglycolic acid, calcium lactate, calcium stearate, ferric stearate and manganese stearate prepared in the step (one) as raw materials, dispersing and mixing the raw materials according to a proportion, and then carrying out melt extrusion granulation by adopting a double-screw extruder to prepare the master batch with the degradation function;
the processing temperature of the double-screw extruder is 130-180 ℃.
Preparation of (III) bioactive functional master batch
The preparation method comprises the following steps of taking PBAT, an auxin promoter, bacillus and an auxiliary agent as raw materials, firstly dispersing and melting the auxiliary agent, the auxin promoter and the bacillus at a high speed at a temperature of 80-90 ℃, then adding the PBAT into a dispersion system, and then extruding and granulating by adopting a low-temperature high-pressure extrusion method to prepare the bioactive functional master batch;
the PBAT is powder of PBAT, and the particle size of the powder is 2.0mm; the auxin promoter is cow milk extract with nitrogen content more than 5%, bacillus is alcaligenes, preferably lactobacillus bulgaricus, and the auxiliary agent is polypropylene glycol 600.
(IV) preparation of high molecular degradable master batch
And (2) taking the degradation functional master batches prepared in the step (II) and the bioactive functional master batches prepared in the step (III) as raw materials, adopting a melt blending method, taking the degradation functional master batches prepared in the step (II) as a main melt, taking the bioactive functional master batches prepared in the step (III) as side materials, and carrying out melt extrusion granulation, wherein the retention time of the side materials in an extruder is controlled to be 30s, and the melt granulation processing temperature is 110-180 ℃.
The melt ratio of the degradation functional master batch prepared in the step (II) to the biological activity functional master batch prepared in the step (III) is 1:3.
The application method of the high-molecular degradable master batch adopts a melt extrusion method, the high-molecular degradable master batch is used as a functional component, the high-molecular resin and an additive are used as main raw materials, and the high-molecular composite material such as a plate, a sheet, a film and the like is prepared by melt processing, wherein the high-molecular resin is one of polyolefin, polyester and polyamide polymer, and the mass fraction of the high-molecular degradable master batch in the high-molecular composite material is 15%.
Example 3
The melt index of the high-molecular degradable master batch is 20g/min (2.16kg, 190 ℃) and the melting range is 135 ℃; the ratio t1/t2 of the 60 ℃ aerobic degradation time t1 to the 60 ℃ anaerobic degradation time t2 of the degradable master batch is 8, and the total content of metal ions with atomic numbers larger than 30 in the degradable master batch is less than 100ppm.
A preparation method of a high-molecular degradable master batch comprises the following specific steps:
the macromolecular degradable master batch comprises the following main components in percentage by weight:
the preparation method of the high-molecular degradable master batch comprises the following steps:
preparation of modified polyglycolic acid
Using glycolic acid as a raw material, adopting a titanium modified catalyst, firstly carrying out esterification reaction on the glycolic acid at 190-210 ℃, adopting nitrogen as protective gas in the esterification reaction process, carrying out normal pressure reaction, carrying out polycondensation reaction at 230-250 ℃ when the esterification water yield is more than 90%, controlling the polycondensation vacuum degree to be 30-500 Pa, and finishing the reaction when the molecular weight is increased to 9800 to prepare the modified polyglycolic acid; the content of the titanium modified catalyst in the modified polyglycolic acid is 100ppm;
the preparation method of the titanium modified catalyst comprises the steps of taking tetrabutyl titanate and glycollic acid as raw materials, taking nitrogen as protective gas, carrying out ester exchange reaction at 120 ℃ for 1-1.5 h, then adopting a vacuum extraction method, controlling the vacuum degree at 120 ℃ to be 1000-5000 Pa, carrying out vacuum extraction on unreacted tetrabutyl titanate and butanol products, and carrying out vacuum extraction for 30min to obtain the titanium modified catalyst; the molar ratio of tetrabutyl titanate to glycolic acid is 1: 4.25.
(II) preparation of master batch with degradation function
Taking the modified polyglycolic acid, calcium lactate, calcium stearate, ferric stearate and manganese stearate prepared in the step (one) as raw materials, dispersing and mixing the raw materials according to a proportion, and then carrying out melt extrusion granulation by adopting a double-screw extruder to prepare the master batch with the degradation function;
the processing temperature of the double-screw extruder is 130-180 ℃.
Preparation of (III) bioactive functional master batch
The method comprises the following steps of taking PBAT, an auxin promoter, bacillus and an auxiliary agent as raw materials, firstly dispersing and melting the auxiliary agent, the auxin promoter and the bacillus at a high speed at a temperature of between 80 and 90 ℃, then adding the PBAT into a dispersion system, and then extruding and granulating by adopting a low-temperature high-pressure extrusion method to prepare a biological activity functional master batch;
the PBAT is powder of PBAT, and the particle size of the powder is 0.15mm; the auxin promoter is cow milk extract with nitrogen content more than 5%, bacillus is alcaligenes, preferably lactobacillus bulgaricus, and the auxiliary agent is polypropylene glycol 600.
(IV) preparation of high molecular degradable master batch
And (2) taking the degradation functional master batches prepared in the step (II) and the bioactive functional master batches prepared in the step (III) as raw materials, adopting a melt blending method, taking the degradation functional master batches prepared in the step (II) as a main melt, taking the bioactive functional master batches prepared in the step (III) as side materials, and carrying out melt extrusion granulation, wherein the retention time of the side materials in an extruder is controlled to be 5 seconds, and the melt granulation processing temperature is 110-180 ℃.
The melt ratio of the degradation functional master batch prepared in the step (II) to the biological activity functional master batch prepared in the step (III) is 1: 1.5.
The application method of the high-molecular degradable master batch adopts a melt extrusion method, the high-molecular degradable master batch is used as a functional component, the high-molecular resin and an additive are used as main raw materials, and the high-molecular composite material such as a plate, a sheet, a film and the like is prepared by melt processing, wherein the high-molecular resin is one of polyolefin, polyester and polyamide polymer, and the mass fraction of the high-molecular degradable master batch in the high-molecular composite material is 5%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (5)
1. The high-molecular degradable master batch is characterized in that the melting index of the high-molecular degradable master batch is 3-30 g/min under the condition of 2.16kg and the temperature of 190 ℃, and the melting range is 90-165 ℃; the ratio t1/t2 of 60 ℃ aerobic degradation time t1 to 60 ℃ anaerobic degradation time t2 of the degradable master batch is 5-10, the total content of metal ions with atomic numbers larger than 30 in the degradable master batch is less than 100ppm, and the main components and the content of the high molecular degradable master batch are as follows:
component content
20 to 40 percent of modified polyglycolic acid
4 to 15 percent of calcium lactate
4 to 10 percent of calcium stearate
2 to 10 percent of ferric stearate
2 to 10 percent of manganese stearate
PBAT 20～40%
0.5 to 1.5 percent of auxin accelerant
0.5 to 1.5 percent of bacillus
The balance of auxiliary agent
The preparation method of the high-molecular degradable master batch comprises the following steps:
the method comprises the following steps: preparation of modified polyglycolic acid
Using glycolic acid as a raw material, adopting a titanium modified catalyst, firstly carrying out esterification reaction on the glycolic acid at the temperature of 190-210 ℃, adopting nitrogen as protective gas in the esterification reaction process, carrying out normal pressure reaction, carrying out polycondensation reaction at the temperature of 230-250 ℃ when the esterification water yield is more than 90%, controlling the polycondensation vacuum degree to be 30-500 Pa, and finishing the reaction when the molecular weight is increased to 8000-12000 to prepare the modified polyglycolic acid; the content of the titanium modified catalyst in the modified polyglycolic acid is 50-200 ppm;
step two: preparing master batch with degradation function
Taking the modified polyglycolic acid, calcium lactate, calcium stearate, ferric stearate and manganese stearate prepared in the step one as raw materials, dispersing and mixing the raw materials according to a proportion, and then carrying out melt extrusion granulation by adopting a double-screw extruder to prepare the master batch with the degradation function;
step three: preparing bioactive functional master batch
The method comprises the following steps of taking PBAT, an auxin promoter, bacillus and an auxiliary agent as raw materials, firstly dispersing and melting the auxiliary agent, the auxin promoter and the bacillus at a high speed at a temperature of between 80 and 90 ℃, then adding the PBAT into a dispersion system, and then extruding and granulating by adopting a low-temperature high-pressure extrusion method to prepare a biological activity functional master batch;
step four: preparing high molecular degradable master batch
Taking the degraded functional master batch prepared in the second step and the bioactive functional master batch prepared in the third step as raw materials, adopting a melt blending method, taking the degraded functional master batch prepared in the second step as a main melt, taking the bioactive functional master batch prepared in the third step as a side material, and carrying out melt extrusion granulation, wherein the retention time of the side material in an extruder is controlled to be 5-30 s, and the melt granulation processing temperature is 110-180 ℃;
the preparation method of the titanium modified catalyst comprises the following steps: taking tetrabutyl titanate and glycollic acid as raw materials, taking nitrogen as protective gas, carrying out ester exchange reaction at 120 ℃ for 1-1.5 h, then adopting a vacuum extraction method, controlling the vacuum degree at 120 ℃ to be 1000-5000 Pa, carrying out vacuum extraction on unreacted tetrabutyl titanate and butanol products, and carrying out vacuum extraction for 30min to obtain a titanium modified catalyst; the molar ratio of tetrabutyl titanate to glycolic acid is 1: 4.15-1: 4.55;
the PBAT is powder of PBAT, and the particle size of the powder is 0.1-2.0 mm; the auxin promoter is cow milk extract with nitrogen content more than 5%, the bacillus is lactobacillus bulgaricus, and the auxiliary agent is polypropylene glycol 600.
2. The biodegradable polymer masterbatch of claim 1, wherein the processing temperature of the twin-screw extruder in the second step is 130-180 ℃.
3. The biodegradable polymer masterbatch of claim 1, wherein the melt ratio of the masterbatch with biodegradable properties obtained in step two to the masterbatch with bioactive properties obtained in step three is 1:0.5 to 1:3.
4. use of the polymeric degradable masterbatch of any one of claims 1-3 in the preparation of polymeric composite materials.
5. The use of claim 4, wherein the polymer degradable masterbatch is in a mass fraction of 3-15% in the polymer composite material.
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