CN115991929A - Biodegradable mulching film with soil protection effect and preparation method thereof - Google Patents
Biodegradable mulching film with soil protection effect and preparation method thereof Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/28—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture specially adapted for farming
Abstract
The invention discloses a biodegradable mulching film with a soil protection effect, which is prepared from the following components in parts by weight: 49-89 parts of PBAT, 10-50 parts of biochar, 0.1-10 parts of compatilizer and 0.1-5 parts of lubricant, and the preparation method comprises the following steps: the blend of the PBAT, the biochar, the compatilizer and the lubricant is simply blended and dried according to the proportion, and is subjected to blending granulation by a double-screw extruder, and is subjected to blow molding by a single-screw extruder to form a film after being dried to constant weight. The beneficial effects are as follows: the equipment is simple, the used biochar production process based on the waste biomass is simple, and the cost is low; the mechanical property and the water vapor barrier property of the prepared biodegradable film are improved, the application of the PBAT polymer in the aspect of agricultural mulching films is enlarged, and the biodegradable film has a large-scale preparation prospect.
Description
Technical Field
The invention belongs to the field of biodegradable films, in particular to a biodegradable mulching film with a soil protection effect and a preparation method thereof, and the PBAT composite film prepared by blow molding has excellent mechanical property and water vapor barrier property through the introduction of low-cost biochar with the soil protection effect, and can be used in the field of agricultural planting mulching films.
Background
The plastic products bring more and more attention to environmental pollution caused by accumulation of waste plastics while bringing convenience to life of people. Traditional petroleum-based plastic products, such as polyethylene and polyvinyl chloride, are difficult to degrade in natural environments, and cause serious 'white pollution'. The development of environmentally friendly biodegradable polymers has become the focus of research in recent decades. The biodegradable polymer can be degraded into CO within six months under certain conditions 2 The water and biomass can effectively relieve the problem of white pollution, and particularly can be used in the application fields difficult to recycle, such as disposable packages, mulching films and the like.
Polybutylene terephthalate-adipate (PBAT) has excellent processing, mechanical and biological degradation properties, and is expected to replace Low Density Polyethylene (LDPE) to be applied to different fields. Among them, the field of agricultural mulching film with high recovery cost and serious pollution is one of sites where PBAT is expected to be applied on a large scale. The agricultural film currently used takes petroleum-based plastics as raw materials, the main component of the low-density polyethylene is not degraded after being remained in the field for decades, broken films are accumulated on a soil cultivation layer year by year after being used for successive years, so that soil hardening and permeability deterioration are caused, the root growth of crops is hindered, and the yield of succeeding crops is reduced. According to the investigation of China department of agriculture, the residual quantity of the mulching film in China is generally 60-90 kg/hectare, and the maximum quantity is 165 kg/hectare at present. Researches show that when the residual film content in the soil is 58.5 kg/hectare, the corn yield is reduced by 11-23%, the wheat yield is reduced by 9-16%, the soybean yield is reduced by 5.5-9%, and the vegetable yield is reduced by 14.6-59.2%. Therefore, the existing agricultural mulching film is greatly concerned in pollution control in China. An effective way to solve this problem is to change the material matrix and develop a biodegradable agricultural mulching film. At present, the existing test results show that the biodegradable mulching film based on PBAT has shown good effects on potato, peanut, tobacco and rice production. However, it is urgent to solve the problems of economy and service properties such as low modulus and poor barrier properties.
Blending or adding low cost inorganic fillers is a widely adopted strategy to solve the above problems. Thermoplastic starch (TPS) is often used for blending modification of biodegradable polymers because of its low cost, but its introduction also leads to further degradation of mechanical properties and moisture barrier properties due to compatibility issues, as well as the intrinsic hydrophilic character of TPS. Other biodegradable polymers are also used for modification of PBAT to prepare mulch specialty materials. The Chinese patent application with publication number of CN 114806106A discloses a preparation method of a special material for the PBAT-based biodegradable mulch film, and the PBAT-based biodegradable mulch film is prepared by a blending method. In chinese patent applications publication nos. CN114874476A, CN114933785A and CN114591609a, there are also disclosed biomass fillers (cellulose, lignin, modified rice hull powder, etc.), nanofillers (e.g. hydrotalcite nanoplatelets), and technical solutions that are also introduced into PBAT to enhance the performance of PBAT and reduce its cost. Nanoclays have also been incorporated into PBAT or blends of PBAT to enhance their processability and moisture barrier properties (ref: akhlish et al Composites Part B: engineering 2021.198,108141).
The biochar is prepared by pyrolysis of waste biomass and is mainly used for soil improvement. Recently, it has been shown that the reinforcing effect and the black dyeing effect are exhibited when added to a polymer matrix. Furthermore, the use of such fillers in agricultural mulch has a number of advantages: the cost is low, and the black and inherent high modulus are expected to improve the mechanical properties of the polymer phase. Furthermore, the natural high porosity of biochar may lead to further enhancement of barrier properties by entrapment of air or water within the pores, which is rarely reported compared to its application as a supercapacitor or adsorbent, etc. With the degradation of PBAT in soil, the biochar is released to be expected to play a role in soil improvement and promotion of PBAT degradation. The prepared black film is expected to be applied to the field of covering agriculture and other packaging applications. The introduction of biochar into PBAT to prepare the biodegradable mulch film with low cost and high performance is not disclosed and reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a biodegradable mulching film with a soil protection effect, which takes polybutylene terephthalate/adipate (PBAT) as a matrix, has low cost and high performance and is used in the field of agricultural crop planting.
In order to solve the problems, the technical scheme provided by the invention is as follows: a biodegradable mulching film with soil protection effect is prepared from the following components in parts by weight: 49-89 parts of PBAT, 10-50 parts of biochar, 0.1-10 parts of compatilizer and 0.1-5 parts of lubricant.
The PBAT composite black film with excellent mechanical property and barrier property is prepared by preparing PBAT/biochar composite material master batch in the presence of a lubricant, and the introduction of a low-content lubricant ensures better inorganic particle dispersion; the biochar with high porosity and low pore diameter is introduced into the PBAT as a filler, so that the defects of high cost, low rigidity and poor barrier property of the PBAT film are overcome; the elongation at break performance of the film is effectively improved through the compounding of the compatilizer and the micromolecule additive.
The biochar is prepared by using waste biomass, wherein the waste biomass comprises, but is not limited to, miscanthus, straw, wood dust or waste coconut shells. In addition, the biochar can also be prepared using waste plastics.
The biochar particles are prepared by high-temperature pyrolysis of waste biomass at 300-1500 ℃ in a nitrogen atmosphere.
The lubricant is a small molecule lubricant including, but not limited to, stearamide and other stearates and their complexes.
The compatibilizers include, but are not limited to, maleic anhydride grafted polybutylene terephthalate/adipate (MA-g-PBAT), which is prepared by maleating PBAT with a free radical initiator and Maleic Anhydride (MA).
The compatilizer is prepared from the following components in parts by weight: 90-95 parts of PBAT, 0.1-10 parts of maleic anhydride and 0.2-5 parts of free radical initiator.
The free radical initiator includes, but is not limited to, benzoyl peroxide or other dialkyl peroxides, which may preferably be 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
The preparation method of the compatilizer comprises the following steps: and (3) maleating the PBAT by using a free radical initiator and Maleic Anhydride (MA), adding the free radical initiator after blending the PBAT and the MA, and then extruding and molding in a double-screw extruder to obtain the MA-g-PBAT.
Wherein the temperature of each section of the twin-screw extruder is set to be 130-250 ℃.
Preferably, the free radical initiator is present in an amount of 0.5 to 3 parts by weight.
Preferably, the Maleic Anhydride (MA) content is between 3 and 9 parts by weight.
The composition of the biodegradable film is biodegradable polymer, inorganic filler and micromolecular additive, and does not contain any undegradable polyester or other additive components.
A preparation method of a biodegradable mulching film with soil protection effect comprises the following steps: blending and granulating the dried PBAT, the biochar, the compatilizer and the lubricant to form composite material particles; and carrying out blow molding on the composite material particles to form a film.
The drying is such that the water content of the PBAT, biochar, compatilizer and lubricant is less than 0.5wt%.
Preferably, the temperature range in which the blend is granulated is 130-250 ℃.
Preferably, the temperature of the blown film is 130-220 ℃, and the temperature of the die is 125-250 ℃.
The PBAT composite film has excellent mechanical property and water vapor barrier property, and can be used in the fields including but not limited to agricultural planting and packaging bags.
The elongation at break of the PBAT composite film is more than 250%.
The water vapor transmittance of the PBAT composite film is reduced by more than 50 percent compared with that of the PBAT.
The soil protection effect of the invention means that all components are biodegradable or environment-friendly, no film residue is left after the soil is buried to cause soil hardening, and the released biochar has the effects of improving soil fertility and repairing soil. The main effects are as follows: (1) The soil hardening caused by the residue of the mulching film is avoided, and (2) the soil fertility increase and the soil restoration caused by the release of the biochar are avoided.
According to the invention, the polybutylene terephthalate/adipate (PBAT) is taken as a matrix, and inorganic biochar filler with high porosity and low pore diameter is introduced into the PBAT to overcome the defects of high cost, low rigidity and poor barrier property of the PBAT film; the film product with high elongation at break is prepared by compounding a compatilizer and a micromolecule additive through blow molding. The biochar filler is harmless to the environment and low in cost, has the capability of improving the fertility of soil, can release and improve the fertility of the soil along with the degradation of PBAT in the soil, and has the advantage that the mechanical property of the biodegradable film is enhanced; because of the introduction of the porous biochar filler, the water vapor permeability of the PBAT is obviously reduced, the soil moisture conservation performance of the PBAT is greatly improved, and the PBAT can be used in the field of mulching films.
Compared with the prior art, the method has the following beneficial effects: the equipment is simple, the used biochar production process based on the waste biomass is simple, and the cost is low; the mechanical property and the water vapor barrier property of the prepared biodegradable film are improved, the application of the PBAT polymer in the aspect of agricultural mulching films is enlarged, and the biodegradable film has a large-scale preparation prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the following description is briefly presented with reference to the drawings which are required to be used in the embodiments or the description of the prior art, it being obvious that the drawings in the following description are some embodiments of the invention and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a photograph of the bubble stability of the PBAT composite film corresponding to the examples and the comparative examples;
FIG. 2 is an electron photograph of the PBAT composite film of example and comparative example 2;
FIG. 3 is a scanning electron microscope image of the poly PBAT composite film prepared in example of the present invention and comparative example 2.
Detailed Description
The technical scheme of the invention is described in detail below through the drawings and specific embodiments. The following examples are further illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
A preparation method of a biodegradable mulching film with soil protection effect comprises the following steps:
(1) Preparation of a compatilizer: after 94 parts of PBAT and 5 parts of maleic anhydride are blended, 1 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane is added, and the mixture is mixed in a twin screw extruder, the extrusion temperature is set to 130/135/140/150/150/140/135/130 ℃ (from a feeding section to a die section), and the screw rotation speed is set to 60rpm;
(2) 10 parts of biochar and 87 parts of PBAT (polybutylene terephthalate) with the water content lower than 0.5 weight percent, 2 parts of compatilizer and 1 part of compound lubricant (stearic acid amide: n-butyl stearate compound according to the mass ratio of 1:1) are mixed and granulated at 180 ℃ and 100rpm in a double screw extruder (a double screw extruder of Coperion, germany); the composite pellets were blow molded using a single screw mini-extruder (model RCP-0625, randcastle, inc.) at blow molding temperatures of 180, 180, 180℃and 170℃and a screw speed of 20rpm.
Example 2
A preparation method of a biodegradable mulching film with soil protection effect comprises the following steps:
(1) Preparation of a compatilizer: after 94 parts of PBAT and 5 parts of maleic anhydride were blended, 1 part of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane as a radical initiator was added, and the mixture was fed into a twin-screw extruder to be mixed, the extrusion temperature was set at 130/135/140/150/150/140/135/130 ℃from a feed section to a die section), and the screw rotation speed was set at 60rpm.
(2) 20 parts of biochar with the water content lower than 0.5wt%, 74 parts of PBAT (poly (butylene terephthalate)) and 5 parts of compatilizer are dried, 1 part of compound lubricant (stearic acid amide: n-butyl stearate compound according to the mass ratio of 1:1) is mixed and granulated at 180 ℃ and 100rpm in a double screw extruder (a double screw extruder of Coperion) to form composite material particles, and the composite material particles are subjected to blow molding by using a single screw micro extruder (RCP-0625 single screw micro extruder model of Randcastle Co., U.S.) at the blow molding temperature of 180, 180, 180 and 170 ℃ (mouth die temperature) and the screw speed of 20rpm.
Comparative example 1
A preparation method of a PBAT blown film comprises the following steps: 100 parts of PBAT matrix is dried for 24 hours in a vacuum oven at 80 ℃, and then added into a single screw extruder for direct extrusion blow molding, thus obtaining the PBAT film.
Comparative example 2
A preparation method of a biodegradable mulch film comprises the following steps: 10 parts of dried biochar and 90 parts of PBAT were pelletized by blending in a twin screw extruder (twin screw extruder from Coperion, corp., germany) at 180℃and 100rpm, and the pellets were blow molded by a single screw micro extruder (RCP-0625 single screw micro extruder from Randcastle Co., U.S.A.), the blow molding temperature was set at 180, 180, 180, 170℃and the screw speed was 20rpm.
Effect verification experiments the bubble stability of the above examples and comparative examples in the film blowing process, as shown in fig. 1, it can be seen from the accompanying drawings that the introduction of biochar did not destroy the excellent film blowing stability of PBAT, and the bubble stability was improved with the increase of the compatibilizing agent compared to 2 parts (example 1) and 5 parts (example 2).
The light transmittance of the biodegradable film and the electron photograph of the biochar dispersion are shown in fig. 2, in which it can be seen that the light transmittance of the film is reduced with the increase of the biochar content (10 parts (example 1) vs.20 parts (example 2)).
From the SEM images shown in fig. 3 of the dispersion of biochar in PBAT and the action of biochar-PBAT matrix interface, it was found that in comparative example 1, the action of biochar and polymer matrix interface was weak without the compatibilizer, and the separation of biochar and matrix was remarkable; after the compatibilization (examples 1 and 2), the biochar particles and the PBAT matrix interface were more effective and the inorganic filler was less dislodged from the matrix. More importantly, as the compatibilizer is added, the size of the biochar agglomerates is reduced and the dispersibility of the biochar in the PBAT is improved.
The tensile properties of the blown films of examples and comparative examples were measured in the Transverse (TD) and Machine (MD) directions of the composite films as shown in table 1 below, and the results were an average of 4 samples. The water vapor barrier properties of the examples and comparative examples were tested as shown in table 1 below, and the results are an average of 2 samples, under conditions of 38.7 ℃ and 100% RH. From the mechanical properties, the introduction of pure biochar increased the modulus of PBAT, but at the same time the elongation at break was also reduced (comparative example 2), which was caused by uneven dispersion of inorganic particles; with the introduction of compatilizer and lubricant, the elongation at break of the material is improved, the elongation at break of the material in the longitudinal direction and the transverse direction is close to or even higher than that of pure PBAT, and the tensile modulus is further increased to more than twice that of the PBAT. From the aspect of water vapor permeability, the introduction of the biochar, especially at high content (20 parts of biochar, example 2), reduces the water vapor permeability to 21% of PBAT, and greatly improves the moisturizing performance of the PBAT film.
TABLE 1PBAT and its composite film mechanics and Water vapor Barrier Properties
Table 2 below gives the estimated cost of the composite film based on the cost of the material, it can be seen that the production cost is reduced by 16% compared with that of the pure PBAT film when the added amount of the biochar is 20 parts with the increase of the biochar content.
Table 2PBAT and composite film material cost estimation
The invention and its embodiments have been described above by way of illustration and not limitation, and the invention is illustrated in the accompanying drawings and described in the drawings in which the actual structure is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention.
Claims (10)
1. The biodegradable mulching film with the soil protection effect is characterized by being prepared from the following components in parts by weight: 49-89 parts of PBAT, 10-50 parts of biochar, 0.1-10 parts of compatilizer and 0.1-5 parts of lubricant.
2. The biodegradable mulch film according to claim 1, wherein the biochar is biochar particles prepared based on waste biomass, including but not limited to miscanthus, straw, wood chips or waste coconut shells.
3. The biodegradable mulch film with soil protecting effect according to claim 2, wherein the biochar particles are prepared by pyrolysis of waste biomass at 300-1500 ℃ under nitrogen atmosphere.
4. A biodegradable mulch film having soil protecting effect according to claim 1, wherein the lubricant includes but is not limited to stearic acid amide and other stearic acids and their complexes.
5. A biodegradable mulch film having soil protecting effect according to claim 1, wherein the compatibiliser comprises, but is not limited to, maleic anhydride grafted polybutylene terephthalate-adipate esters.
6. The biodegradable mulch film with soil protecting effect according to claim 1, wherein the compatilizer is prepared from the following components in parts by weight: 90-95 parts of PBAT, 0.1-10 parts of maleic anhydride and 0.2-5 parts of free radical initiator.
7. The biodegradable mulch film with soil protecting effect according to claim 6, wherein said compatibilizing agent is prepared by the steps of: adding a free radical initiator after blending the PBAT and the MA, and then extruding and forming in a double-screw extruder, wherein the temperature of each section of the double-screw extruder is set to be 130-250 ℃.
8. A biodegradable mulch film having soil protecting effect according to claim 1, wherein the free radical initiator includes but is not limited to 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane and other benzoyl peroxides or other dialkyl peroxides.
9. The method for producing a biodegradable mulch film having soil protecting effect according to any one of claims 1 to 8, comprising the steps of: blending and granulating the dried PBAT, the biochar, the compatilizer and the lubricant to form composite material particles; blowing the composite material particles into a film; the temperature range of blending granulation is 130-220 ℃, and the temperature range of blow molding film forming is 125-250 ℃.
10. The method of producing a biodegradable mulch film having soil protecting effect according to claim 9, wherein the drying is such that the water content of PBAT, biochar, compatilizer and lubricant is less than 0.5wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310000962.6A CN115991929A (en) | 2023-01-03 | 2023-01-03 | Biodegradable mulching film with soil protection effect and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310000962.6A CN115991929A (en) | 2023-01-03 | 2023-01-03 | Biodegradable mulching film with soil protection effect and preparation method thereof |
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| Publication Number | Publication Date |
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| CN115991929A true CN115991929A (en) | 2023-04-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202310000962.6A Pending CN115991929A (en) | 2023-01-03 | 2023-01-03 | Biodegradable mulching film with soil protection effect and preparation method thereof |
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| Country | Link |
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| CN (1) | CN115991929A (en) |
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