CN114736496A - Degradable mulching film and preparation method thereof - Google Patents
Degradable mulching film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a degradable mulching film and a preparation method thereof, belonging to the technical field of high polymer materials and comprising 80 parts of plastic particles, 15 parts of carbon black, 5 parts of ionic liquid, 1.8 parts of chain extender, 0.5 part of antioxidant and 0.5 part of ultraviolet absorbent by mass; the two plastic base materials are kneaded with the plasticizer, the chain extender and the graphene composite filler to prepare plastic particles, wherein both ends of the plasticizer molecule are provided with C ═ O bonds which can generate interaction with the C ═ O bonds on the PLA and the PBS, so that the polar connection in the polymer base materials is weakened, the interaction force between the molecular chains is weakened, and the two base materials can be fully and uniformly mixed; zirconium silicate powder can increase the wear resistance and corrosion resistance of the prepared mulching film, graphene can increase the lubricity of plastic particles, stress is counteracted in the subsequent stretching process, cracks are reduced, and the stretchability of the prepared mulching film is increased, so that the service life is prolonged.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a degradable mulching film and a preparation method thereof.
Background
The mulching film is a film for covering the ground, can improve the soil temperature, maintain the soil moisture and structure, prevent pests from invading crops, and play a role in promoting the growth of the crops. The agricultural mulching film has wide application and various varieties. The mulching film is a petrochemical product and mainly made of polyethylene, polyvinyl chloride and the like, wherein the black plastic mulching film can effectively prevent soil moisture from evaporating and inhibit weed from growing, and is mainly suitable for the cultivation of the regenerated land of the weeds and vegetables in high-temperature seasons. After the crops are harvested, the broken mulching film remains in the soil and is difficult to degrade, causing serious pollution and damage to the soil.
In order to increase the environmental friendliness of the mulching film, a plurality of mulching films using easily degradable polymer materials as raw materials, which are easily degraded by microorganisms under specific environments, are available. The black mulching film is generally used in a high-temperature environment, is easy to bond with soil in the high-temperature and high-humidity environment, is easy to break after being dragged and moved, and increases the use cost. Therefore, the degradable mulching film with better stretching effect is needed to meet the use requirement.
Disclosure of Invention
The invention aims to provide a degradable mulching film and a preparation method thereof, which aim to solve the problems in the background art.
The purpose of the invention can be realized by the following technical scheme:
the degradable mulching film comprises the following raw materials in parts by mass:
80 parts of plastic particles, 15 parts of carbon black, 5 parts of ionic liquid, 1.8 parts of chain extender, 0.5 part of antioxidant and 0.5 part of ultraviolet absorber.
Further, the preparation method of the plastic particles comprises the following steps: mixing PLA particles, PBS particles, a plasticizer and a graphene composite filler according to a ratio of 150: 120: 85: 50, adding the mixture into a kneader, kneading the mixture evenly, extruding the mixture by a double-screw extruder and pelletizing the mixture to obtain plastic particles.
Further, the chain extender is a QH-LK4468 polylactic acid chain extender purchased from Shanghai Qihe chemical company Limited; the antioxidant is antioxidant 1010; the ultraviolet absorbent is ultraviolet absorbent uv 531.
Further, the preparation method of the graphene composite filler comprises the following steps: adding a silane coupling agent KH570 into absolute ethyl alcohol, uniformly stirring under the condition of 300-500r/min, and then adding zirconium silicate powder to obtain a sol solution; adding graphene into the sol solution, and performing ultrasonic dispersion for 20-30min to ensure that the silane coupling agent KH750 plays a role in hydrophobic modification on the graphene; and then centrifuging and drying to obtain the graphene composite filler.
Further, the dosage ratio of the silane coupling agent KH750 to the absolute ethyl alcohol to the zirconium silicate powder to the graphene is 3 g: 1 kg: 150-200 g: 85 g.
Further, the ionic liquid is prepared by the following steps: under the condition of ice-water bath, adding butyl phosphorus hydroxide into absolute ethyl alcohol, uniformly stirring to obtain a solution A, and dissolving octadecyl phosphonic acid by using the absolute ethyl alcohol to obtain a solution B; slowly dripping the solution B into the solution A under the condition of magnetic stirring, performing reflux reaction for 14-15 hours after dripping is finished, taking absolute ethyl alcohol as a reaction solvent, removing the absolute ethyl alcohol by rotary evaporation after the reaction is finished, placing the product into a drying box, and drying for 12 hours at the temperature of 40-45 ℃ to obtain ionic liquid; ionic liquids can increase the compatibility and thermal stability of the resulting film.
Further, the dosage ratio of the butyl phosphorus hydroxide to the absolute ethyl alcohol in the solution A is 3 g: 15 mL; the dosage ratio of the octadecyl phosphonic acid to the absolute ethyl alcohol in the solution B is 0.5 g: 5 mL; the dosage ratio of the solution A to the solution B is 3 mL: 1 mL.
Further, the preparation method of the plasticizer comprises the following steps: adding oleic acid, isosorbide, sulfamic acid and toluene into a flask, and carrying out reflux reaction under the conditions of nitrogen protection and 120 ℃ to ensure that two hydroxyl groups on the isosorbide and carboxyl groups on the oleic acid are subjected to esterification reaction, the sulfamic acid is used as a catalyst, and the toluene plays a role of a water-carrying agent; and (2) measuring the acid value of the reaction system every 1h in the reflux reaction process, reducing the temperature to room temperature after the acid value of the reaction system is unchanged, washing the product for 3-5 times by using a sodium bicarbonate solution with the mass fraction of 10%, then washing the product by using a saturated sodium chloride solution until a washing solution is neutral, finally washing the product for 2-3 times by using deionized water, standing the washed product for 18-24h, taking the upper layer liquid, and performing rotary evaporation to further remove impurities to obtain the black oily plasticizer.
Further, the dosage ratio of the oleic acid, the isosorbide, the sulfamic acid and the toluene is 250 g: 110 g: 15 g: 35-40 mL.
The preparation method of the degradable mulching film comprises the following steps: drying plastic particles and carbon black for 12-16h at the temperature of 60-80 ℃, then mixing the plastic particles and the carbon black with ionic liquid, a chain extender, an antioxidant and an ultraviolet absorbent, adding the mixture into a high-speed stirrer, uniformly stirring the mixture, and performing melt extrusion and grain cutting by using a double-screw extruder at the temperature of 175 plus 190 ℃ to obtain composite master batches;
and adding the composite master batch into a single-screw blow molding machine, wherein the single-screw blow molding machine has five temperature sections, the temperature of a first area is set to be 150-plus-155 ℃, the temperature of a second area is set to be 160-plus-175 ℃, the temperature of a third area is set to be 170-plus-190 ℃, the temperature of a fourth area is set to be 170-plus-190 ℃, the temperature of a fifth area is set to be 160-plus-190 ℃, the rotating speed of a screw is 50r/min, and the traction speed is 0.2-0.3m/s, and blow molding of the composite master batch is carried out to obtain the degradable mulching film.
The invention has the beneficial effects that:
the plastic granules are prepared by using PLA and PBS as base materials, and the PLA and the PBS have good biodegradability and can be gradually decomposed by microorganisms in a certain humidity and temperature environment; the two plastic materials are kneaded with the plasticizer, the chain extender and the graphene composite filler to prepare plastic particles, the plasticizer is synthesized through catalysis of oleic acid and isosorbide, and compared with the conventional plasticizer, the plasticizer is more environment-friendly, the two ends of the plasticizer molecule are provided with C ═ O bonds, and the plasticizer molecule can interact with the C ═ O bonds on PLA and PBS, so that polar connection in two independent polymer base materials is weakened, the original interaction force between the molecular chains in the base materials is weakened, the flexibility of the molecular chain is improved, and the two base materials can be fully and uniformly mixed; the silane coupling agent is diluted by absolute ethyl alcohol, then the zirconium silicate powder is added to prepare sol, the graphene and the zirconium silicate powder are uniformly dispersed by ultrasonic dispersion after the graphene is added, the hydrophobic property and compatibility of the graphene composite filler can be improved by the treatment of the silane coupling agent, the wear resistance and corrosion resistance of the prepared mulching film can be improved by the zirconium silicate powder, the lubricity of plastic particles can be improved by the graphene, stress is eliminated in the subsequent stretching process, the generation of cracks is reduced in the using process, the stretchability of the prepared mulching film is favorably improved, and the service life of the mulching film is prolonged; the ionic liquid has the functions of toughening and lubricating, so that the plastic particles, the carbon black and other components are uniformly mixed, the molecular chain of the polymer is prolonged by adding the chain extender, the elasticity of the prepared mulching film is improved, and the service life of the mulching film is further prolonged by the antioxidant and the light ultraviolet absorbent.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing plastic particles, comprising the steps of:
adding 2.5kg of oleic acid, 1.1kg of isosorbide, 150g of sulfamic acid and 350mL of toluene into a flask, and carrying out reflux reaction under the conditions of nitrogen protection and 120 ℃ to ensure that two hydroxyl groups on the isosorbide and carboxyl groups on the oleic acid are subjected to esterification reaction, the sulfamic acid is used as a catalyst, and the toluene plays a role of a water-carrying agent; and (2) measuring the acid value of the reaction system every 1h in the reflux reaction process, reducing the temperature to room temperature after the acid value of the reaction system is unchanged, washing the product for 3 times by using a sodium bicarbonate solution with the mass fraction of 10%, then washing the product by using a saturated sodium chloride solution until the washing solution is neutral, finally washing the product for 2 times by using deionized water, standing the washed product for 18h, taking the upper layer liquid, and performing rotary evaporation to further remove impurities to obtain the black and oily plasticizer.
Adding 6g of silane coupling agent KH570 into 2kg of absolute ethyl alcohol, uniformly stirring under the condition of 300r/min, and then adding 300g of zirconium silicate powder to obtain sol solution; adding 85g of graphene into the sol solution, and performing ultrasonic dispersion for 20min to ensure that the silane coupling agent KH750 plays a role in hydrophobic modification on the graphene; and then centrifuging and drying to obtain the graphene composite filler.
1.5kg of PLA particles, 1.2kg of PBS particles, 850g of plasticizer and 500g of graphene composite filler are added into a kneader and uniformly kneaded, and then extruded and cut into particles by a double-screw extruder to obtain plastic particles.
Example 2
Preparing plastic particles, comprising the steps of:
adding 2.5kg of oleic acid, 1.1kg of isosorbide, 150g of sulfamic acid and 385mL of toluene into a flask, and carrying out reflux reaction under the conditions of nitrogen protection and 120 ℃ to ensure that two hydroxyl groups on the isosorbide and carboxyl groups on the oleic acid are subjected to esterification reaction, the sulfamic acid is used as a catalyst, and the toluene plays a role of a water-carrying agent; and (2) measuring the acid value of the reaction system every 1h in the reflux reaction process, reducing the temperature to room temperature after the acid value of the reaction system is unchanged, washing the product for 4 times by using a sodium bicarbonate solution with the mass fraction of 10%, then washing the product by using a saturated sodium chloride solution until the washing solution is neutral, finally washing the product for 2 times by using deionized water, standing the washed product for 20h, taking the upper layer liquid, and performing rotary evaporation to further remove impurities to obtain the black and oily plasticizer.
Adding 6g of silane coupling agent KH570 into 2kg of absolute ethyl alcohol, uniformly stirring under the condition of 400r/min, and then adding 350g of zirconium silicate powder to obtain sol solution; adding 85g of graphene into the sol solution, and performing ultrasonic dispersion for 25min to ensure that the silane coupling agent KH750 plays a role in hydrophobic modification on the graphene; and then centrifuging and drying to obtain the graphene composite filler.
1.5kg of PLA particles, 1.2kg of PBS particles, 850g of plasticizer and 500g of graphene composite filler are added into a kneader and uniformly kneaded, and then extruded and cut into particles by a double-screw extruder to obtain plastic particles.
Example 3
Preparing plastic particles, comprising the steps of:
adding 2.5kg of oleic acid, 1.1kg of isosorbide, 150g of sulfamic acid and 400mL of toluene into a flask, and carrying out reflux reaction under the conditions of nitrogen protection and 120 ℃ to ensure that two hydroxyl groups on the isosorbide and carboxyl groups on the oleic acid are subjected to esterification reaction, the sulfamic acid is used as a catalyst, and the toluene plays a role of a water-carrying agent; and (2) measuring the acid value of the reaction system every 1h in the reflux reaction process, reducing the temperature to room temperature after the acid value of the reaction system is unchanged, washing the product for 5 times by using a sodium bicarbonate solution with the mass fraction of 10%, then washing the product by using a saturated sodium chloride solution until the washing solution is neutral, finally washing the product for 3 times by using deionized water, standing the washed product for 24h, taking the upper layer liquid, and performing rotary evaporation to further remove impurities to obtain the black and oily plasticizer.
Adding 6g of silane coupling agent KH570 into 2kg of absolute ethyl alcohol, stirring uniformly under the condition of 500r/min, and then adding 400g of zirconium silicate powder to obtain sol solution; adding 85g of graphene into the sol solution, and performing ultrasonic dispersion for 30min to ensure that the silane coupling agent KH750 plays a role in hydrophobic modification on the graphene; and then centrifuging and drying to obtain the graphene composite filler.
1.5kg of PLA particles, 1.2kg of PBS particles, 850g of plasticizer and 500g of graphene composite filler are added into a kneader and uniformly kneaded, and then extruded and cut into particles by a double-screw extruder to obtain plastic particles.
Example 4
The preparation method of the degradable mulching film comprises the following steps:
under the condition of ice-water bath, adding 3g of butyl phosphorus hydroxide into 15mL of absolute ethyl alcohol, uniformly stirring to obtain solution A, and dissolving 0.5g of octadecylphosphonic acid in 5mL of absolute ethyl alcohol to obtain solution B; slowly dripping 5mL of the solution B into 15mL of the solution A under the condition of magnetic stirring, carrying out reflux reaction for 14h after dripping is finished, taking absolute ethyl alcohol as a reaction solvent, carrying out rotary evaporation to remove the absolute ethyl alcohol after the reaction is finished, placing the product in a drying oven, and drying for 12h at 40 ℃ to obtain the ionic liquid.
800g of the plastic granules prepared in the example 1 and 150g of carbon black are dried for 12-16h at the temperature of 60-80 ℃, then mixed with 50g of ionic liquid, 18g of QH-LK4468 polylactic acid chain extender, 5g of antioxidant 1010 and 5g of ultraviolet absorbent uv531, added into a high-speed stirrer and stirred uniformly, and subjected to melt extrusion and grain cutting by a double-screw extruder at the temperature of 175-190 ℃ to obtain the composite master batch.
And adding the composite master batches into a single-screw blow molding machine, wherein the single-screw blow molding machine has five temperature sections, the temperature of a first area is set to be 150 ℃, the temperature of a second area is set to be 160 ℃, the temperature of a third area is set to be 170 ℃, the temperature of a fourth area is set to be 170 ℃, the temperature of a fifth area is set to be 160 ℃, the rotating speed of a screw is 50r/min, the traction speed is 0.2m/s, and the composite master batches are subjected to blow molding to form the degradable mulching film.
Example 5
Preparing the ionic liquid, comprising the following steps:
under the condition of ice-water bath, adding 3g of butyl phosphorus hydroxide into 15mL of absolute ethyl alcohol, uniformly stirring to obtain solution A, and dissolving 0.5g of octadecyl phosphonic acid by using 5mL of absolute ethyl alcohol to obtain solution B; slowly dripping 5mL of the solution B into 15mL of the solution A under the condition of magnetic stirring, performing reflux reaction for 14.5h after dripping is finished, taking absolute ethyl alcohol as a reaction solvent, removing the absolute ethyl alcohol by rotary evaporation after the reaction is finished, placing the product in a drying oven, and drying for 12h at 42 ℃ to obtain the ionic liquid.
800g of the plastic granules prepared in the example 2 and 150g of carbon black are dried for 12-16h at the temperature of 60-80 ℃, then mixed with 50g of ionic liquid, 18g of QH-LK4468 polylactic acid chain extender, 5g of antioxidant 1010 and 5g of ultraviolet absorbent uv531, added into a high-speed stirrer and stirred uniformly, and subjected to melt extrusion and grain cutting by a double-screw extruder at the temperature of 175-190 ℃ to obtain the composite master batch.
And adding the composite master batches into a single-screw blow molding machine, wherein the single-screw blow molding machine has five temperature sections, the temperature of a first area is set to be 150 ℃, the temperature of a second area is set to be 170 ℃, the temperature of a third area is set to be 180 ℃, the temperature of a fourth area is set to be 180 ℃, the temperature of a fifth area is set to be 180 ℃, the rotating speed of a screw is 50r/min, the traction speed is 0.25m/s, and the composite master batches are subjected to blow molding to form the degradable mulching film.
Example 6
The preparation method of the ionic liquid comprises the following steps:
under the condition of ice-water bath, adding 3g of butyl phosphorus hydroxide into 15mL of absolute ethyl alcohol, uniformly stirring to obtain solution A, and dissolving 0.5g of octadecyl phosphonic acid by using 5mL of absolute ethyl alcohol to obtain solution B; slowly dripping 5mL of the solution B into 15mL of the solution A under the condition of magnetic stirring, performing reflux reaction for 15h after dripping is finished, taking absolute ethyl alcohol as a reaction solvent, removing the absolute ethyl alcohol by rotary evaporation after the reaction is finished, placing the product in a drying oven, and drying for 12h at 45 ℃ to obtain the ionic liquid.
800g of the plastic granules prepared in the embodiment 3 and 150g of carbon black are dried for 12-16h at the temperature of 60-80 ℃, then mixed with 50g of ionic liquid, 18g of QH-LK4468 polylactic acid chain extender, 5g of antioxidant 1010 and 5g of ultraviolet absorbent uv531, added into a high-speed stirrer and uniformly stirred, and subjected to melt extrusion and grain cutting by a double-screw extruder at the temperature of 175-190 ℃ to obtain the composite master batch.
And adding the composite master batches into a single-screw blow molding machine, wherein the single-screw blow molding machine has five temperature sections, the temperature of a first area is 155 ℃, the temperature of a second area is 175 ℃, the temperature of a third area is 190 ℃, the temperature of a fourth area is 190 ℃, the temperature of a fifth area is 190 ℃, the rotating speed of a screw is 50r/min, the traction speed is 0.3m/s, and the degradable mulching film is prepared by blow molding the composite master batches into a film.
Comparative example 1: the mulching film is prepared on the basis of example 6 without adding ionic liquid, and the rest steps are kept unchanged.
Comparative example 2: plastic particles were prepared on the basis of example 3 without adding a plasticizer, the remaining steps were kept unchanged, and then a mulching film was prepared according to the method of example 6.
Comparative example 3: plastic particles are prepared without adding graphene composite filler on the basis of the embodiment 3, the rest steps are kept unchanged, and then the mulching film is prepared according to the method of the embodiment 6.
And (3) carrying out performance tests on the examples 4-6 and the comparative examples 1-3, testing the mechanical properties of the mulching films according to GB/T1040.3-2006, selecting each group of mulching films, cutting the mulching films into specifications of 20cm multiplied by 20cm, carrying out soil burying tests in 7 months and 8 months, burying each group of mulching films in soil with high soil microbial activity, wherein the burying depth is 15cm, and observing the residual quantity (percentage of the mulching film area) of the mulching films at the bottom of each month. The results are shown in table 1:
TABLE 1
As can be seen from table 1, the mulching films prepared in examples 4 to 6 have better elongation at break, the amount of residual mulching film after 1 month of the soil burial test is relatively higher for the mulching film with the graphene composite filler, and the degradation speed is accelerated at the 2 nd month.
It should be noted that, in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The degradable mulching film is characterized by comprising the following raw materials in parts by mass: 80 parts of plastic particles, 15 parts of carbon black, 5 parts of ionic liquid, 1.8 parts of chain extender, 0.5 part of antioxidant and 0.5 part of ultraviolet absorber;
the plastic particles are prepared by the following steps:
adding a silane coupling agent KH570 into absolute ethyl alcohol, uniformly stirring, and adding zirconium silicate powder to obtain a sol solution; adding graphene into the sol solution, performing ultrasonic dispersion for 20-30min, centrifuging, and drying to obtain a graphene composite filler; mixing PLA particles, PBS particles, a plasticizer and a graphene composite filler according to a ratio of 150: 120: 85: adding the mixture into a kneader according to the mass ratio of 50, kneading, extruding and granulating to obtain plastic particles.
2. The degradable mulching film according to claim 1, wherein the amount ratio of the silane coupling agent KH570 to the absolute ethyl alcohol to the zirconium silicate powder to the graphene is 3 g: 1 kg: 150-200 g: 85 g.
3. The degradable mulching film according to claim 1, wherein the plasticizer is prepared by a method comprising the following steps: adding oleic acid, isosorbide, sulfamic acid and toluene into a flask, carrying out reflux reaction under the conditions of nitrogen protection and 120 ℃, measuring the acid value of a reaction system every 1h, washing the product at room temperature and standing for 18-24h after the acid value of the reaction system is not changed, and taking the upper liquid to carry out rotary evaporation to obtain the plasticizer.
4. The degradable mulching film of claim 3, wherein the oleic acid, the isosorbide, the sulfamic acid and the toluene are used in a ratio of 250 g: 110 g: 15 g: 35-40 mL.
5. The degradable mulching film according to claim 1, wherein the ionic liquid is prepared by a method comprising the following steps: under the condition of ice-water bath, adding butyl phosphorus hydroxide into absolute ethyl alcohol, uniformly stirring to obtain solution A, and dissolving octadecyl phosphonic acid in absolute ethyl alcohol to obtain solution B; slowly dripping the solution B into the solution A under the condition of magnetic stirring, carrying out reflux reaction for 14-15h after dripping is finished, carrying out rotary evaporation to remove absolute ethyl alcohol after the reaction is finished, placing the product in a drying box, and drying for 12h at the temperature of 40-45 ℃ to obtain the ionic liquid.
6. The degradable mulching film according to claim 5, wherein the dosage ratio of the butyl phosphorus hydroxide to the absolute ethyl alcohol in the solution A is 3 g: 15 mL; the dosage ratio of the octadecyl phosphonic acid to the absolute ethyl alcohol in the solution B is 0.5 g: 5 mL; the dosage ratio of the solution A to the solution B is 3 mL: 1 mL.
7. The preparation method of the degradable mulching film according to claim 1, wherein the method comprises the following steps:
and (2) adding the composite master batch into a single-screw blow molding machine, wherein the single-screw blow molding machine is provided with five temperature sections, the temperature of a first area is set to be 150-155 ℃, the temperature of a second area is set to be 160-175 ℃, the temperature of a third area is set to be 170-190 ℃, the temperature of a fourth area is set to be 170-190 ℃, the temperature of a fifth area is set to be 160-190 ℃, the rotation speed of a screw is 50r/min, and the traction speed is 0.2-0.3m/s, and performing blow molding on the composite master batch to form a film, so as to obtain the degradable mulching film.
8. The preparation method of the degradable mulching film according to claim 7, wherein the preparation method of the composite master batch comprises the steps of drying the plastic particles and the carbon black for 12-16 hours at 60-80 ℃, uniformly mixing the plastic particles and the carbon black with the ionic liquid, the chain extender, the antioxidant and the ultraviolet absorber, and performing melt extrusion and granulation by using a double-screw extruder at 175-190 ℃ to obtain the composite master batch.
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| CN117946507A (en) * | 2024-03-26 | 2024-04-30 | 青州市鲁冠塑料有限公司 | Preparation method of biodegradable weeding and warming mulch film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117946507A (en) * | 2024-03-26 | 2024-04-30 | 青州市鲁冠塑料有限公司 | Preparation method of biodegradable weeding and warming mulch film |
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Application publication date: 20220712 |