CN113278265A - Degradable lignin-based composite agricultural mulching film and preparation method thereof - Google Patents
Degradable lignin-based composite agricultural mulching film and preparation method thereof Download PDFInfo
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- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
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Abstract
The invention discloses a degradable lignin-based composite agricultural mulching film and a preparation method thereof, wherein the lignin-based composite agricultural mulching film is prepared by blending and tape casting the following components in parts by weight: 60-95 parts of aliphatic polyester resin; 1-40 parts of modified lignin or lignin; 0.1-1 part of a coupling agent; 0.1-1 part of an opening agent; 1-5 parts of a plasticizer; 1-3 parts of a dispersing agent. According to the invention, lignin is used as a raw material, the compatibility with matrix resin is improved by modifying the lignin of the raw material, the prepared mulching film is brown and semitransparent in appearance, smooth and uniform in texture, excellent in mechanical property and degradation property and suitable for the fields of agricultural materials, packaging materials, environment-friendly bags, nets for civil engineering greening, seed culture belts and the like, and the degradation period is controlled within 2-24 months. The mulching film disclosed by the invention has good mechanical properties, has the effects of warming, preserving soil moisture, preventing insects, weeding and the like, and can be applied to crops such as rice, corn, cotton, sugarcane, vegetables and the like.
Description
Technical Field
The invention belongs to the field of degradable films, and particularly relates to a bioplastic film modified by blending aliphatic polyester and modified lignin and a preparation method thereof. Is especially suitable for agricultural mulching film, packing material, etc.
Background
The mulching film is one of the most important material resources in agricultural production, and can provide a better growth environment for the growth of crops. The agricultural yield and income are greatly improved by farmers by using the plastic film mulching cultivation technology, and the technology also drives the agricultural production mode and productivity to be changed greatly. The traditional agricultural mulching film is undegradable, the using amount is large, the recovery is difficult, the residual agricultural mulching film is accumulated year by year, the serious influence is directly brought to soil and crops, the serious white pollution is caused, the agricultural environment is polluted, and the production capacity of the land is greatly influenced. Therefore, the development of low-cost, multifunctional and biodegradable agricultural mulching films is one of the effective ways to solve the pollution of agricultural films.
Aliphatic polyesters are a class of high molecular compounds having good biodegradability. The main chain of the polyester is mostly formed by connecting aliphatic structural units through ester bonds which are easy to hydrolyze, and the main chain is easily degraded into nontoxic water-soluble oligomers or monomers by a large number of microorganisms or enzymes in animals and plants which exist in nature, and then the oligomers or monomers are converted into energy, carbon dioxide and water by microorganisms. With the increasing awareness of environmental protection and the urgent need for degradable biomaterials, the development, preparation and application of aliphatic polyester degradable materials are rapidly popularized, become new research hotspots, and are highly concerned by many researchers.
As a biodegradable natural polymer, the lignin has abundant reserves, high yield and low utilization rate. The industrial lignin is mainly derived from paper-making waste liquid and biorefinery industry, but only 2% of lignin is commercially applied to plastics and rubber, and the rest lignin is mostly discharged into rivers in the form of waste liquid or is burnt after concentration, so that the waste of resources is caused, and the environment is seriously polluted. The lignin has poor processability and is difficult to be independently prepared into a product, but the lignin macromolecules contain a large number of benzene ring structures and various active functional groups, and can be blended with different polymers through intermolecular interaction (such as hydrogen bonds, van der waals force and the like) to prepare the high-molecular composite material with biocompatibility, degradability, heat resistance and ultraviolet shielding effect. In general, various additives such as reinforcing agents, antioxidants, photo-thermal stabilizers and the like are added in the preparation of the composite material, and lignin is a natural high polymer material with multiple functional groups, can realize multifunctional superposition, is an ideal additive and can reduce the use of other additives.
Patent CN201010604201 discloses a lignin-filled polyester composite material and a preparation method thereof, the method is to blend lignin and polyester plastic, and perform extrusion granulation to obtain the lignin-filled polyester composite material, although the content of lignin in the method can reach 40 wt%, the mechanical property of the obtained material is poor, and the breaking elongation is only 22.59% under the condition that the content of lignin is 40 wt%. In GB13735-92, the elongation at break of agricultural ground covering films is required to be more than or equal to 120%, and in GB/T4456-2008, the elongation at break of packaging plastic films is required to be more than or equal to 100%.
Disclosure of Invention
The invention aims to provide a degradable lignin-based composite agricultural mulching film and a preparation method thereof aiming at the defects of the prior art.
The specific technical scheme for realizing the purpose of the invention is as follows:
a degradable lignin-based composite agricultural mulching film is characterized in that: the lignin-based composite agricultural mulching film is formed by mixing, casting and filming the following components in parts by weight:
60-95 parts of aliphatic polyester resin;
1-40 parts of modified lignin or lignin;
0.1-1 part of a coupling agent;
0.1-1 part of an opening agent;
1-5 parts of a plasticizer;
1-3 parts of a dispersing agent;
wherein: the modified lignin is one of maleic anhydride modified lignin or epoxy modified lignin;
the modified lignin is obtained by the following steps:
maleic anhydride-modified lignin: dissolving lignin in 1-2 mol/L sodium hydroxide solution, after completely dissolving the lignin, adding maleic anhydride according to the mass ratio of the lignin to the maleic anhydride of 1: 1-2, reacting in an oil bath kettle at 40-70 ℃ for 4-8 h, dropwise adding 1-2 mol/L acid after the reaction is finished to adjust the pH value to 1-2 to separate out a product, centrifugally precipitating, washing with water for several times, and freeze-drying;
the acid is hydrochloric acid or sulfuric acid;
epoxidation of modified lignin: dissolving lignin in 1-2 mol/L sodium hydroxide solution, adding epoxy chloropropane according to the mass ratio of 1-2: 1 of lignin to epoxy chloropropane after the lignin is completely dissolved, reacting in an oil bath kettle at 40-70 ℃ for 4-8 h to generate a mud-like substance, centrifugally precipitating after the reaction is finished, washing for several times, and freeze-drying;
and (3) freeze drying: freeze-drying at-40-65 deg.C for 16-48 h;
the aliphatic polyester resin is one or the combination of two of Polycaprolactone (PCL), poly (butylene succinate-co-butylene terephthalate) (PBST), Polyhydroxyalkanoate (PHA), polybutylene terephthalate-adipate (PBAT) and polylactic acid (PLA).
The opening agent is one or the combination of several of erucamide, oleamide and silicon dioxide.
The coupling agent is one or a combination of more of silane coupling agents KH550, KH560, KH570 and KH 590.
The plasticizer is one or a combination of several of Epoxidized Soybean Oil (ESO), acetyl tributyl citrate (ATBC), triethyl citrate (TEC) and dioctyl phthalate (DOP).
The dispersant is one or a combination of stearic acid, oleic acid and titanate.
The preparation method of the degradable lignin-based composite agricultural mulching film comprises the following specific steps of:
step 1: pretreatment of raw materials: placing 60-95 parts of aliphatic polyester resin and 1-40 parts of modified lignin or lignin in a forced air drying oven, and drying at 50-70 ℃ to remove water;
step 2: premixing raw materials: adding 60-95 parts of the aliphatic polyester resin dried in the step 1, 1-40 parts of modified lignin or lignin, 0.1-1 part of a coupling agent, 0.1-1 part of an opening agent, 1-5 parts of a plasticizer and 1-3 parts of a dispersing agent into a high-speed mixer, and mixing at the rotating speed of 1000-2000 r/min for 15-25 min to obtain a premix;
and step 3: and (3) extruding and granulating: adding the premix into a double-screw reaction extruder, wherein the double-screw reaction extruder is in the same direction, the length-diameter ratio of screws is 25-35: l, the rotating speed of the screws is 50-20 rpm, and the temperature of each zone is controlled as follows: the first zone is 100-130 ℃, the second zone is 100-140 ℃, the third zone is 100-150 ℃, the fourth zone is 110-170 ℃, the fifth zone is 110-170 ℃, the sixth zone is 110-140 ℃ and the seventh zone is 100-150 ℃, materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then extrusion granulation is carried out, so that master batches are obtained;
and 4, step 4: extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the degradable lignin-based composite agricultural mulching film is prepared by the steps of enabling a first zone to be 100-130 ℃, a second zone to be 100-140 ℃, a third zone to be 100-150 ℃, a fourth zone to be 110-170 ℃, a fifth zone to be 110-170 ℃, a sixth zone to be 110-140 ℃, a seventh zone to be 100-150 ℃, the rotating speed of a screw to be 50-100 rpm, controlling the temperature of a traction roller of an extrusion casting machine to be 20-60 ℃, and the traction speed to be 10-20 m/min, cooling by an air ring, and coiling.
The degradable lignin-based composite agricultural mulching film prepared by the invention still has good mechanical properties when the content of the modified lignin is high. The invention relates to a degradable lignin-based composite agricultural mulching film and a preparation method thereof, the film is brown and semitransparent in appearance, smooth and uniform in texture, controllable in degradation rate, good in mechanical property and degradation property, and suitable for the fields of agricultural materials, packaging materials, environment-friendly bags, nets for civil greening, seed culture belts and the like, and the degradation period is controlled to be 2-24 months. The modified lignin/aliphatic polyester bioplastic is prepared by carrying out composite blending modification on aliphatic polyester by changing a processing technology, the mechanical property and the degradation property of the product are greatly improved, when the content of lignin is 40%, the tensile strength and the elongation at break can respectively reach 18.21MPa and 504.26% by technology adjustment, and the technical problem that when the content of lignin is high, the tensile strength and the elongation at break are poor is solved. The invention aims to improve the compatibility between matrixes through modification, the preparation process is simple, the raw materials are low in price and environment-friendly, and the prepared product has excellent mechanical properties and ultraviolet shielding effect and has good application prospect.
Drawings
FIG. 1 is a schematic view of a lignin-based composite agricultural mulching film prepared in example 1 of the present invention.
Detailed Description
The following examples are provided to illustrate the present invention in detail, but the present invention is not limited to the following embodiments.
Preparing modified lignin:
maleic anhydride modified lignin: adding 10g of lignin and 10g of maleic anhydride under the condition of a sodium hydroxide solution with the concentration of 2mol/L, reacting for 7h in an oil bath kettle at 50 ℃, adding 2mol/L hydrochloric acid to adjust the pH value to be 2, precipitating by centrifugation, washing for 6 times, and then freeze-drying for 48h at-20 ℃.
Modified lignin of epichlorohydrin: adding 10g of lignin and 5g of epichlorohydrin under the condition of a sodium hydroxide solution with the concentration of 2mol/L, carrying out reaction in an oil bath kettle at 70 ℃ for 6h, carrying out centrifugal precipitation after the reaction is finished, washing for 6 times, and carrying out freeze drying at-20 ℃ for 48 h.
Example 1
1) Pretreatment of raw materials: according to the weight parts, the raw materials PBST90 parts and the enzymatic hydrolysis lignin 10 parts are placed in a blast drying oven, and dried and dewatered at 50-70 ℃;
2) premixing raw materials: adding 10 parts of enzymatic hydrolysis lignin, 10 parts of PBST90 parts of erucamide opener, 1 part of KH560 coupling agent, 1 part of stearic acid dispersant and 1 part of dioctyl phthalate plasticizer into a high-speed mixer together, and mixing for 20min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃ and the seventh zone is 110 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then the materials are extruded and granulated, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃, the seventh zone is 110 ℃, the screw rotation speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film (shown in figure 1) is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 26.06MPa, the breaking elongation of 900.36% and the right-angle tearing strength of 190.21 kN/m.
Example 2
1) Pretreatment of raw materials: according to the weight parts, raw materials PBST80 parts and alkali lignin 20 parts are placed in a blast drying oven, and dried and dewatered at 50-70 ℃;
2) premixing raw materials: adding 20 parts of alkali lignin, 80 parts of PBST, 1 part of erucamide opening agent, 1 part of KH560 coupling agent, 1 part of stearic acid dispersant and 1 part of dioctyl phthalate plasticizer into a high-speed mixer together, and mixing for 20min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃ and the seventh zone is 110 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then the materials are extruded and granulated, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃, the seventh zone is 110 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 20.51MPa, the breaking elongation of 720.32% and the right-angle tearing strength of 156.16 kN/m.
Example 3
1) Pretreatment of raw materials: putting 70 parts of PBST and 30 parts of lignosulfonate in parts by weight into a blast drying oven, and drying at 50-70 ℃ to remove water;
2) premixing raw materials: adding 30 parts of lignosulfonate, 70 parts of PBST and 1 part of an opening agent erucamide into a high-speed mixer together, and mixing for 15min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃ and the seventh zone is 110 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then the materials are extruded and granulated, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃, the seventh zone is 110 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 30 ℃, the traction speed is 10m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 19.51MPa, the breaking elongation of 632.41% and the right-angle tearing strength of 140.36 kN/m.
Example 4
1) Pretreatment of raw materials: putting 60 parts of PBST (polyparaffin-based polyethylene terephthalate) and 40 parts of enzymatic hydrolysis lignin in a forced air drying oven according to parts by weight, and drying at 50-70 ℃ to remove water;
2) premixing raw materials: adding 40 parts of lignin, 60 parts of PBST, 1 part of erucamide opening agent, 1 part of KH560 coupling agent, 1 part of stearic acid dispersant and 1 part of dioctyl phthalate plasticizer into a high-speed mixer together, and mixing for 20min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃ and the seventh zone is 110 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then the materials are extruded and granulated, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃, the seventh zone is 110 ℃, the screw rotation speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, the tensile strength of the obtained film is 17.52MPa, the elongation at break is 423.62%, and the right-angle tearing strength is 120.56 kN/m.
Example 5
1) Pretreatment of raw materials: putting 90 parts by weight of PBST (poly (p-phenylene benzobisoxazole)) and 10 parts by weight of maleic anhydride modified lignin into a forced air drying oven, and drying at 50-70 ℃ to remove water;
2) premixing raw materials: adding 10 parts of maleic anhydride modified lignin, 90 parts of PBST, 1 part of an erucamide as an opening agent, 1 part of dioctyl phthalate (DOP) as a plasticizer and 1 part of stearic acid as a dispersing agent into a high-speed mixer, and mixing for 20min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃ and the seventh zone is 110 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then the materials are extruded and granulated, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃, the seventh zone is 110 ℃, the screw rotation speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 27.84MPa, the breaking elongation of 925.43% and the right-angle tearing strength of 195.47 kN/m.
Example 6
1) Pretreatment of raw materials: placing 80 parts by weight of PBST (poly-p-phenylene benzobisoxazole) and 20 parts by weight of maleic anhydride modified lignin in a forced air drying oven, and drying at 50-70 ℃ to remove water;
2) premixing raw materials: adding 20 parts of maleic anhydride modified lignin, 80 parts of PBST, 1 part of an opening agent erucamide, 1 part of plasticizer epoxy soybean oil and 1 part of dispersant stearic acid into a high-speed mixer together, and mixing for 20min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃ and the seventh zone is 110 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then the materials are extruded and granulated, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃, the seventh zone is 110 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 23.33MPa, the breaking elongation of 802.23% and the right-angle tearing strength of 176.28 kN/m.
Example 7
1) Pretreatment of raw materials: according to the weight parts, the raw materials PBST70 parts and the maleic anhydride modified lignin 30 parts are placed in a blast drying oven, and dried and dewatered at 50-70 ℃;
2) premixing raw materials: adding 30 parts of maleic anhydride modified lignin, 30 parts of PBST70 parts, 1 part of an opening agent erucamide, 1 part of a plasticizer epoxidized soybean oil and 1 part of a dispersant stearic acid into a high-speed mixer together, and mixing for 20min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃ and the seventh zone is 110 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then the materials are extruded and granulated, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃, the seventh zone is 110 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 21.87MPa, the breaking elongation of 697.46% and the right-angle tearing strength of 159.81 kN/m.
Example 8
1) Pretreatment of raw materials: putting the PBST60 and 40 parts of maleic anhydride modified lignin serving as raw materials in a forced air drying oven according to parts by weight, and drying at 50-70 ℃ to remove water;
2) premixing raw materials: adding 40 parts of maleic anhydride modified lignin, 60 parts of PBST, 1 part of an erucamide opening agent, 1 part of acetyl tributyl citrate (ATBC) serving as a plasticizer and 1 part of stearic acid serving as a dispersing agent into a high-speed mixer, and mixing at the rotating speed of 1000r/min for 25min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃ and the seventh zone is 110 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then the materials are extruded and granulated, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃, the seventh zone is 110 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 60 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, the tensile strength of the obtained film is 18.21MPa, the elongation at break is 504.26%, and the right-angle tearing strength is 132.23 kN/m.
Example 9
1) Pretreatment of raw materials: putting raw materials PBST60 parts, PCL20 parts and 20 parts of maleic anhydride modified lignin in a blast drying oven according to parts by weight, and drying at 50-70 ℃ to remove water;
2) premixing raw materials: adding 20 parts of maleic anhydride modified lignin, 60 parts of PBST, 20 parts of PCL, 1 part of an erucamide opening agent, 1 part of acetyl tributyl citrate (ATBC) plasticizer and 1 part of stearic acid dispersant into a high-speed mixer, and mixing at the rotating speed of 2000r/min for 20min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃ and the seventh zone is 110 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then the materials are extruded and granulated, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃, the seventh zone is 110 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, the tensile strength of the obtained film is 25.58MPa, the breaking elongation is 762.49%, and the right-angle tearing strength is 168.53 kN/m.
Example 10
1) Pretreatment of raw materials: putting 60 parts of PBST, 20 parts of PLA and 20 parts of maleic anhydride modified lignin in parts by weight into a forced air drying oven, and drying at 50-70 ℃ to remove water;
2) premixing raw materials: adding 20 parts of maleic anhydride modified lignin, 60 parts of PBST, 20 parts of PLA, 1 part of an erucamide opening agent, 1 part of acetyl tributyl citrate (ATBC) plasticizer and 1 part of stearic acid dispersant into a high-speed mixer, and mixing for 20min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 150 ℃, the fifth zone is 170 ℃, the sixth zone is 165 ℃ and the seventh zone is 160 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then extrusion granulation is carried out, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 150 ℃, the fifth zone is 170 ℃, the sixth zone is 165 ℃, the seventh zone is 160 ℃, the screw rotation speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 33.58MPa, the breaking elongation of 540.49 percent and the right-angle tearing strength of 156.57 kN/m.
Example 11
1) Pretreatment of raw materials: putting raw materials PBST60 parts, PBAT20 parts and 20 parts of maleic anhydride modified lignin in a forced air drying oven according to parts by weight, and drying and dewatering at 50-70 ℃;
2) premixing raw materials: adding 20 parts of maleic anhydride modified lignin, 60 parts of PBST, 20 parts of PBAT, 1 part of an erucamide opening agent, 1 part of acetyl tributyl citrate (ATBC) plasticizer and 1 part of stearic acid dispersant into a high-speed mixer, and mixing for 20min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 135 ℃, the sixth zone is 135 ℃ and the seventh zone is 135 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then extrusion granulation is carried out, thus obtaining master batches;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 135 ℃, the sixth zone is 135 ℃, the seventh zone is 135 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 26.58MPa, the elongation at break of 790.49% and the right-angle tearing strength of 166.53 kN/m.
Example 12
1) Pretreatment of raw materials: putting 60 parts of PBST, 20 parts of PHA and 20 parts of maleic anhydride modified lignin in parts by weight into a blast drying oven, and drying at 50-70 ℃ to remove water;
2) premixing raw materials: adding 20 parts of maleic anhydride modified lignin, 60 parts of PBST, 20 parts of PHA, 1 part of an erucamide opening agent, 1 part of acetyl tributyl citrate (ATBC) plasticizer and 1 part of stearic acid dispersant into a high-speed mixer, and mixing for 20min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 125 ℃, the fourth zone is 130 ℃, the fifth zone is 135 ℃, the sixth zone is 130 ℃ and the seventh zone is 130 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then extrusion granulation is carried out, thus obtaining master batches;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 135 ℃, the sixth zone is 130 ℃, the seventh zone is 130 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 26.27MPa, the elongation at break of 780.49% and the right-angle tearing strength of 156.78 kN/m.
Example 13
1) Pretreatment of raw materials: placing raw materials PBST60 parts, PBS20 parts and maleic anhydride modified lignin 20 parts in a forced air drying oven according to parts by weight, and drying and dewatering at 50-70 ℃;
2) premixing raw materials: adding 20 parts of maleic anhydride modified lignin, 60 parts of PBST, 20 parts of PBS, 1 part of an erucamide opening agent, 1 part of acetyl tributyl citrate (ATBC) plasticizer and 1 part of stearic acid dispersing agent into a high-speed mixer, and mixing for 20min at the rotating speed of 2000r/min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 135 ℃, the fifth zone is 135 ℃, the sixth zone is 130 ℃ and the seventh zone is 130 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then extrusion granulation is carried out, thus obtaining master batches;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 135 ℃, the sixth zone is 130 ℃, the seventh zone is 130 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at20 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 24.33MPa, the breaking elongation of 653.23% and the right-angle tearing strength of 165.28 kN/m.
Example 14
1) Pretreatment of raw materials: according to the weight parts, the raw material PBST80 parts and the epoxidized modified lignin 20 parts are placed in a forced air drying oven, and the drying and the water removal are carried out at the temperature of 50-70 ℃;
2) premixing raw materials: adding 20 parts of epoxidized modified lignin, 80 parts of PBST, 1 part of an erucamide opening agent, 1 part of acetyl tributyl citrate (ATBC) serving as a plasticizer and 1 part of stearic acid serving as a dispersing agent into a high-speed mixer, and mixing at the rotating speed of 2000r/min for 20min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃ and the seventh zone is 110 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then the materials are extruded and granulated, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 130 ℃, the sixth zone is 120 ℃, the seventh zone is 110 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 20m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 26.21MPa, the elongation at break of 785.28% and the right-angle tearing strength of 184.83 kN/m.
Example 15
1) Pretreatment of raw materials: placing 60 parts of PBST, 20 parts of PBS and 20 parts of epoxidized modified lignin in parts by weight into a forced air drying oven, and drying at 50-70 ℃ to remove water;
2) premixing raw materials: adding 20 parts of epoxy modified lignin, 60 parts of PBST, 20 parts of PBS, 1 part of an erucamide opening agent, 1 part of acetyl tributyl citrate (ATBC) plasticizer and 1 part of stearic acid dispersant into a high-speed mixer, and mixing at the rotating speed of 2000r/min for 20min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 135 ℃, the fifth zone is 135 ℃, the sixth zone is 130 ℃ and the seventh zone is 130 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then extrusion granulation is carried out, thus obtaining master batches;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 130 ℃, the fifth zone is 135 ℃, the sixth zone is 130 ℃, the seventh zone is 130 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 28.43MPa, the elongation at break of 713.53% and the right-angle tearing strength of 168.27 kN/m.
Example 16
1) Pretreatment of raw materials: placing 60 parts of PBST, 20 parts of PLA and 20 parts of epoxidized modified lignin in parts by weight into a forced air drying oven, and drying and dewatering at 50-70 ℃;
2) premixing raw materials: adding 20 parts of epoxidized modified lignin, 60 parts of PBST, 20 parts of PLA, 1 part of erucamide serving as an opening agent, 1 part of acetyl tributyl citrate (ATBC) serving as a plasticizer and 1 part of stearic acid serving as a dispersing agent into a high-speed mixer, and mixing at the rotating speed of 2000r/min for 20min to obtain a premix;
3) and (3) extrusion granulation treatment: adding the premix into a double-screw reaction extruder, wherein the screw reaction extruder is a co-rotating double-screw extruder, the length-diameter ratio of screws is 25: l, the rotating speed of the screws is 50rpm, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 150 ℃, the fifth zone is 170 ℃, the sixth zone is 165 ℃ and the seventh zone is 160 ℃, the materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then extrusion granulation is carried out, so that the master batch is obtained;
4) extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the first zone is 110 ℃, the second zone is 120 ℃, the third zone is 130 ℃, the fourth zone is 150 ℃, the fifth zone is 170 ℃, the sixth zone is 165 ℃, the seventh zone is 160 ℃, the screw rotating speed is 60rpm, the temperature of a traction roller of the extrusion casting machine is controlled at 25 ℃, the traction speed is 15m/min, the degradable lignin-based composite agricultural mulching film is obtained after cooling and coiling through an air ring, and the obtained film has the tensile strength of 31.08MPa, the elongation at break of 652.59% and the right-angle tearing strength of 176.67 kN/m.
Example 17
The soil burying experiment is a method for burying the degradable plastic film into soil with a certain depth and regularly observing the degradation condition of the plastic film. The soil burying experiment shows the biodegradation performance of the degradable plastic film because the soil contains a large amount of microorganisms and enzymes.
The degradation rates of examples 1 to 4 of the present invention were respectively tested for 7 days, 15 days, 30 days, 60 days, and 180 days according to the standard GB/T20197-2006, and the results are shown in table 1.
The degradable lignin-based composite agricultural mulching film (150mm multiplied by 0.025mm) is buried under the moderately alkaline soil (the depth is about 10cm), and after different degradation times (7,15,30,60 and 180 days) are observed, the mass loss rate is defined as the degradation rate, and the calculation formula is as follows:
wherein: Δ M is mass loss rate, M0And MtRespectively the quality before and after the film soil is buried.
TABLE 1 quality loss of lignin-based composite agricultural mulch soil degradation
Claims (6)
1. The degradable lignin-based composite agricultural mulching film is characterized by being prepared by mixing, casting and forming the following components in parts by weight:
60-95 parts of aliphatic polyester resin;
1-40 parts of modified lignin or lignin;
0.1-1 part of a coupling agent;
0.1-1 part of an opening agent;
1-5 parts of a plasticizer;
1-3 parts of a dispersing agent;
wherein: the modified lignin is one of maleic anhydride modified lignin or epoxy modified lignin;
the modified lignin is obtained by the following steps:
maleic anhydride-modified lignin: dissolving lignin in 1-2 mol/L sodium hydroxide solution, after completely dissolving the lignin, adding maleic anhydride according to the mass ratio of lignin to maleic anhydride =1: 1-2, reacting in an oil bath kettle at 40-70 ℃ for 4-8 h, dropwise adding 1-2 mol/L acid after the reaction is finished, adjusting the pH value to 1-2, precipitating a product, centrifuging, precipitating, washing with water for several times, and freeze-drying;
the acid is hydrochloric acid or sulfuric acid;
epoxidation of modified lignin: dissolving lignin in 1-2 mol/L sodium hydroxide solution, adding epoxy chloropropane according to the mass ratio of 1-2: 1 of lignin to epoxy chloropropane after the lignin is completely dissolved, reacting in an oil bath kettle at 40-70 ℃ for 4-8 h to generate a mud-like substance, centrifugally precipitating after the reaction is finished, washing for several times, and freeze-drying;
and (3) freeze drying: freeze-drying at-40-65 deg.C for 16-48 h;
the aliphatic polyester resin is one or the combination of two of polycaprolactone, poly (butylene succinate-co-butylene terephthalate), polyhydroxyalkanoate, polybutylene terephthalate-adipate and polylactic acid.
2. The degradable lignin-based composite agricultural mulching film according to claim 1, wherein the opening agent is one or a combination of several of erucamide, oleamide and silica.
3. The degradable lignin-based composite agricultural mulching film according to claim 1, wherein the coupling agent is one or a combination of silane coupling agents KH550, KH560, KH570 and KH 590.
4. The degradable lignin-based composite agricultural mulch of claim 1, wherein the plasticizer is one or a combination of epoxidized soybean oil, acetyl tributyl citrate, triethyl citrate and dioctyl phthalate.
5. The degradable lignin-based composite agricultural mulching film according to claim 1, wherein the dispersant is one or a combination of stearic acid, oleic acid and titanate.
6. The preparation method of the degradable lignin-based composite agricultural mulching film according to any one of claims 1 to 5, which comprises the following steps in parts by weight:
step 1: pretreatment of raw materials: placing 60-95 parts of aliphatic polyester resin and 1-40 parts of modified lignin or lignin in a forced air drying oven, and drying at 50-70 ℃ to remove water;
step 2: premixing raw materials: adding 60-95 parts of the aliphatic polyester resin dried in the step 1, 1-40 parts of modified lignin or lignin, 0.1-1 part of a coupling agent, 0.1-1 part of an opening agent, 1-5 parts of a plasticizer and 1-3 parts of a dispersing agent into a high-speed mixer, and mixing at the rotating speed of 1000-2000 r/min for 15-25 min to obtain a premix;
and step 3: and (3) extruding and granulating: adding the premix into a double-screw reaction extruder, wherein the double-screw reaction extruder is in the same direction, the length-diameter ratio of screws is 25-35: l, the rotating speed of the screws is 50-20 rpm, and the temperature of each zone is controlled as follows: the first zone is 100-130 ℃, the second zone is 100-140 ℃, the third zone is 100-150 ℃, the fourth zone is 110-170 ℃, the fifth zone is 110-170 ℃, the sixth zone is 110-140 ℃ and the seventh zone is 100-150 ℃, materials are effectively mixed through the shearing action of a double-screw reaction extruder, and then extrusion granulation is carried out, so that master batches are obtained;
and 4, step 4: extrusion tape casting: the master batch is firstly placed in a charging barrel of an extrusion casting machine, and the temperature of each zone is controlled as follows: the degradable lignin-based composite agricultural mulching film is prepared by the steps of enabling a first zone to be 100-130 ℃, a second zone to be 100-140 ℃, a third zone to be 100-150 ℃, a fourth zone to be 110-170 ℃, a fifth zone to be 110-170 ℃, a sixth zone to be 110-140 ℃, a seventh zone to be 100-150 ℃, the rotating speed of a screw to be 50-100 rpm, controlling the temperature of a traction roller of an extrusion casting machine to be 20-60 ℃, and the traction speed to be 10-20 m/min, cooling by an air ring, and coiling.
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