CN107936507B - Mulching film for inhibiting weed growth and preparation method thereof - Google Patents
Mulching film for inhibiting weed growth and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- 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
- A01G13/0256—Ground coverings
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/095—Carboxylic acids containing halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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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
A mulching film for inhibiting the growth of weeds is prepared from the following components in parts by weight: 100 parts of polylactic acid, 50-70 parts of poly (butylene adipate)/terephthalate, 5-10 parts of acetyl ethyl citrate, 0.1-1 part of antioxidant, 0.5-3 parts of anti-ultraviolet auxiliary agent and 5-10 parts of carbon black master batch. Mixing herbicide into carbon black by utilizing the adsorption function of the carbon black, stirring and mixing at a high speed, granulating under the action of a biodegradable resin carrier to prepare a carbon black master batch, and adding the carbon black master batch into a degradable mulching film material in proportion to blow-mold a film; during the mixing treatment, the herbicide enters the internal gaps of the carbon black and is wrapped by the carbon black, so that the herbicide is not separated out when the mulching film is blown.
Description
Technical Field
The invention relates to a mulching film for inhibiting weed growth, which is mainly used for covering a mulching film, can effectively inhibit the growth of weeds and belongs to the field of processing and application of high polymer materials.
Background
With the development of the plastic industry, the plastic products have wider and wider application, wherein the agricultural plastic mulching film for covering crops is widely applied due to the effects of heat preservation, moisture preservation and the like; however, the non-degradability of petroleum-based resin causes great pollution to the soil environment, so that the non-degradable mulching film is replaced by a few degradable mulching films at present; the mulching film is beneficial to the growth of crops, and meanwhile, the breeding of weeds is also serious, so that manual weeding or herbicide beating is needed, and the labor cost is high; the herbicide mulching film is a new chemical weeding method developed in recent years, and has certain effects on reducing labor cost, reducing toxicity of pesticides to human bodies and reducing environmental pollution.
The currently applied herbicide mulching film is prepared into a film by adopting modes of spraying, smearing and the like, and the herbicide is blended in raw materials for modification and granulation, but a large amount of manpower and material resources are wasted when the herbicide is smeared; there are also many patents in this respect, such as patent application No. 201210525950.7, a weeding mulching film capable of being completely biodegraded, which is composed of PBAT, PBAT + PLA or PBAT + PPC and herbicide, chain extender, and release agent, the PBAT, PBAT + PPC or PBAT + PLA and herbicide, chain extender, and release agent are uniformly stirred by a stirrer, and then the blended material is subjected to extrusion modification and granulation by a twin-screw extruder; the patent with application number 95108803.3 discloses a controllable light and biological double-degradation weeding agricultural mulching film, which comprises 50-70 parts of polyethylene resin, 30-50 parts of modified starch, 0.02-0.30 part of photosensitizer, 0.01-0.08 part of oxidizing promoter, 0.02-0.30 part of degradation control agent and 0.08-0.2 part of herbicide. The film is added with the herbicide, so that the degradable mulching film has the function of controlling weeds in the degradation process; the patent of application No. 201510563522.7, a controllable degradable insecticidal weed control full-biodegradable mulching film for crops, which comprises 70-79% of polyalkyl alkanoate, 8-25% of polylactic acid, 1-4% of nano calcium powder, 0.05-0.25% of chlorantraniliprole, 0.05-0.25% of paraquat, 0.1-0.5% of carbendazim and a biodegradable, and is prepared by mixing, kneading at high speed and then blowing the film for molding; the application number is 201610985359.8, an application of a biodegradable weeding mulching film in potato cultivation comprises 70-97% of biodegradable resin and 3-30% of biodegradable herbicide master batch, wherein the master batch comprises 10-60% of herbicide, 0.5-7% of sorbitol laurate and propylene glycol fatty acid ester, and the herbicide precipitation loss cannot be prevented through ultrasonic treatment. Comprehensive analysis of the above patents shows that the herbicide is added directly to the plastic or made into a master batch of herbicide and then added to the plastic for extrusion film blowing. It is known that if the compatibility of the herbicide with the plastic blend is excellent, the herbicide will not precipitate in the plastic and will not serve the purpose of weeding; the herbicide and the blended plastic must be incompatible, and the herbicide can be separated out in the process of rainwater and sunlight exposure to achieve the weeding effect; however, when the herbicide incompatible with plastics is added into the plastics, the herbicide is very easy to precipitate, often weeds do not grow, the herbicide is completely precipitated or remains a few, and even a large amount of herbicide is precipitated in the storage and transportation process of the mulching film, so that the concentration of the herbicide in the mulching film is greatly reduced, and the weeding effect cannot be achieved.
Disclosure of Invention
In order to solve the problems, the invention utilizes the adsorption function of the carbon black, the herbicide is mixed into the carbon black, the mixture is stirred and mixed at a high speed, then the mixture is granulated to prepare carbon black master batch under the action of a biodegradable resin carrier, and then the carbon black master batch is added into a degradable mulching material in proportion to blow a film; during the mixing treatment, the herbicide enters the internal gaps of the carbon black and is wrapped by the carbon black, so that the herbicide is not separated out when the mulching film is blown.
The technical scheme of the invention is as follows: a mulching film for inhibiting the growth of weeds is prepared from the following components in parts by weight: 100 parts of polylactic acid, 50-70 parts of poly adipic acid/butylene terephthalate (PBAT), 5-10 parts of ethyl acetylcitrate, 0.1-1 part of antioxidant, 0.5-3 parts of anti-ultraviolet auxiliary agent and 5-10 parts of carbon black master batch.
Wherein the polylactic acid is levorotatory light or racemic light polylactic acid, the number average molecular weight is between 3 and 15 ten thousand, the molecular weight distribution is between 1 and 2, and the crystallinity is between 20 and 60 percent.
The PBAT is a copolymer of butanediol adipate and butanediol terephthalate, has the characteristics of PBA and PBT, and has the density of 1.10-1.30 g/cm3The glass transition temperature is-25 to-35 ℃, the melting point is 110-120 ℃, and the product is produced by BASF corporation.
The acetyl ethyl citrate is acetylated on the basis of ethyl citrate, so that the binding force between the acetyl ethyl citrate and base resin is increased, the precipitation of a plasticizer is reduced, and the flexibility and the processing performance of the material are improved.
Wherein the antioxidant is preferably compounded by 2, 6-di-tert-butyl-4-methylphenol and 2, 4, 6-tri [2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -4-methyl-6-tert-butylphenol ] -cyanurate, and the weight ratio is 1: (0.5-1).
The anti-ultraviolet auxiliary agent is compounded by a light stabilizer UV-3853S and a light stabilizer Tinuvin 119, and the weight ratio is 1: 1, the light stabilizer UV-3853S is C12-21And C18Unsaturated fatty acid-2, 2,6, 6-tetramethyl-4-piperidine ester, which has excellent light stability effect; the light stabilizer Tinuvin 119 is a triazine-piperidine condensate with high relative molecular mass, and the unique molecular structure enables the condensate to have acid resistance; low volatility and migration resistance.
Wherein the carbon black masterbatch is prepared from the following components in parts by weight: 40-60 parts of Polycaprolactone (PCL); carbon black: 10-20 parts; herbicide: 10-20 parts; carbon black dispersant: 1-10 parts; 5-10 parts of citric acid ester.
The Polycaprolactone (PCL) is biodegradable polyester, has the molecular weight of 1000-3000, has good processing fluidity and is used for master batch carrier resin.
The carbon black is produced by Kabet and has the brand number of M717 carbon black, and the carbon black has the characteristics of good blackness, easy dispersion and good adsorbability.
The herbicide is 4, 6-bis (isopropylamino) -2-methylthio-1, 3, 5-triazine or 2-methyl-4-chlorophenoxyacetic acid.
The carbon black dispersion treatment agent is NDZ-131 brand compound monoalkoxy titanate.
The citric acid ester is butyl citrate, is a biodegradable plasticizer, and is beneficial to uniformly mixing the carbon black and the polycaprolactone by adding the citric acid ester.
The preparation method of the full-biodegradable mulching film for inhibiting weeds comprises the following steps:
(1) preparing a herbicide solution: mixing the acetone or ethanol solvent and the herbicide according to the ratio of 1-1.5: 1, mixing and stirring the mixture according to a proportion, and preparing the herbicide into an acetone or ethanol solution;
(2) weighing carbon black, a herbicide solution (which is weighed according to the proportion of the actual dosage of the herbicide converted into the solution), a carbon black dispersion treatment agent, butyl citrate and polycaprolactone according to the proportion, putting the carbon black dispersion treatment agent, the butyl citrate and the polycaprolactone into a high-speed mixer together for mixing treatment, and heating to 50-70 ℃ to ensure that acetone or ethanol is fully volatilized; the high-speed mixer adopts stepless speed change mixing, the speed and the speed are combined, the slow stirring speed is 450-1500 turns/min, and the high-speed stirring speed is 1200-1500 turns/min. The carbon black is favorable for quickly adsorbing and coating the herbicide, the mixing time is 5-10 minutes, and the mixed materials are discharged;
(3) weighing PLA, PBAT, ethyl acetylcitrate, antioxidant, anti-ultraviolet auxiliary agent and mixed carbon black master batch in proportion, putting the weighed materials into a high-speed stirrer to mix for 5min, and discharging the materials;
(4) extruding and granulating the mixed materials in a double-screw extruder at the extrusion granulation temperature of 110-170 ℃, and cutting the materials into granules by a plastic granulator;
(5) and blowing the prepared granules into a film on a film blowing machine at the temperature of 170-195 ℃, wherein the film thickness is more than 6 mu m, and obtaining the weed-inhibiting mulching film.
The invention has the following beneficial effects: the degradable mulching film is prepared by mixing a herbicide in carbon black, fully adsorbing the herbicide in the internal gaps of the carbon black by utilizing the adsorption effect of the carbon black, preparing a carbon black master batch by granulation under the action of a biodegradable resin carrier, and then adding the carbon black master batch into biodegradable resin for blow molding; the mulching film has the advantages that during storage and transportation, the herbicide cannot run off due to adsorption and coating of the carbon black internal voids, but during use of the mulching film, the herbicide can slowly separate out under the action of light and heat, and water drops formed by evaporation of surface water on the surface of the mulching film flow to the surface of the land, so that the weeding effect is achieved; particularly, the more the herbicide is separated out along with the direct irradiation of the strong solar light at noon, the excellent effect on killing weeds is achieved, and the degradable mulching film can be completely biodegraded into carbon dioxide and water without polluting soil and environment.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
In the examples, the PLA polylactic acid is given by Revole 110, Zhejiang Haizhen biomaterial, Inc., density of 1.25. + -. 0.05,melting point 140-; the grades and indices of PBAT are as follows: the trade name TH801T, Dongguan kernel biodegradable plastics Co., Ltd, the melting point 110-3。
The antioxidant is compounded by 2, 6-di-tert-butyl-4-methylphenol and 2, 4, 6-tri [2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -4-methyl-6-tert-butylphenol ] -cyanurate, and the weight ratio is 1: 1.
the molecular weight of PCL is 2000; the carbon black is carbon black with a trademark of M717 produced by cabot, and the herbicide is 4, 6-bis (isopropylamino) -2-methylthio-1, 3, 5-triazine; the carbon black dispersing agent is composite monoalkoxy titanate with the brand of NDZ-131.
The carbon black master batch is prepared from the following components in parts by weight: 40 parts of Polycaprolactone (PCL); carbon black: 20 parts of (1); herbicide: 20 parts of (1); carbon black dispersion treating agent: 10 parts of (A); butyl citrate: 10 parts.
The anti-ultraviolet auxiliary agent is compounded by a light stabilizer UV-3853S and a light stabilizer Tinuvin 119, and the weight ratio is 1: 1.
table 1 shows the formulations of examples 1 to 6 of the present invention, and the formulations of examples 7 to 9 of the present invention and comparative examples 1 to 3.
TABLE 1 formulations, kg, of inventive examples 1-6
。
TABLE 2 formulations in kg of inventive examples 7-9 and comparative examples 1-3
Comparative example 1 the amount of carbon black masterbatch was reduced based on example 9, comparative example 2 the amount of carbon black masterbatch was increased based on example 9, and comparative example 3 employed carbon black masterbatch without addition of a carbon black dispersion treatment agent.
The preparation method of the full-biodegradable mulching film for inhibiting weeds comprises the following steps:
(1) preparing a herbicide solution: mixing the herbicide with acetone or ethanol solvent according to the weight ratio of 1.5: 1, mixing and stirring the mixture according to a proportion, and preparing the herbicide into an ethanol solution;
(2) weighing carbon black, a herbicide solution (which is weighed according to the proportion converted from the actual dosage of the herbicide), a carbon black dispersion treatment agent, butyl citrate and polycaprolactone according to the proportion, putting the carbon black dispersion treatment agent, the butyl citrate and the polycaprolactone into a high-speed mixer together for mixing treatment, and heating to 60 ℃ to ensure that acetone or ethanol is fully volatilized; the high-speed mixer adopts stepless speed change mixing, the speed and the speed are combined, the slow stirring speed is 450-1500 turns/min, and the high-speed stirring speed is 1200-1500 turns/min. The carbon black is favorable for quickly adsorbing and coating the herbicide, the mixing time is 10 minutes, and the mixed materials are discharged;
(3) weighing PLA, PBAT, ethyl acetylcitrate, antioxidant, anti-ultraviolet auxiliary agent and mixed carbon black master batch in proportion, putting the weighed materials into a high-speed stirrer to mix for 5min, and discharging the materials;
(4) extruding and granulating the mixed materials in a double-screw extruder at the extrusion granulation temperature of 110-170 ℃, and cutting the materials into granules by a plastic granulator;
(5) and blowing the prepared granules on a film blowing machine at the temperature of 170-195 ℃ to form a film with the thickness of 8 mu m to obtain the weed-inhibiting mulching film.
The results of the performance tests of the examples and comparative examples are shown in Table 3.
TABLE 3
。
The test results of the precipitation performance of the mulching films of the examples and the comparative examples under certain conditions are shown in the table 4.
Table 4 precipitation performance test results of examples and comparative examples of degraded mulching film
And (3) testing conditions are as follows: putting a certain weight of mulching film sample into a solution with 3% detergent concentration, soaking at room temperature for 168 hours, taking out, standing at room temperature for drying for 48 hours, weighing and calculating the weight loss of the mulching film, wherein the lower the numerical value is, the less the mulching film is difficult to precipitate, and the more the mulching film is seriously precipitated in percentage.
As can be seen from the performance test results, the anti-precipitation herbicide capability of the mulching film blown by the biodegradable mulching film master batch is better than that of the comparative example.
Tests on planted peanuts show that the pesticide in the mulching film is slow-released and long in pesticide effect time, and under the same planting conditions, the yield of the peanuts in the embodiment 9 is 18% higher than that of the peanuts in the comparison proportion 1, 12% higher than that of the peanuts in the comparison proportion 2 and 10% higher than that of the peanuts in the comparison proportion 3.
Claims (6)
1. A mulching film for inhibiting weed growth is prepared from the following components in parts by weight: 100 parts of polylactic acid, 50-70 parts of poly (butylene adipate)/terephthalate, 5-10 parts of acetyl ethyl citrate, 0.1-1 part of antioxidant, 0.5-3 parts of anti-ultraviolet auxiliary agent and 5-10 parts of carbon black master batch;
the carbon black master batch is prepared from the following components in parts by weight: 40-60 parts of polycaprolactone, 10-20 parts of carbon black, 10-20 parts of herbicide, 1-10 parts of carbon black dispersion treatment agent and 5-10 parts of citric acid ester; the carbon black dispersion treatment agent is composite monoalkoxy titanate with the brand of NDZ-131.
2. The mulching film for inhibiting the growth of weeds of claim 1, wherein the polycaprolactone is a biodegradable polyester with a molecular weight of 1000-3000.
3. The mulching film for inhibiting the growth of weeds of claim 1, wherein said carbon black is carbon black of cabot M717.
4. The mulch film for inhibiting the growth of weeds of claim 1 wherein the herbicide is 4, 6-bis (isopropylamino) -2-methylthio-1, 3, 5-triazine or 2-methyl-4-chlorophenoxyacetic acid.
5. The weed growth inhibiting mulch of claim 1, wherein the citrate ester is butyl citrate.
6. A method of preparing a mulching film for suppressing the growth of weeds of claim 1, comprising the steps of, in order:
(1) preparing a herbicide solution: mixing the acetone or ethanol solvent and the herbicide according to the ratio of 1-1.5: 1, mixing and stirring the mixture according to the proportion, and preparing the solid powder herbicide into an acetone or ethanol solution;
(2) weighing carbon black, a herbicide solution, a carbon black dispersion treatment agent, butyl citrate and polycaprolactone in proportion, putting the weighed materials into a high-speed mixer together for mixing treatment, and heating to 50-70 ℃ to ensure that acetone or ethanol is fully volatilized; the high-speed mixer adopts stepless speed change mixing, the speed and the speed are combined, the low-speed stirring speed is 450-; the carbon black is favorable for adsorbing and coating the herbicide quickly, the mixing time is 5-10 minutes, and the mixed material is discharged to obtain a carbon black master batch, wherein the herbicide solution is weighed according to the solution proportion converted from the actual dosage of the herbicide;
(3) weighing PLA, PBAT, ethyl acetylcitrate, antioxidant, anti-ultraviolet auxiliary agent and mixed carbon black master batch in proportion, putting the weighed materials into a high-speed stirrer to mix for 5min, and discharging the materials;
(4) extruding and granulating the mixed materials in a double-screw extruder at the extrusion granulation temperature of 110-170 ℃, and cutting the materials into granules by a plastic granulator;
(5) and blowing the produced granules on a film blowing machine at the temperature of 170-195 ℃ to obtain the mulching film for inhibiting the growth of weeds.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101496515A (en) * | 2009-03-09 | 2009-08-05 | 张掖市大弓农化有限公司 | Butralin wettable powder |
| CN103497403A (en) * | 2013-09-29 | 2014-01-08 | 广州甘蔗糖业研究所 | Herbicide master batch as well as preparation method and application thereof |
| CN103709778A (en) * | 2013-12-18 | 2014-04-09 | 成都菲斯特化工有限公司 | Carbon black master batch for herbicide-containing plastic mulching films and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101496515A (en) * | 2009-03-09 | 2009-08-05 | 张掖市大弓农化有限公司 | Butralin wettable powder |
| CN103497403A (en) * | 2013-09-29 | 2014-01-08 | 广州甘蔗糖业研究所 | Herbicide master batch as well as preparation method and application thereof |
| CN103709778A (en) * | 2013-12-18 | 2014-04-09 | 成都菲斯特化工有限公司 | Carbon black master batch for herbicide-containing plastic mulching films and preparation method thereof |
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