CN103497403B - Herbicide master batch as well as preparation method and application thereof - Google Patents
Herbicide master batch as well as preparation method and application thereof Download PDFInfo
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- CN103497403B CN103497403B CN201310459832.5A CN201310459832A CN103497403B CN 103497403 B CN103497403 B CN 103497403B CN 201310459832 A CN201310459832 A CN 201310459832A CN 103497403 B CN103497403 B CN 103497403B
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- herbicide
- herbicide master
- weedicide
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- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 69
- 239000004009 herbicide Substances 0.000 title claims abstract description 67
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004698 Polyethylene Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000002362 mulch Substances 0.000 claims description 34
- 241000196324 Embryophyta Species 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 10
- 238000005453 pelletization Methods 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- AAEVYOVXGOFMJO-UHFFFAOYSA-N prometryn Chemical compound CSC1=NC(NC(C)C)=NC(NC(C)C)=N1 AAEVYOVXGOFMJO-UHFFFAOYSA-N 0.000 claims description 4
- CAWXEEYDBZRFPE-UHFFFAOYSA-N Hexazinone Chemical compound O=C1N(C)C(N(C)C)=NC(=O)N1C1CCCCC1 CAWXEEYDBZRFPE-UHFFFAOYSA-N 0.000 claims description 3
- RMFGNMMNUZWCRZ-UHFFFAOYSA-N Humulone Natural products CC(C)CC(=O)C1=C(O)C(O)(CC=C(C)C)C(O)=C(CC=C(C)C)C1=O RMFGNMMNUZWCRZ-UHFFFAOYSA-N 0.000 claims description 3
- HKPHPIREJKHECO-UHFFFAOYSA-N butachlor Chemical compound CCCCOCN(C(=O)CCl)C1=C(CC)C=CC=C1CC HKPHPIREJKHECO-UHFFFAOYSA-N 0.000 claims description 3
- VMSLCPKYRPDHLN-NRFANRHFSA-N humulone Chemical compound CC(C)CC(=O)C1=C(O)C(CC=C(C)C)=C(O)[C@@](O)(CC=C(C)C)C1=O VMSLCPKYRPDHLN-NRFANRHFSA-N 0.000 claims description 3
- WVQBLGZPHOPPFO-UHFFFAOYSA-N 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(1-methoxypropan-2-yl)acetamide Chemical compound CCC1=CC=CC(C)=C1N(C(C)COC)C(=O)CCl WVQBLGZPHOPPFO-UHFFFAOYSA-N 0.000 claims description 2
- KZNDFYDURHAESM-UHFFFAOYSA-N 2-chloro-n-(2-ethyl-6-methylphenyl)-n-(propan-2-yloxymethyl)acetamide Chemical compound CCC1=CC=CC(C)=C1N(COC(C)C)C(=O)CCl KZNDFYDURHAESM-UHFFFAOYSA-N 0.000 claims description 2
- VTNQPKFIQCLBDU-UHFFFAOYSA-N Acetochlor Chemical compound CCOCN(C(=O)CCl)C1=C(C)C=CC=C1CC VTNQPKFIQCLBDU-UHFFFAOYSA-N 0.000 claims description 2
- -1 Stam F-34 Chemical compound 0.000 claims description 2
- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 claims description 2
- RQVYBGPQFYCBGX-UHFFFAOYSA-N ametryn Chemical compound CCNC1=NC(NC(C)C)=NC(SC)=N1 RQVYBGPQFYCBGX-UHFFFAOYSA-N 0.000 claims description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims description 2
- PUIYMUZLKQOUOZ-UHFFFAOYSA-N isoproturon Chemical compound CC(C)C1=CC=C(NC(=O)N(C)C)C=C1 PUIYMUZLKQOUOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 36
- 238000000034 method Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 5
- 238000009333 weeding Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 229920013716 polyethylene resin Polymers 0.000 abstract description 2
- 239000010408 film Substances 0.000 abstract 3
- 229920006243 acrylic copolymer Polymers 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 230000000361 pesticidal effect Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241001232787 Epiphragma Species 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 241001233957 eudicotyledons Species 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention belongs to the field of agricultural thin films and discloses herbicide master batch as well as a preparation method and application thereof. The herbicide master batch comprises the following components by mass percentage: 25%-75% of PE (Poly Ethylene) resin, 10%-60% of a herbicide and 2%-15% of a modifying agent. The herbicide master batch provided by the invention adopts the modifying agents including an ethylene-vinyl alcohol copolymer and an ethylene-acrylic copolymer and the like to pre-treat the herbicide; in the processing process, the modifying agents are fused and then are coated on the surface of the herbicide so as to form a core-shell structure which takes the herbicide as a core and takes the modifying agents as the shell, effectively protect the herbicide and reduce the loss caused by thermal decomposition of the herbicide at a high temperature in a preparation process of the herbicide master batch and a mulching film. The herbicide master batch provided by the invention is used for preparing the weeding mulching film; the herbicide master batch is dispersed uniformly, the releasing speed of the herbicide is slowed, the pesticide effect time can be prolonged, and the weeding effect can still be up to be more than 90% after the mulching film covers for 60 days.
Description
Technical field
The invention belongs to agricultural film field, particularly a kind of Herbicide master batch and its preparation method and application.
Background technology
China is in the seventies introduction in last century plastics agricultural mulching, after crop employing plastic mulching cultivation technology, the ecotope of a relatively-high temperature high humidity is defined under film, be conducive to crop germination growth, crop yield therefore can be made to have a good harvest, but meanwhile, this hot and humid ecotope is also conducive to growing of weeds, weeds and crop strive water, strive fertilizer, so that affect the normal growth of crop, finally cause crop in poor harvest.Therefore after generally taking first spray herbicide in practical application plastic mulching cultivation technology process, the method for epiphragma carrys out management of weeds.But this kind of way increases the cost of labor in proportion of crop planting process undoubtedly, and certain condition restriction (area of lack of water adopts this kind of method to have certain difficulty) can be subject to, in addition, traditional weedicide sprays the loss that mode can cause weedicide in spray process, and produces environmental pollution.Weed removal mulch film is a kind of product innovation integrating weeding and other functions of mulch film, effectively can solve weeding problem under the film in common ground film overwrite procedure; And due to saving of work and time, decrease the planting cost of peasant; In addition, weedicide is added to the effective rate of utilization that can improve weedicide in mulch film, realize the minimizing of weedicide consumption.
Current weed removal mulch film mainly adopts following several method to prepare: one is directly mix with macromolecule resin by weedicide to adopt blow moulding to prepare weed removal mulch film (CN102888040A, CN1927919A) afterwards, weed removal mulch film prepared by this method exists that dispersing herbicides is uneven, difficulty of processing greatly and the problem such as production efficiency is low; Two is adopt the modes such as spraying or coating, bonding weedicide to be coated in mulch film surface (CN87101414.9), this solves the homogeneity of weedicide coating, but this method can cause the loss of weedicide in the course of processing, and be just coated in mulch film surface due to weedicide, its effect of herbicides release rate is fast, and later stage herbicidal effect is difficult to be guaranteed; Three is that weedicide and macromolecule resin are prepared into master batch, then the master batch of preparation is added in macromolecule resin and be blow molded into mulch film (CN1260115A, CN102898714A), mulch film prepared by this kind of method, the dispersing uniformity of weedicide in mulch film can be solved to a certain extent, and the production efficiency that can effectively improve in weed removal mulch film preparation process, but this preparation method's weedicide will bear higher processing temperature, this requires that weedicide at high temperature has certain chemical stability, and the range of choice of weedicide is extremely restricted.
In addition, there is a common technological deficiency in above-mentioned three kinds of weed removal mulch film preparation methods---do not solve the compatibility problem between most low molecule polarity weedicides and nonpolar macromolecule matrix (PE).Because weedicide commercially available is at present all micromolecular compound, and the weedicide of large absolutely number has certain polarity, therefore with the poor compatibility of nonpolar polyethylene (PE) resin, interface binding power is more weak, but all effective pre-treatment and modification are not carried out to weedicide in above-mentioned several weed removal mulch film preparation method, thus the consistency effectively do not improved between weed removal mulch film Semi-polarity weedicide and PE resin matrix, cause prepare weed removal mulch film in use weedicide release rate is too fast, effect of herbicides is shorter, the problems such as herbicidal effect difference, affect application and the popularization of weed removal mulch film.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of Herbicide master batch.
Another object of the present invention is to the preparation method that a kind of above-mentioned Herbicide master batch is provided.
Another object of the present invention is to provide above-mentioned Herbicide master batch preparing the application in weed removal mulch film.
Object of the present invention is realized by following proposal:
A kind of Herbicide master batch, comprises the component of following massfraction:
PE resin 25 ~ 75%
Weedicide 10 ~ 60%
Properties-correcting agent 2 ~ 15%.
Described properties-correcting agent refers at least one in ethylene-vinyl alcohol copolymer (EVOH) and ethylene acrylic acid co polymer (EAA).
Preferably, described properties-correcting agent refers to ethylene acrylic acid co polymer.Properties-correcting agent is the multipolymer of vinyl, vinyl segment in its molecular chain and PE resin have good consistency and bonding force, and vinyl alcohol (EVOH) in modifier molecules chain and vinylformic acid (EAA) part are owing to having stronger polarity, therefore with the weedicide of polarity, there is good consistency and bonding force, thus properties-correcting agent add the consistency can improving PE resin and weedicide.
Described weedicide refers at least one in alachlor, acetochlor, the third careless amine, Butachlor technical 92, metolachlor, Stam F-34, propisochlor, isoproturon, atrazine, prometryn, ametryn, piperazine humulone and hexazinone.
Preferably, the processing aid of described Herbicide master batch also containing 1 ~ 5wt%.
Described processing aid refers at least one in lubricant, dispersion agent and oxidation inhibitor.
Above-mentioned lubricant, dispersion agent and oxidation inhibitor are this area common agents.
The PE resin of the disposable type that described PE resin can use for this area.
A preparation method for above-mentioned Herbicide master batch, comprises following concrete steps:
By part PE resin, weedicide, properties-correcting agent pre-mixing, and ultrasonic activation; Again with remaining PE resin high-speed mixing, extruding pelletization, obtains Herbicide master batch.
Described part PE resin refers to 10 ~ 30wt% of PE resin total amount;
Described pre-mixing refers to mix 3 ~ 5min in mixing machine.
Described ultrasonic activation refers to ultrasonic 3 ~ 25min under 100 ~ 500W power.Ultrasonic wave can utilize its energy produced, strengthen the reactive behavior between the polar functional group of weedicide and properties-correcting agent Semi-polarity or low-pole functional group, thus the bonding force of weedicide and properties-correcting agent is strengthened, finally can prepare weedicide and the good master batch of PE resin compatible.
Described high-speed mixing refers to mix 1 ~ 5min under 600 ~ 1200rpm speed.
Each section of temperature of described extruding pelletization is 110 ~ 160 DEG C.
In above-mentioned mixing and extruding pelletization process, processing aid can be added, as at least one in lubricant, dispersion agent and oxidation inhibitor.
Above-mentioned Herbicide master batch is preparing the application in weed removal mulch film.
Mechanism of the present invention is:
Adopt the multipolymer (EVOH, EAA) of vinyl to be properties-correcting agent, vinyl segment and the PE resin of properties-correcting agent have good consistency, and the polarity of properties-correcting agent or low-pole part and weedicide have stronger bonding force.Compared with prior art, by ultrasonic technique, the functional group reactions that can strengthen weedicide and properties-correcting agent is active, and strengthens the bonding force of weedicide and properties-correcting agent further, thus the interface compatibility of weedicide and PE resin is significantly improved, obtain the good master batch of consistency; And with employing ethylene vinyl acetate (EVA) for compared with properties-correcting agent, EVOH and EAA has stronger molecular polarity, thus close with the weedicide polarity of polarity, bonding force is stronger, modified effect is more obvious.
The present invention has following advantage and beneficial effect relative to prior art:
(1) employ in Herbicide master batch of the present invention EVOH and/or EAA as weedicide and PE resin interface modifier, and carry out enhancing activation by ultrasonic technique, the consistency of weedicide and PE resin be significantly improved, interaction force enhancing;
(2) weedicide surface is coated on after the properties-correcting agent melting that the present invention uses; thus to define weedicide be core; properties-correcting agent is the nucleocapsid structure of shell; effective protection is defined to weedicide, thus decreases the loss that in weeding master batch and mulch film preparation process, weedicide at high temperature causes due to thermolysis.
(3) by Herbicide master batch of the present invention for the preparation of in weed removal mulch film, Herbicide master batch can be made to be dispersed in mulch film, the consistency of weedicide and PE resin is improved, interaction force strengthens, thus the rate of release of weedicide is slowed down, extend its effective drug duration, effectively improve utilization ratio and the utilising efficiency of weedicide, decrease weedicide to run off the groundwater pollution caused, membrane covering after 60 days herbicidal effect still can reach more than 90%.
Accompanying drawing explanation
Fig. 1 is the TGA curve of the Herbicide master batch that embodiment 1 and embodiment 4 prepare.
Fig. 2 is the SEM figure of the Herbicide master batch that embodiment 1 and embodiment 4 prepare, and wherein, a is the Herbicide master batch of embodiment 4, and b is the Herbicide master batch of embodiment 1.
Fig. 3 is the SEM figure of the weed removal mulch film that the Herbicide master batch of embodiment 1 and embodiment 4 prepares, and wherein, a is the weed removal mulch film that the Herbicide master batch of embodiment 4 prepares, and b is the weed removal mulch film that the Herbicide master batch of embodiment 1 prepares.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1: the preparation of Herbicide master batch
Careless for 10kg third amine, 25kg prometryn, 15kg PE resin 7144F, 8kg EAA resin 2002(du pont company are produced) and 1kg Zinic stearas pre-mixing 3min in mixing machine; 25min is activated in the ultrasonic generator of power 100W; Add 40kg PE resin 2426h, 1.7kg PE wax CH-2 and 0.3kg oxidation inhibitor AT168 600rpm high-speed mixing 1min in high-speed mixer again, at 110 ~ 160 DEG C, in twin screw extruder, carry out extruding pelletization, namely obtain Herbicide master batch.
Embodiment 2: the preparation of Herbicide master batch
By 10kg piperazine humulone, 10kg PE resin 7144F, 2kg EVOH resin E105B(Kuraray) and 1kg Zinic stearas pre-mixing 5min in mixing machine; 10min is activated in the ultrasonic generator of power 300W; Add 65kg PE resin 7050,1.7kg PE wax CH-2 and 0.3kg oxidation inhibitor AT1010 800rpm high-speed mixing 5min in high-speed mixer again, at 110 ~ 160 DEG C, in twin screw extruder, carry out extruding pelletization, namely obtain Herbicide master batch.
Embodiment 3: the preparation of Herbicide master batch
By 20kg Butachlor technical 92,40kg hexazinone, 15kg PE resin 7144F, 15kg EVOH resin E105B(Kuraray) and 1.5kg Zinic stearas pre-mixing 4min in mixing machine; 3min is activated in the ultrasonic generator of power 500W; Add 10kg PE resin 7042,2.2kg PE wax CH-2 and 0.3kg oxidation inhibitor AT168 1200rpm high-speed mixing 2min in high-speed mixer again, at 110 ~ 160 DEG C, in twin screw extruder, carry out extruding pelletization, namely obtain Herbicide master batch.
Embodiment 4: the preparation of contrast Herbicide master batch
Careless for 10kg third amine, 25kg prometryn, 15kg PE resin 7144F, 8kg ethylene vinyl acetate copolymer (EVA) V4110F(are raised sub-BASF) and 1kg Zinic stearas pre-mixing 3min in mixing machine; 25min is activated in the ultrasonic generator of power 100W; Add 40kg PE resin 2426h, 1.7kg PE wax CH-2 and 0.3kg oxidation inhibitor AT168 again at high-speed mixer high speed mixing 1min, at 110 ~ 160 DEG C, in twin screw extruder, carry out extruding pelletization, namely obtain Herbicide master batch.
Embodiment 5: the performance measurement of Herbicide master batch
Carry out the performance measurement of TGA thermal weight loss to the Herbicide master batch that embodiment 1 and 4 prepares, weedicide is as blank.The results are shown in Table 1, Fig. 1.
From table 1, Fig. 1, the Herbicide master batch obtained after properties-correcting agent pre-treatment of the present invention has higher thermal weight loss temperature, for reducing the high temperature consumption of weedicide and keeping the drug effect of weedicide to have vital role.
The thermal weight loss performance index of table 1 Herbicide master batch
| Sample | The temperature of weightless 5%/DEG C | The temperature of weightless 10%/DEG C |
| Embodiment 1 Herbicide master batch | 199.9 | 221.8 |
| Embodiment 4 Herbicide master batch | 190.8 | 207.2 |
| Weedicide | 176.3 | 189.0 |
SEM scanning is carried out to the Herbicide master batch that embodiment 1 and 4 index obtains, the results are shown in Figure 2.
As seen from Figure 2, add properties-correcting agent of the present invention and adopt ultrasound-enhanced activate after, the interface of weedicide particle and PE matrix is fuzzy (Fig. 2 b), and illustrate that its interface interaction power strengthens, the interface compatibility of weedicide and PE matrix improves; And using the interface of EVA pretreated weedicide particle and PE matrix clear, both consistency is poor, and (Fig. 2 is a).
After Herbicide master batch embodiment 1 and 4 prepared mixes with PE resin (70%LLDPE7042N and 30%HDPE TR144), blowing processing is carried out in Single screw extrusion blow moulding machine, the processing temperature in forcing machine Zhong Ge district is 130 ~ 200 DEG C, finally rolling is carried out to the film of blowing, obtain weed removal mulch film, measure its herbicidal performance, common ground film, as blank, the results are shown in Table 2.The weed removal mulch film that the Herbicide master batch of embodiment 1 and 4 prepares carries out SEM scanning, sees Fig. 3.
As seen from Figure 3, compared with the weed removal mulch film adopting the pretreated master batch of EVA to prepare, adopt weed removal mulch film prepared by Herbicide master batch of the present invention, the hole on its mulch film surface is regular, and size is homogeneous.This be due to properties-correcting agent add and hyperacoustic enhancing activation improves the interface compatibility of weedicide and PE matrix, thus make both have good interface compatibility.
The herbicidal performance index of table 2 weed removal mulch film
Note: CK is common ground film.
From table 2, the weed removal mulch film adopting the master batch of the inventive method to prepare still can reach more than 90% to single dicots preventive effect in use after 60 days, this is because properties-correcting agent and hyperacoustic enhancing activation make the interaction force between weedicide and PE matrix strengthen, thus the speed making weedicide discharge from mulch film slows down, the effective drug duration of weedicide extends.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a Herbicide master batch, is characterized in that the component comprising following massfraction:
PE resin 25 ~ 75 %
Weedicide
10 ~ 60 %
Properties-correcting agent 2 ~ 15 %;
Described properties-correcting agent refers at least one in ethylene-vinyl alcohol copolymer and ethylene acrylic acid co polymer.
2. Herbicide master batch according to claim 1, is characterized in that: described weedicide refers at least one in alachlor, acetochlor, the third careless amine, Butachlor technical 92, metolachlor, Stam F-34, propisochlor, isoproturon, atrazine, prometryn, ametryn, piperazine humulone and hexazinone.
3. Herbicide master batch according to claim 1, is characterized in that: described Herbicide master batch contains the processing aid of 1 ~ 5 wt%.
4. Herbicide master batch according to claim 3, is characterized in that: described processing aid refers at least one in lubricant, dispersion agent and oxidation inhibitor.
5. Herbicide master batch according to claim 1, is characterized in that: described properties-correcting agent refers to ethylene acrylic acid co polymer.
6. a preparation method for the Herbicide master batch according to any one of claim 1 ~ 2, is characterized in that comprising following concrete steps: by part PE resin, weedicide, properties-correcting agent pre-mixing, and ultrasonic activation; Again with remaining PE resin high-speed mixing, extruding pelletization, obtains Herbicide master batch.
7. the preparation method of Herbicide master batch according to claim 6, is characterized in that: described part PE resin refers to 10 ~ 30 wt% of PE resin total amount; Described pre-mixing refers to mix 3 ~ 5 min in mixing machine; Described ultrasonic activation refers to ultrasonic 3 ~ 25 min under 100 ~ 500 W power.
8. the preparation method of Herbicide master batch according to claim 6, is characterized in that: described high-speed mixing refers to mix 1 ~ 5 min under 600 ~ 1200 rpm speed; Each section of temperature of described extruding pelletization is 110 ~ 160 DEG C.
9. the Herbicide master batch according to any one of Claims 1 to 5 is preparing the application in weed removal mulch film.
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| CN105746528A (en) * | 2016-03-31 | 2016-07-13 | 太仓市新华粮食生产专业合作社 | Weed killer composition |
| CN107759993B (en) * | 2017-12-03 | 2019-09-13 | 山东天野生物降解新材料科技有限公司 | It can inhibit the whole life cycle design masterbatch and preparation method thereof of weed growth |
| CN107903597B (en) * | 2017-12-03 | 2020-01-14 | 山东天野生物降解新材料科技有限公司 | Full-biodegradable mulching film for inhibiting weeds and preparation method thereof |
| CN107936507B (en) * | 2017-12-03 | 2020-01-14 | 山东天野生物降解新材料科技有限公司 | Mulching film for inhibiting weed growth and preparation method thereof |
| CN107936494B (en) * | 2017-12-03 | 2019-10-11 | 山东天野生物降解新材料科技有限公司 | A kind of whole life cycle design masterbatch and preparation method thereof inhibiting weeds |
| CN111171426A (en) * | 2020-01-08 | 2020-05-19 | 济南圣雷石化科技有限公司 | Mulching film weed control master batch and preparation method thereof |
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| CN1563169A (en) * | 2004-04-12 | 2005-01-12 | 苏道勇 | Agglomerate of weeding mulching film |
| CN102276966A (en) * | 2011-08-02 | 2011-12-14 | 广州甘蔗糖业研究所 | Biodegradable weeding mulching film masterbatch, weeding mulching film and preparation method thereof |
| CN102898714A (en) * | 2012-11-07 | 2013-01-30 | 常璟 | Weeding mulching film masterbatch and preparation method thereof |
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| CN1563169A (en) * | 2004-04-12 | 2005-01-12 | 苏道勇 | Agglomerate of weeding mulching film |
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