CN110330773A - A kind of controllable full-biodegradable mulch and preparation method thereof - Google Patents

A kind of controllable full-biodegradable mulch and preparation method thereof Download PDF

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Publication number
CN110330773A
CN110330773A CN201910653039.6A CN201910653039A CN110330773A CN 110330773 A CN110330773 A CN 110330773A CN 201910653039 A CN201910653039 A CN 201910653039A CN 110330773 A CN110330773 A CN 110330773A
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parts
mulch
agent
controllable full
biodegradable
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穆正洋
栗国民
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Shenzhen Lilian Environmental Material Co Ltd
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Shenzhen Lilian Environmental Material Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • C08J2423/08—Copolymers of ethene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
    • 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
    • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2435/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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Abstract

The invention belongs to biodegradation material is modified and applied technical field, it is related to a kind of controllable full-biodegradable mulch and preparation method thereof.The controllable full-biodegradable mulching film raw material includes following parts by weight proportion: 1-50 parts of high-crystallinity polylactic acid, polyadipate/10-90 parts of butylene terephthalate, 0-50 parts of lined polymethyl ethylene carbonate, 0.1-2 parts of plasticizer, 0.1-2 parts of chain extender, 0.1-1 parts of lubricant, 0.1-1 parts of dispersing agent, 0.1-1 parts of opening agent, 1-3 parts of compatilizer, 0.1-8 parts of gas barrier agent, 0-1 parts of antioxidant, 0-1 parts of light stabilizer, 0.1-2 parts of anti-hydrolysis agent, 0-3 parts of antibacterial agent.It will be uniformly mixed after each pretreatment of raw material, squeezed out and controllable full-biodegradable mulch, ground film thickness 0.005-0.020mm is made in blow molding.Whole life cycle design good mechanical properties of the present invention, heat preservation soil moisture conservation function admirable, can be voluntarily degradable, Plastic-film disintegration rate can especially be regulated and controled according to " the mulch film function phase " of different regions different crops mulch, to meet the needs of different regions different crops.

Description

A kind of controllable full-biodegradable mulch and preparation method thereof
Technical field
The invention belongs to biodegradation material is modified and applied technical field, and in particular to a kind of controllable full-biodegradable Film and preparation method thereof.
Background technique
Due to having the function of heat preservation soil moisture conservation, be covered on clear PE plastic film on crops can with increasing both production and income, but by In its non-degradable, " white pollution " to overflow is also brought.
Since ultra-thin mulch is widely used and lacks used plastic collection technology and mechanism, the rate of recovery of China's mulch is insufficient 2/3, the mulch of a large amount of residuals in the soil destroys soil texture, hinders the migration of soil moisture and nutrient, affects Crop growthing development.With in soil mulch residual quantity it is increasingly soaring, originally the mulch of increasing crop yield can be made but to start Lead to the underproduction.
The regional correlation of Xinjiang Academy of Land Reclamation &. Cultivation experiments have shown that, when land equalization residual-film amount is 77.9kg/ hectares, At 167.6kg/ hectares, 279.0kg/ hectares and 372.2kg/ hectares, cotton underproduction rate is respectively 3.82%, 7.45%, 11.71% and 18.92%.The main reason for conclusion that Xinjiang Academy of Land Reclamation &. Cultivation provides is, the cotton underproduction is residual mulching film, with The amplitude of the increase of mulch residual quantity, the cotton underproduction has the tendency that aggravation.
Chinese Academy of Agricultural Sciences's monitoring data show that long-term overlay film farmland mulch residual quantity is 5~15 kgs/acre at present, Influence very serious is generated on soil texture, plant growth and ecological environment.
Since the planting patterns of various regions is different, worn-out agricultural film mechanization recovery apparatus differs greatly, and region is poor for applicability, because The mechanical investment of this configuration recycling is very high.After machinery recycling, it is still desirable to it is manually secondary to pick up receipts, cause cost recovery to continue height Position.Now, the recycling of residual film mostly uses greatly manual type, and recycling is not thorough, low efficiency, and the mulch recycled is mostly just located in Reason, is deposited on ridge or field road, can not only pollute environment again, also create the great wasting of resources.
The requirement of " mulch is degradable " is complied with, also circulate a large amount of " degradable " mulch on the market at present, mainly includes Photodegradation film, thermal-oxidative degradation mulch, starch filled mulch etc., but the bulk composition of actually these " degradable " mulches remains unchanged Polyethylene, be cracked into after use fragment bury in the soil can not it is degradable, can not also recycle, directly contribute serious two Secondary pollution.Therefore, the research of whole life cycle design and application are by expectation.
Many problems are encountered during research and extension, especially, full-biodegradable material vapor itself is saturating It is excessive higher, cause mulch soil moisture conservation performance bad, and degradation process is not sufficiently stable and controllably.In view of whole life cycle design material Expect the characteristic of itself, still need to overcome Railway Project before large-scale application: first is that operability, mulch tensile strength must meet overlay film behaviour The requirement of work, especially in large-scale do mechanization operation agriculture district, it is desirable that ground film dynamic performance meets mechanization plastic film mulch operation；Second is that Functionality will meet the functional requirement that Meteorological effect suppression grass etc. is conducive to plant growth after overlay film；Third is that controllability, i.e. mulch are broken Splitting and degrading just start after completing its basic function, especially be unable to premature rupture and degradation.
The degradation process of whole life cycle design is illuminated by the light, temperature, moisture and soil environment are affected, particular organisms Degradative plastic film may only meet the requirement of certain crops in an area, but in another area, since environment is different and makees Object grows the difference to environmental requirement, and this Biodegradable mulch may be just completely inadaptable.
Statistical data shows that Chinese mulch dosage increases to 145.5 ten thousand t in 2015 from 0.6 ten thousand t of nineteen eighty-two, covering More than 11.3 ten thousand hms of the area from nineteen eighty-two2It is expanded to 1831.8 ten thousand hm in 20152.Application region is gradually expanded from outskirts of a town vegetable field Northern cold drought-hit area, Southwest Mountainous Areas are arrived greatly, and finally all provinces (area) are promoted in the whole nation, wherein northwest corn and cotton produce It is that mulch uses by force that area, Northeast China grey bristle production district, North China peanut and cotton production areas, southwestern tobacco producing region and all vegetables, which concentrate producing region, Spend higher region.
The Different Crop of different regions has " the mulch film function phase " of a covering mulch, i.e., " a certain crop is a certainly Area requires the mulch of covering that the best number of days for cracking and degrading can just occur after completing its basic function, that is, mulch covers Lid farmland soil face is able to maintain the complete number of days of film surface ", mulch should keep substantially complete before this number of days, maintain Meteorological effect With the functions such as management of weeds, after this number of days, these functions disappear substantially, and this requires researchers will be according to regional environment item Part and crop require to carry out the research and development of the whole life cycle design of controllable degradation time.
Traditional PE mulch recycling is inherently very difficult, as the enhancing of people's environmental consciousness, mulch recycle laws and regulations Perfect, rural laborer missing and used plastic collection cost of labor continuous rising, common PE mulch and Biodegradable mulch Comprehensive use cost will become closer to, and Biodegradable mulch substitution common PE mulch is the necessary of film-mulching technique development Road, the application prospect of Biodegradable mulch is very considerable.
Summary of the invention
The present invention above-mentioned whole life cycle design application in encounter aiming at the problem that and deficiency, propose that a kind of mechanical property is excellent Good, vapor water barriers performance is good, in compost environment can completely spontaneous degradation, according to different regions different crops cover ground The whole life cycle design and preparation method thereof of " mulch film function phase " controllable degradation time of film.
The present invention for mulch need to have excellent mechanical property, vapor water barriers performance and can it is spontaneous degradable and drop Solve time controllable characteristic, adopt the technical scheme that: by plasticizer, chain extender, high-crystallinity polylactic acid, gas barrier agent, Lubricant, dispersing agent, compatilizer, antioxidant, light stabilizer, anti-hydrolysis agent and antibacterial agent introduce full-biodegradable material system In, it using double-screw extruding pelletizing generally in the art and is blown by adjusting each component ratio with complete biodegradable resin alloy Film molding equipment prepares a kind of controllable full-biodegradable mulch.
In technical solution of the present invention, the raw material of the controllable full-biodegradable mulch include that following parts by weight are matched Than: 1-50 parts of high-crystallinity polylactic acid, polyadipate/10-90 parts of butylene terephthalate, lined polymethyl ethylene carbonate 0-50 It is part, 0.1-2 parts of plasticizer, 0.1-2 parts of chain extender, 0.1-1 parts of lubricant, 0.1-1 parts of dispersing agent, 0.1-1 parts of opening agent, compatible 1-3 parts of agent, 0.1-8 parts of gas barrier agent, 0-1 parts of antioxidant, 0-1 parts of light stabilizer, 0.1-2 parts of anti-hydrolysis agent, antibacterial agent 0-3 Part.
The high-crystallinity polylactic acid is general thin grade polylactic acid as made from crystalline modified, density 1.30 ± 0.05g/cm3, 3~8g/10min of melting means (190 DEG C, 2.16Kg), 170~180 DEG C of fusing point, tensile strength >=45~53MPa are broken Split elongation >=8~15%, 5~10KJ/m of impact strength2(Izod)。
Polyadipate/the butylene terephthalate, density 1.22g/cm3, melting means 4.0g/10min (190 DEG C, 2.16Kg), 115~125 DEG C of fusing point, tensile strength >=21MPa, elongation at break >=670%.
The lined polymethyl ethylene carbonate weight average molecular weight is 3-10 ten thousand, and passes through termination process.
The plasticizer is polyethylene glycol -200, polyethylene glycol -300, polyethylene glycol-400, polyethylene glycol -500, gathers Ethylene glycol -1500, Polyethylene glycol-2000, polyethylene glycol -3000, polyethylene glycol-4000, polyethylene glycol-6000, polyethylene glycol - 8000, polyethylene glycol-1000 0, tributyl citrate, tributyl 2-acetylcitrate, D-sorbite, epoxidized soybean oil, adipic acid One or more of dibutyl ester.
The chain extender is ethylene-methyl acrylate-glyceryl methacrylate terpolymer, hexa-methylene One or more of diisocyanate, epoxies chain extender.
The lubricant is one or more of stearic acid, zinc stearate, calcium stearate, magnesium stearate.
The dispersing agent is makeup grade White Mineral Oil, polyethylene wax, oxidized polyethylene wax, glycerin monostearate, double hard One or more of glycerol, microcrystalline wax.
The opening agent is oleamide, erucyl amide, ethylene bis stearic acid amide (EBS), artificial synthesized unformed One or more of silica, talcum powder, diatomite.
The compatilizer is cumyl peroxide, dibenzoyl peroxide, phenylethylene-maleic anhydride random copolymerization One or more of object, olefin copolymer graft glycidyl methacrylate.
The gas barrier agent is organobentonite, organic coating lithium aluminium silicate, organic modified nano montmorillonite, organic One of modified Nano aluminum oxide.
The antioxidant is compound antioxygen made of main antioxidant 1010 and auxiliary anti-oxidant 168 compound according to a certain percentage Agent.
The light stabilizer is made of ultraviolet absorbing agent and hindered amine light stabilizer compound according to a certain percentage Composite light stabilizer.
The anti-hydrolysis agent is carbodiimides monomer, aromatic polycarbodiimide, diphenylmethane diisocyanate Ester, Toluene-2,4-diisocyanate, one of 4- diisocyanate, 2- oxazoline compound.
The antibacterial agent is the chloro- N- octyl -3- isothiazolinone of 4,5- bis-, Kathon CG, N- methyl 1,2- benzisothiazole Quinoline -3- ketone, N- normal-butyl 1,2-benzisothiazolin-3-one, N- n-octyl 1,2-benzisothiazolin-3-one, Bravo, oneself One or more of azoles alcohol, Tebuconazole, carbendazim.
A kind of preparation method of controllable full-biodegradable mulch of the invention, preparation step and condition are as follows:
1) by high-crystallinity polylactic acid, the polyadipate/butylene terephthalate, lined polymethyl ethylene in the claims 1 Carbonic ester is 4~6 hours dry under conditions of before in 60 DEG C；
2) compatilizer in the claims 10 is 2~3 hours dry under conditions of before in 90 DEG C；
3) by high-crystallinity polylactic acid, the polyadipate/butylene terephthalate, lined polymethyl ethylene carbonate after drying process Weighed in the ratio in the claims 1, weigh it is good after put into high-speed mixer, start to stir at low speed, while stirring according to It is secondary be added pretreated plasticizer, dispersing agent, lubricant, opening agent, gas barrier agent, chain extender, compatilizer, antioxidant, Light stabilizer, anti-hydrolysis agent, antibacterial agent stir at low speed 3~15 minutes, then high-speed stirred 10~20 minutes, will after mixing Material be added double screw extruder extruding pelletization；
4) it is 120~200 DEG C, 150~450rpm of screw speed that the double screw extruder, which squeezes out processing temperature, screw slenderness ratio 36~48:1；
5) pellet made from extruding pelletization is 4~6 hours dry under conditions of 60 DEG C；
6) 5) plastic film blow molding machine is added in the pellet after middle drying process and controllable entirely biological drop is made through blowing step Mulch, ground film thickness 0.005-0.020mm are solved, the machining temperature of plastic film blow molding is 150~190 DEG C, Blow-up ratio is 2~4:1, screw slenderness ratio >=25:1.
The process that the present invention prepares above-mentioned controllable full-biodegradable mulch is simple, and process units is dress generally in the art It sets, such as high-speed mixer, double screw extruder, plastic film blow molding machine.
Compared with prior art, the beneficial effects of the present invention are:
1, high-crystallinity polylactic acid has been selected in controllable full-biodegradable mulch raw material of the present invention, performance advantage is Crystallinity is high, and crystal itself is piled up closely, crystalline portion air-tightness height, the crystal of crystallinity height then air-tightness height and good barrier property Moiety content is high, helps to improve the vapor water barriers performance of mulch, i.e. soil moisture conservation performance；Meanwhile high-crystallinity polylactic acid tension The tensile strength of mulch can be improved in excellent strength, is conducive to large-scale mechanization plastic film mulch operation；In addition, in crystallization type polylactic acid The degradation rate of crystal region is more much slower than unformed area, so the degradation for selecting high-crystallinity polylactic acid to advantageously reduce mulch is fast Rate extends its degradation time.
2, polyadipate/butylene terephthalate has been selected in controllable full-biodegradable mulch raw material of the present invention (PBAT), its advantage is that elongation at break it is high, processing film forming it is excellent, Blown Film after being blended with other biological degradable material, Film flexibility is good, and intensity is high.PBAT is a kind of non-crystalline polymer, compared with the unformed area of PLA, degradation rate compared with Slowly, therefore, select PBAT that can reduce the degradation rate of mulch on the whole as the main substrate of mulch.Biodegradation material is in soil Degradation in earth is more complicated process, and the principal element for influencing degradation rate includes the molecular structure of material, molecular weight, knot The internal causes such as brilliant degree and external environment effect (such as temperature and humidity, illumination, oxygen, pH value, bacterium type).PLA unformed area Degradation with PBAT is the hydrolysis of ester bond first, and the two is compared, and the rate of PBAT ester linkage hydrolyzing is significantly less than PLA unformed area, This is because in PBAT strand contain a large amount of phenyl ring, with biggish steric hindrance, thus hinder hydrolysate with And in the soil liquid-attack of the OH to the adjacent ester bond of phenyl ring, reduce the ester linkage hydrolyzing rate of PBAT；Moreover, PBAT ester bond Big pi bond on C=O and adjacent phenyl rings in middle carbonyl carbon forms conjugated system can equally make so that molecular structure is more stable The hydrolysis rate of PBAT ester bond reduces.
3, the lined polymethyl ethylene carbonate (PPC) and gas barrier selected in the present invention help to improve the soil moisture conservation of mulch Function strengthens the moisture-keeping function to soil, while hindering the migration and fortune of vapor, oxygen molecule between PLA/PBAT macromolecular It is dynamic, attack of the hydrone to ester bond on macromolecular chain is reduced, hydrolysis rate is reduced, also reduction oxygen and strand contact several Rate reduces the degradation of optical and thermal oxygen.Lined polymethyl ethylene carbonate (PPC) flexibility is excellent, is easy to blowfilm shaping, is a kind of gas resistance Every the excellent full-biodegradable material of property.The microcosmic laminated structure of gas barrier agent inserts between PLA/PBAT/PPC macromolecular, by It is acted in the high-barrier of lamella, gas molecule need to can just be diffused around the lamella, and lamella enough in this way is in polymer It is formed a kind of " labyrinth " structure in system, is added significantly to the tortuous and length of vapor and oxygen molecule diffusion path Degree, diffusion rate decline to a great extent, and the barrier property of mulch is made to get a promotion.
4, the compatilizer selected in the present invention is conducive to improve the interface between inorganic gas barrier agent and biodegradable plastic Compatibility conducive to evenly dispersed and intercalation of the inorganic gas barrier in biodegradable plastic, while also improving not of the same race Interface compatibility between class biodegradation material.
5, the chain extender selected in the present invention can increase the molecular weight of PLA/PBAT/PPC molecule, while cause PLA/ More branched structures are generated on PBAT/PPC strand, the melt strength of material can be improved, and improve variety classes biodegrade The compatibility of storeroom keeps the processing film forming of material more excellent.Furthermore molecular weight increases and branched structure increases The degradation rate of mulch can be reduced.
6, the lubricant and dispersing agent selected in the present invention are conducive to the mixing of inorganic gas barrier and biodegradable plastic, Dispersed homogeneous degree of the inorganic gas barrier in polymeric system is greatly improved, is conducive to inorganic barrier dosage form at more more evenly Intercalation configuration, play the synergistic effect with compatilizer；Meanwhile improving the smooth degree of film.
7, the antioxidant selected in the present invention can reduce the thermal-oxidative degradation rate of whole life cycle design.PLA,PBAT, PPC is to thermally labile, after squeezing out melt-processed, due to oxygen in the impurity such as heated, stress, moisture, soda acid and air Effect is easily degraded.The present invention uses the Hinered phenols antioxidant 1010 of stability and high efficiency for primary antioxidant, gives as hydrogen Body captures PLA, PBAT, PPC molecule and decomposes the alkoxy free group RO and peroxylradicals ROO generated, with phosphite ester Kind antioxidant 168 is that auxiliary antioxidant ionizes hydroperoxide decomposition ROOH, is constituted the compound antioxidant system of binary with this, inhibited Thermal-oxidative degradation.
8, the present invention stablizes collaboration system using the light that ultraviolet absorbing agent and hindered amine light stabilizer are constituted and can drop The optical and thermal oxygen degradation rate of low whole life cycle design.The amine functional group that is obstructed in hindered amine light stabilizer is in aerobic state After lower absorption luminous energy, NO free radical NO can be changed into, NO free radical can capture PLA/PBAT/PPC photooxidation drop Alkyl living radical caused by solving, to inhibit chain reaction of degrading；Amido in hindered amine light stabilizer can be with Hydrogen in hydroperoxides resolves into NO free radical after combining, and then reacts with living radical, is allowed to be converted into stable Alcohol, ketone compound；Hindered amine nitrogen-oxygen free-radical can make the singlet oxygen in excitation state return to base by the approach of transmitting energy State, so that singlet oxygen be prevented to cause the progress of degradation reaction.Hindered amine light stabilizer and ultraviolet absorbing agent and antioxidant There is good synergistic effect.Such stabilizer and resin have good compatibility, are able to satisfy the requirement of ground membrane product.
9, the anti-hydrolysis agent selected in the present invention is able to suppress the hydrolysis of biodegradable plastic, exists in Biodegradable polyester Unreacted carboxyl, when polymer meets water or moisture for a long time, polyester segment can occur hydrolysis and be broken generation carboxyl.Carboxyl There is facilitation to polyester hydrolysis, using anti-hydrolysis agent, reacts away the carboxyl in system, generate stable uride, inhibit Hydrolysis continues, to improve the anti-hydrolytic performance of Biodegradable polyester.For because of chain rupture caused by hydrolyzing, resistant to hydrolysis There are also certain " repairing " effects for agent.
10, the antibacterial agent selected in the present invention can effectively inhibit the biodegradation of microorganism, extend Plastic-film disintegration Time.Antibacterial agent high temperature resistant in the present invention, antibacterial agent are added by way of squeezing out with other raw material blended meltings, And the processing temperature of biodegradation material is generally higher.It is various to participate in biodegradable microbe species, based on various moulds, There are also bacterium/actinomyces to participate in degradation simultaneously, therefore the antibacterial bacterium of selected antibacterial agent spectrum is wide, and is especially focused on antifungi energy Power.In view of mulch is degraded in the soil, selected antibacterial agent is safety low-poison, and do not harm the crops growth.
Controllable full-biodegradable mulch of the present invention is taken plasticizer, chain extender, high-crystallinity polylactic acid, gas barrier Agent, lubricant, dispersing agent, compatilizer, antioxidant, light stabilizer, anti-hydrolysis agent and antibacterial agent introduce full-biodegradable material In system, by adjusting the ratio of each component, technical solution with complete biodegradable resin alloy, extruding pelletization, blowfilm shaping, It realizes whole life cycle design high-tensile, meet extensive mechanization plastic film mulch operation, soil moisture conservation function is excellent, and degradation time can The purpose of control.
The device that the present invention prepares above-mentioned controllable full-biodegradable mulch is device generally in the art, and production technology is mature, Process is simple and easy, does not need additionally to increase production cost.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, the scope of the present invention is not limited to implement Example, those skilled in the art make any change within the scope of the claims and shall fall within the protection scope of the present invention.
For the crops of several type areies, China, " the mulch film function phase " of mulch, the invention patent are covered according to it Specifically enumerate following embodiment.
The mechanical performance index of whole life cycle design and steam penetrating capacity are up to state standards in following embodiment The requirement of " the agricultural covered ground film of GB/T 35795-2017 complete biodegradable ", wherein steam penetrating capacity is according to country 38 DEG C, relative humidity 90% in standard " GB/T 1037-1988 plastic film and the cup type method of sheet material water vapor permeability test method " Condition test.
Embodiment 1
" the mulch film function phase " about 40 days of the tobacco covering mulch of southwestern low altitude area
The raw material of the whole life cycle design of the present embodiment weigh each component by following parts by weight:
25 parts of high-crystallinity polylactic acid, 75 parts of polyadipate/butylene terephthalate, 0.3 part of epoxidized soybean oil, poly- second two 0.6 part of alcohol -8000,0.6 part of hexamethylene diisocyanate, 0.2 part of calcium stearate, 0.3 part of oxidized polyethylene wax, oleic acid acyl 0.4 part of amine, 0.03 part of cumyl peroxide, 1.5 parts of atactic styrene-maleic anhydride copolymer, organic modified nano cover de- Native 3 parts, 0.3 part of composite antioxidant, 1.5 parts of methyl diphenylene diisocyanate, the chloro- N- octyl -3- isothiazolinone 2 of 4,5- bis- Part.
Preparation step and condition are as follows:
1) by high-crystallinity polylactic acid, polyadipate/butylene terephthalate, drying 4 is small under conditions of before in 60 DEG C When；
2) atactic styrene-maleic anhydride copolymer is 2 hours dry under conditions of before in 90 DEG C；
3) high-crystallinity polylactic acid, the polyadipate/butylene terephthalate after drying process are pressed into above-mentioned weight ratio Weigh it is good after put into high-speed mixer, start to stir at low speed, stirring while sequentially adds pretreated epoxidized soybean oil, poly- Ethylene glycol -8000, hexamethylene diisocyanate, calcium stearate, oxidized polyethylene wax, oleamide, cumyl peroxide, Atactic styrene-maleic anhydride copolymer, organic modified nano montmorillonite, composite antioxidant, methyl diphenylene diisocyanate, 4,5- bis- chloro- N- octyl -3- isothiazolinone, stir at low speed 3 minutes, then high-speed stirred 10 minutes, by object after mixing Double screw extruder extruding pelletization is added in material；
4) it is 120~200 DEG C, screw speed 350rpm, screw slenderness ratio 44:1 that double screw extruder, which squeezes out processing temperature,；
5) pellet made from extruding pelletization is 4 hours dry under conditions of 60 DEG C；
6) plastic film blow molding machine is added in the pellet after above-mentioned drying process and controllable full biology drop is made through blowing step Mulch is solved, the machining temperature of plastic film blow molding is 150~190 DEG C, and blow-up ratio is 2~4:1, screw rod major diameter Compare 28:1.
Its testing performance index the results are shown in Table 1
Embodiment 2
" the mulch film function phase " about 65 days of the peanut covering mulch of northeast Base of Liaohe Plain
The raw material of the whole life cycle design of the present embodiment weigh each component by following parts by weight:
15 parts of high-crystallinity polylactic acid, 80 parts of polyadipate/butylene terephthalate, 5 parts of lined polymethyl ethylene carbonate, acetyl 0.3 part of tributyl citrate, 0.4 part of polyethylene glycol-4000, ethylene-methyl acrylate-glyceryl methacrylate three 0.8 part of membered copolymer, 0.2 part of stearic acid, 0.4 part of glycerin monostearate, 0.3 part of ethylene bis stearic acid amide, olefin-copolymerization 1.8 parts of object graft glycidyl methacrylate, 4 parts of organobentonite, 0.5 part of composite antioxidant, composite light stabilizer 0.6 Part, 1.2 parts of aromatic polycarbodiimide, 1.5 parts of N- n-octyl 1,2-benzisothiazolin-3-one.
Preparation step and condition are as follows:
1) high-crystallinity polylactic acid, polyadipate/butylene terephthalate, lined polymethyl ethylene carbonate is preceding in 60 in use It is 4 hours dry under conditions of DEG C；
2) olefin copolymer graft glycidyl methacrylate is 2 hours dry under conditions of before in 90 DEG C；
3) by high-crystallinity polylactic acid, the polyadipate/butylene terephthalate, lined polymethyl ethylene carbonate after drying process High-speed mixer is put into after weighing by above-mentioned weight ratio, starts to stir at low speed, stirring while has sequentially added to be located in advance The tributyl 2-acetylcitrate of reason, polyethylene glycol-4000, ethylene-methyl acrylate-glyceryl methacrylate ternary are total Polymers, stearic acid, glycerin monostearate, ethylene bis stearic acid amide, olefin copolymer grafted methacrylic acid glycidol Ester, organobentonite, composite antioxidant, composite light stabilizer, aromatic polycarbodiimide, N- n-octyl 1,2- benzisothia Oxazoline -3- ketone stirs at low speed 5 minutes, then high-speed stirred 12 minutes, and double screw extruder is added in material after mixing and is squeezed It is granulated out；
4) it is 120~200 DEG C, screw speed 350rpm, screw slenderness ratio 44:1 that double screw extruder, which squeezes out processing temperature,；
5) pellet made from extruding pelletization is 4 hours dry under conditions of 60 DEG C；
6) plastic film blow molding machine is added in the pellet after above-mentioned drying process and controllable full biology drop is made through blowing step Mulch is solved, the machining temperature of plastic film blow molding is 150~190 DEG C, and blow-up ratio is 2~4:1, screw rod major diameter Compare 28:1.
Its testing performance index the results are shown in Table 2
Embodiment 3
" the mulch film function phase " about 75 days of the cotton covering mulch of Western Junggar Basin, Xinjiang, China edge
The raw material of the whole life cycle design of the present embodiment weigh each component by following parts by weight:
15 parts of high-crystallinity polylactic acid, 70 parts of polyadipate/butylene terephthalate, 15 parts of lined polymethyl ethylene carbonate, lemon 0.3 part of lemon acid tributyl, 0.5 part of polyethylene glycol-6000,1 part of epoxies chain extender, 0.3 part of zinc stearate, the makeup white mine of grade It is 0.5 part of oil, 0.2 part of erucyl amide, 0.05 part of dibenzoyl peroxide, 2 parts of atactic styrene-maleic anhydride copolymer, organic 6 parts of coating alumina silicate potassium, 0.5 part of composite antioxidant, 0.7 part of composite light stabilizer, 1 part of 2- oxazoline compound, Bravo 2 Part.
Preparation step and condition are as follows:
1) high-crystallinity polylactic acid, polyadipate/butylene terephthalate, lined polymethyl ethylene carbonate is preceding in 60 in use It is 4 hours dry under conditions of DEG C；
2) atactic styrene-maleic anhydride copolymer is 2 hours dry under conditions of before in 90 DEG C；
3) by high-crystallinity polylactic acid, the polyadipate/butylene terephthalate, lined polymethyl ethylene carbonate after drying process High-speed mixer is put into after weighing by above-mentioned weight ratio, starts to stir at low speed, stirring while has sequentially added to be located in advance The tributyl citrate of reason, polyethylene glycol-6000, epoxies chain extender, zinc stearate, makeup grade White Mineral Oil, erucyl amide, mistake Dibenzoyl, atactic styrene-maleic anhydride copolymer, organic coating lithium aluminium silicate, composite antioxidant, complex light is aoxidized to stablize Agent, 2- oxazoline compound, Bravo stir at low speed 7 minutes, then high-speed stirred 15 minutes, and material after mixing is added Enter double screw extruder extruding pelletization；
4) it is 120~200 DEG C, screw speed 350rpm, screw slenderness ratio 44:1 that double screw extruder, which squeezes out processing temperature,；
5) pellet made from extruding pelletization is 4 hours dry under conditions of 60 DEG C；
6) plastic film blow molding machine is added in the pellet after above-mentioned drying process and controllable full biology drop is made through blowing step Mulch is solved, the machining temperature of plastic film blow molding is 150~190 DEG C, and blow-up ratio is 2~4:1, screw rod major diameter Compare 28:1.
Its testing performance index the results are shown in Table 3
Above embodiments are for that can understand and apply the invention convenient for those skilled in the art, referring to preferably Embodiment describes the invention in detail, those skilled in the art obviously can to technical solution of the present invention into Row modification or equivalent replacement, and apply the general principles described here to other examples without by creativeness Labour.Therefore, the present invention is not limited to the above embodiments, those skilled in the art's announcement according to the present invention, does not depart from this The improvement and modification that invention scope is made all should be within protection scope of the present invention.

Claims (10)

1. a kind of controllable full-biodegradable mulch, which is characterized in that the mulching film raw material is made of the component of following parts by weight:
2. a kind of controllable full-biodegradable mulch according to claim 1, which is characterized in that the high-crystallinity polylactic acid It is general thin grade polylactic acid as made from crystalline modified, 1.30 ± 0.05g/cm of density3, 3~8g/10min of melting means (190 DEG C, 2.16Kg), 170~180 DEG C of fusing point, tensile strength >=45~53MPa, elongation at break >=8~15%, impact strength 5~ 10KJ/m2(Izod)。
3. a kind of controllable full-biodegradable mulch according to claim 1, which is characterized in that the lined polymethyl ethylene carbonic acid Ester weight average molecular weight is 3-10 ten thousand, and passes through termination process.
4. a kind of controllable full-biodegradable mulch according to claim 1, which is characterized in that the compatilizer is peroxidating Diisopropylbenzene (DIPB), dibenzoyl peroxide, atactic styrene-maleic anhydride copolymer, the contracting of olefin copolymer grafted methacrylic acid One or more of water glyceride.
5. a kind of controllable full-biodegradable mulch according to claim 1, which is characterized in that the gas barrier agent is to have One of machine bentonite, organic coating lithium aluminium silicate, organic modified nano montmorillonite, organic modified nano aluminum oxide.
6. a kind of controllable full-biodegradable mulch according to claim 1, which is characterized in that the antioxidant is main antioxygen Composite antioxidant made of agent 1010 and auxiliary anti-oxidant 168 compound according to a certain percentage.
7. a kind of controllable full-biodegradable mulch according to claim 1, which is characterized in that the light stabilizer is ultraviolet Composite light stabilizer made of light absorbers and hindered amine light stabilizer compound according to a certain percentage.
8. a kind of controllable full-biodegradable mulch according to claim 1, which is characterized in that the anti-hydrolysis agent is carbonization Diimine monomer, aromatic polycarbodiimide, methyl diphenylene diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, 2- oxazole One of quinoline compound.
9. a kind of controllable full-biodegradable mulch according to claim 1, which is characterized in that the antibacterial agent is 4,5- bis- Chloro- N- octyl -3- isothiazolinone, Kathon CG, N- methyl 1,2- benzisothiazole-3-ketone, N- normal-butyl 1,2- benzisothia One of oxazoline -3- ketone, N- n-octyl 1,2-benzisothiazolin-3-one, Bravo, hexaconazole, Tebuconazole, carbendazim or It is several.
10. a kind of preparation method of controllable full-biodegradable mulch, which is characterized in that the preparation step and condition are as follows:
1) by high-crystallinity polylactic acid, the polyadipate/butylene terephthalate, lined polymethyl ethylene in the claims 1 Carbonic ester is 4~6 hours dry under conditions of before in 60 DEG C；
2) compatilizer in the claims 10 is 2~3 hours dry under conditions of before in 90 DEG C；
3) by high-crystallinity polylactic acid, the polyadipate/butylene terephthalate, lined polymethyl ethylene carbonate after drying process Weighed in the ratio in the claims 1, weigh it is good after put into high-speed mixer, start to stir at low speed, while stirring according to It is secondary be added pretreated plasticizer, dispersing agent, lubricant, opening agent, gas barrier agent, chain extender, compatilizer, antioxidant, Light stabilizer, anti-hydrolysis agent, antibacterial agent stir at low speed 3~15 minutes, then high-speed stirred 10~20 minutes, will after mixing Material be added double screw extruder extruding pelletization；
4) it is 120~200 DEG C, 150~450rpm of screw speed that the double screw extruder, which squeezes out processing temperature, screw slenderness ratio 36~48:1；
5) pellet made from extruding pelletization is 4~6 hours dry under conditions of 60 DEG C；
6) 5) plastic film blow molding machine is added in the pellet after middle drying process and controllable entirely biological drop is made through blowing step Mulch, ground film thickness 0.005-0.020mm are solved, the machining temperature of plastic film blow molding is 150~190 DEG C, Blow-up ratio is 2~4:1, screw slenderness ratio >=25:1.
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