CN103408827A - Degradable environmental-friendly mulching film and preparation method thereof - Google Patents

Degradable environmental-friendly mulching film and preparation method thereof Download PDF

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CN103408827A
CN103408827A CN2013103843052A CN201310384305A CN103408827A CN 103408827 A CN103408827 A CN 103408827A CN 2013103843052 A CN2013103843052 A CN 2013103843052A CN 201310384305 A CN201310384305 A CN 201310384305A CN 103408827 A CN103408827 A CN 103408827A
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butyl
acid
tert
ester
mulch film
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CN103408827B (en
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陆海荣
孙建设
燕维福
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Shen Jing
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Hebei Aokebai Environmental Protection Technology Co Ltd
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Abstract

The invention relates to an environmental-friendly mulching film which can endow universal plastics with properties of photothermal oxidative degradation and biodegradation. The invention specifically discloses a degradable material which is prepared from photothermal oxidative degradation granules, a thermal stabilizer, a photostabilizer, an antioxidant, a biodegradation guiding agent and the like; and after the degradable material is added to the universal plastics (such as polyethylene, polypropylene, polystyrene and the like), the plastics can be subjected to photothermal oxidative degradation and biodegradation. The environmental-friendly mulching film capable of being subjected to oxidative biodegradation can be produced through preparing a degradable master batch from the degradable material and low-density and low-melting-point polyethylene by a twin-screw granulator and adding the degradable master batch to mulching film production. The degradable environmental-friendly mulching film disclosed by the invention not only has the advantages of simplicity in preparation, low production cost, environmental friendliness and no pollution, but also has very good time controllability; and the degradation time of the mulching film can be changed through adjusting the content of ingredients of the mulching film, so that the requirements of different crops for growth are met, and the mulching film is very applicable to the needs of agricultural planting.

Description

A kind of degradable Environment protection mulch film and manufacture method thereof
Technical field
The present invention relates to the degradable material technical field, relate in particular to a kind of degradable Environment protection mulch film and manufacture method thereof.
Background technology
Membrane covering is one of dry farming and water-saving irrigation and key measures of increase crop growth phase, and plastic mulching cultivation technology has improved the scientific and technological level of grain-production effectively.But along with the increase of membrane covering area, traditional mulch film can not be degraded, be difficult to again reclaim, residual membrane pollution problem is on the rise.If only by increasing the ground film thickness, improved the mulch film rate of recovery, can not accomplish that not only 100% reclaims, also can increase peasant burden, cause the waste of material.But therefore research and development natural degradation mulch film, realizing that the mulch film waste goes back to nature has become the emphasis brainstorm subject of plastics industry circle since the nineties.The research of degradative plastic film both at home and abroad at present mainly concentrates in the research of Biodegradable mulch, photodegradation film, the two degradative plastic films of photo bio and oxidation Biodegradable mulch.
Chinese patent application numbers 95191396, adopt the novel high molecular polymers such as microorganism polyester, aliphatic polyester or poly(lactic acid) to manufacture degradative plastics.This degradative plastics biodegradation rate is fast, but synthetic difficulty is large, cost is high, physical and mechanical property is difficult to meet many application.
Chinese patent application number 200610051802 dependence are added amylose starch and are made biodegradable starch-resin composition.Although starch can be biodegradable, the plastics macromole in goods is difficult to degraded.After starch degradation, can stay some duck eyes on plastics, or the plastics film based article of full wafer be become to the fragment of difficult degradation.In addition, the physical and mechanical property of the plastics after interpolation starch is greatly affected, and is difficult to be processed into high strength or micron-sized film.As adopt film-blowing process, and because starch at high temperature is easy to burn, usually causing breaking of bubble pipe, impact is produced continuously.
Chinese patent application numbers 98106850.2, number of patent application 200980128631 etc., adopt the way of adding photosensitizers to make photodegradable plastics.Photochemical catalyst degraded plastic has environmental friendliness, the advantage such as cheap.But photodegradable plastics can only, in the situation that plastics are exposed to illumination could degrade, as unglazed photograph, can't be degraded.In addition, it is very big that the degradation time of photodegradable plastics is subject to processing the impact of technique, causes the time control poor-performing.
The way of Chinese patent application number 02128406 employing photosensitizers, stablizer and Biodegradable resin is made the photo bio degradable film.Photo biodegradable plastics combines the advantage of photodegradation and starch based degradative plastics, and the photodegradation part can be degraded under illumination, and the starch part can be degraded under soil.But because in plastics, having added more starch, the weather resistance of the plastics film of making is poor, when manufacturing degradative plastic film, be difficult to ensure that card meets the growth requirement of farm crop.
The oxidized-biodegradable plastic that U.S. Pat 005854304 is manufactured by organic acid salt (cobalt stearate, cerium stearate etc.) and the natural poly-basic organic acid (citric acid, fumaric acid etc.) of containing transition metal in plastic substrate.The plastics that oxidized-biodegradable plastic makes as a class comprehensive utilization oxidative degradation and biodegradation technique, not only overcome photodegradable plastics degradation-labile defect not when unglazed or illumination is not enough, also overcome general complete biodegradable plastics processed complex, cost high, be difficult for the drawback of promoting.But such oxidized-biodegradable plastic is not provided under different light, heat and oxidizing condition the time-controllable to degradative plastics.
Summary of the invention
In order to solve the problems such as processed complex, cost time control property high, degradation time that existing degradative plastic film exists is poor, the present invention proposes a kind of degradable Environment protection mulch film and manufacture method thereof.
The present invention adopts following technical scheme:
Degradable environment friendly material of the present invention comprises oxidative degradation composition and antioxidant, and the weight percent of this material is composed as follows:
Oxidative degradation composition 60-90%
Antioxidant 10-40%
Wherein, the oxidative degradation composition is octyl ferrocene, positive capryloyl ferrocene, the hendecene acyl Ferrocene, iron stearate, manganese stearate, cobalt stearate, copper stearate, cerium stearate, Lanthanum Stearate, Praseodymium Stearate, lauric acid iron, lauric acid manganese, cobalt laurate, lauric acid copper, the lauric acid cerium, the lauric acid lanthanum, the lauric acid praseodymium, iron octoate, manganese octoate, cobalt octoate, cupric octoate, cerium octoate, sad lanthanum, sad praseodymium, ferric dimethyl dithiocarbamate, the diethyldithiocar bamic acid cerium, lanthanum diethyldithiocarbamate, the diethyldithiocar bamic acid praseodymium, dibutyl dithiocaarbamate iron, the dibutyl dithiocaarbamate cerium, the dibutyl dithiocaarbamate lanthanum, the dibutyl dithiocaarbamate praseodymium, Methyl disulfide is for tertiary iron phosphate, Methyl disulfide is for Cerium monophosphate, Methyl disulfide is for lanthanum orthophosphate, Methyl disulfide is for praseodymium phosphate, diethyldithiophosphoric acid iron, the diethyldithiophosphoric acid cerium, the diethyldithiophosphoric acid lanthanum, the diethyldithiophosphoric acid praseodymium, dibutyl phosphorodithioic acid iron, dibutyl phosphorodithioic acid cerium, dibutyl phosphorodithioic acid lanthanum, dibutyl phosphorodithioic acid praseodymium, titanium dioxide, one or more in ferric oxide and manganese oxide,
Antioxidant is 1-hydroxy-3-methyl-4-isopropyl benzene, 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-4-normal-butyl phenol, 4-methylol-2, the 6-di-tert-butylphenol, butylhydroxy anisole, 2-(1-methylcyclohexyl)-4, the 6-xylenol, 2-methyl-4, the 6-dinonyl phenol, 2,4,6-tri-butyl-phenol, β-positive octadecanol ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, styrenated phenol, 4,4 '-dihydroxybiphenyl, 2,2 '-methylene bis (4-methyl-6-tert-butylphenol), 4,4 '-methylene bis (2,6 di t butyl phenol), 2,2 '-methylene bis (6-α-methylbenzyl p-cresol), 2,2 '-bis-(4-hydroxy phenyl) propane, 4,4 '-Ding fork two (3 methy 6 tert butyl phenol), 1,1 '-bis-(4-hydroxybenzene) cyclic group alkane, two [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol of 2,2 ' methene, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, two [two (3 '-tertiary butyl-4 '-hydroxy phenyl) butyric acid of 3,3-] glycol ester, four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, two [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic esters of 1,6-hexanol, 2,5 di tert butyl hydroquinone, 2,5-, bis-tert-pentyl Resorcinol, triglycol is two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, the hydroquinone dibenzyl ether, 2,5,7,8-tetramethyl--2-(4 ', 8 ', 12 '-trimethylammonium tridecyl) chroman-6-alcohol acetate, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctyl alcohol ester, 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 3,9 ,-bis-2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-propionyl oxygen] and-1,1-dimethyl ethane } 2,4,8,10-tetra-oxidation volutions-[5,5] undecane, the 2-tertiary butyl-6-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-4-aminomethyl phenyl acrylate, 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl acrylate, 3-aryl-benzofuranone, the amino p-cresol of 2,6-di-t-butyl-alpha, alpha-dimethyl, 6-(4-hydroxyl-3,5-di-tert-butyl amido)-2, two (the octylsulfo)-1,3,5-triazines of 4-, two (4-hydroxyl-3,5-di-t-butyl the phenoxy group)-2-n-octyl sulfo--1,3,5-triazines of 4,6-, 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 4,4 '-thiobis (2-methyl-6-tert-butylphenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol), 2,2 '-thiobis [3-(3,5-and tert-butyl-hydroxy phenyl) ethyl propionate, 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) 1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H)-triketone, isocyanuric acid three [β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl ethyl ester], 1,1 '-thiobis (2-phenol), two (3,5-di-tert-butyl-hydroxy phenyl) thioether, 3,5-di-tert-butyl-4-hydroxyl benzyl di(2-ethylhexyl)phosphate (18) ester, 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid, two (3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acids, two (3,5-di-t-butyl-4-hydroxybenzene propionyl) hydrazine, 2, two [ethyl-3-(3,5-the di-tert-butyl-hydroxy phenyl)] propionic esters of 2 '-oxalyl amido, two (benzyl hydrazides), N-(4-hydroxyphenyl) Stearyl Amine, N, N '-phenylbenzene azanol, N, N '-bis-(octadecyl azanol), the different tridecane ester of (3,5-di-t-butyl-4-hydroxyphenyl) methyl-thioacetic acid, 4,6-bis-(hot thiomethyl) ortho-cresol, the different suffering of tricresyl phosphite (or last of the ten Heavenly stems) ester, phosphorous acid benzene two isodecyl esters, isooctyl diphenyl phosphite, diphosphorous acid tetramethylolmethane distearyl alcohol ester, tricresyl phosphite (octadecyl ester), phosphorous acid ester three (nonylphenol), tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, the hot fat of two (2, the 4-di-t-butyl bibenzyl) phosphorous acid of 2-, four (2,4-di-tert-butylphenols)-4,4 '-xenyl diphosphites, thio-2 acid stearyl alcohol ester, the two dodecane esters of thio-2 acid, thio-2 acid two lauric acid, two 14 esters of thio-2 acid, two (octadecyl) disulphide, one or more in tetramethylolmethane four (3-lauryl thiopropionate) and Resorcinol mono benzoate.
Environment-friendly materials of the present invention also comprise biodegradation promotor, and the weight percent of this material is composed as follows:
Oxidative degradation composition 20-90%
Antioxidant 5-40%
Biodegradation promotor 1-40%
Wherein, biodegradation promotor is N-lauroyl glutamate, treated starch, polylactide, poly butylene succinate, polycaprolactone or gathers (3-hydroxybutyrate ester).
Degradable environment friendly material of the present invention also comprises thermo-stabilizer and photostabilizer, and the weight percent of this material is composed as follows:
Oxidative degradation composition 20-90%
Antioxidant 5-40%
Thermo-stabilizer 1-20%
Photostabilizer 1-20%
Wherein, thermo-stabilizer is barium stearate, calcium stearate, Zinic stearas, strontium stearate, Magnesium Stearate, barium laurate, calcium laurate, zinc laurate, Magnesium monolaurate, ricinolic acid barium, ricinolic acid calcium, zinc ricinate, barium naphthenate, calcium naphthenate, zinc naphthenate, magnesium naphthenate, 2 ethyl hexanoic acid barium, 2 ethyl hexanoic acid calcium, 2 ethyl hexanoic acid zinc, toxilic acid monoesters, hydrotalcite, zeolite or alkali formula phosphorous acid calcium aluminium;
Photostabilizer is salicylic acid, Methyl Salicylate, Whitfield's ointment-4-tertiary butyl phenyl ester, 4 tert octylplhenyl salicylate, 4,4 '-isopropylidene two-(phenol salicylate), Whitfield's ointment-2-ethylhexyl, menthyl salicylate, 4-(Whitfield's ointment)-2,2,6,6-tetramethyl piperidine alcohol ester, 2,4 dihydroxyl benzophenone, ESCALOL 567, Octabenzone, 2-hydroxyl-4-dodecyloxy benzophenone, 2-hydroxyl-4-benzyloxy benzophenone, 2 ' 2,4,4 '-tetrahydroxybenzophenone, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-bis-alpha, alpha-dimethylbenzyls) benzene a pair of horses going side by side triazole, 2,4,6-tri-(2 '-hydroxyl-4 '-n-butylphenyl)-1,3,5-triazines, 2-[4, two (2,4-the xylyl)-2-(1,3,5-triazines base) of 6-]-the 5-phenol octyloxy, sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester, three (1,2,2,6,6-pentamethyl--4-piperidyl) phosphorous acid ester, [(1-(β-ethyl)-2-2-6,6-tetramethyl--4-piperidyl) succinic acid] ester, poly--[6-[(1,1,3,3-tetramethyl butyl)-imino-]-1,3,5-triazines-2,4-bis-bases] [2-(2,2,6,6-tetramethyl--4-piperidyl)-inferior amino]-hexa-methylene-[4-(2,2,6,6-tetramethyl--4-piperidyl)-inferior amino] }, poly--{ [6-(morpholine-4-yl)-1,3,4-triazine-2,4-bis-bases] [2-(2,2,6,6-tetramethyl--4-piperidyl)-inferior amino]-hexa-methylene-[4-(2,2,6,6-tetramethyl--4-piperidyl)-inferior amino] }, 1,2-bis-(3,3,5,5-tetramethyl-piperazine-2-ketone-1-yl) ethane, 1,1 ', 1 "-{ 1,3, 5-triazine-2,4,6-tri-bases three [(cyclohexyl imino-)-2,1-second two bases] } three [3, 3,5,5-tetramethyl-piperazinones or 1,1 ', 1 "-{ 1,3,5-triazines-2,4,6-tri-bases three [(cyclohexyl imino-)-2,1-second two bases] } three [3,3,4,5,5-pentamethyl-piperazinones.
Degradable environment friendly material of the present invention also comprises biodegradation promotor, and the weight percent of this material is composed as follows:
Oxidative degradation composition 10-90%
Antioxidant 5-30%
Thermo-stabilizer 1-20%
Photostabilizer 1-20%
Biodegradation promotor 1-30%
Wherein, biodegradation promotor is N-lauroyl glutamate, treated starch, polylactide, poly butylene succinate, polycaprolactone or gathers (3-hydroxybutyrate ester).
Degradable Environment protection mulch film of the present invention, this Environment protection mulch film has added weight percent in manufacturing processed be the degradation master batch of 2-20%, degradation master batch is comprised of polyethylene, polypropylene or the polystyrene of degradable environment friendly material as above and low density, low melting point, and wherein to account for the weight percent of degradation master batch be 2-30% to degradable environment friendly material.
Degradable Environment protection mulch film of the present invention, the weight percent of environment-friendly materials consists of: oxidative degradation composition and biodegradation promotor total amount are 70% ~ 80%, the total amount of thermo-stabilizer, photostabilizer and antioxidant is 20% ~ 30%, the weight percentage of this kind environment-friendly materials in mulch film is 0.4% ~ 1%, degradative plastic film is coventional type, and the time that mulch film started to degrade in the crop growth phase in April to July is 40 days ~ 60 days.
Environment protection mulch film of the present invention, the weight percent of environment-friendly materials consists of: oxidative degradation composition and biodegradation promotor total amount are 40% ~ 60%, the total amount of thermo-stabilizer, photostabilizer and antioxidant is 40% ~ 60%, the weight percentage of this kind environment-friendly materials in mulch film is 0.4% ~ 1%, degradative plastic film is slow type, and the time that mulch film started to degrade in the crop growth phase in April to September is greater than 60 days.
Degradable Environment protection mulch film of the present invention, the weight percent of environment-friendly materials consists of: oxidative degradation composition and biodegradation promotor total amount are 80% ~ 90%, the total amount of thermo-stabilizer, photostabilizer and antioxidant is 10% ~ 20%, the weight percentage of this kind environment-friendly materials in mulch film is 0.4% ~ 1%, degradative plastic film is Quick-type, and the time that mulch film started to degrade in the crop growth phase in April to September is 10 days ~ 40 days.
When the total amount of thermo-stabilizer composition, photostabilizer composition and antioxidant composition was 10% ~ 50%, the prolongation of latency of degradative plastics, degraded were slowly; When oxidative degradation composition and biodegradation promotor composition total amount were 50% ~ 90%, prolonged short the latent period of degradative plastics, and degraded fast.
The preparation process of degradative plastic film comprises the following steps:
At first prepare to take by proportioning each component of degradable environment friendly material, and each component is dry respectively, then put into shearing stirrer, utilize high shear force to make each composition carry out physics fusion and chemical reaction.The rotating speed of shear mixer should be greater than 500rpm, so that each component is disperseed fully and mixed.Then, this mixing material can be directly adds the Low Density Polyethylene of low melting point in 2% ~ 30% ratio (as Exxon Mobil LD654, fusing point is 96 oC) in, add dual-screw pelletizer, make degradation master batch.Dual-screw pelletizer adopts metering feeding, makes each component that identical time of fusion be arranged in dual-screw-stem machine, produces the uniform degradation master batch of quality, guarantees the quality of degradative plastic film.Band Horizontal stirring oar in the feeding body, to prevent the material frame bridge.The dual-screw pelletizer screw diameter is 35.6mm, and spiral groove depth is 6mm, and screw slenderness ratio is 40, and screw element adopts involute spline to connect with mandrel, modular construction.The modular construction cylindrical shell divides eight sections, and the first paragraph cylindrical shell is feed cylinder.The feeding section adopts the large helical pitch screw element of dark screw channel, is beneficial to the mass transport of feeding section.The 4th section cylindrical shell is nature exhaust cylindrical shell, deviates from filler component and is heated afterwards and the former gas entrained into, and increases the stability of material.The 7th section cylindrical shell is the vacuum exhaust cylindrical shell, in order to slough low molecular weight volatile component and moisture.The 8th section cylindrical shell is for extruding cylindrical shell.All the other cylindrical shells, comprise that second segment, the 3rd section, the 5th section and the 8th section cylindrical shell are the cylindrical shell of remaining silent.During granulation, the top temperature of cylindrical shell does not surpass 150 oC, the discharge port temperature of the 8th section cylindrical shell should be lower than 130 oC.Control lower prilling temperature, particularly discharge port temperature, can reduce the degree of component oxidation in cylindrical shell, to guarantee the quality of degradation master batch.The forcing machine revolution is 400 ~ 800 rev/mins.The distance of the discharge port of the 8th section cylindrical shell and cooling water tank should be less than 30cm.Master batch enters the tank cooling at once after extruding, then use natural wind air-dry, pelletizing.
Above-mentioned degradation master batch is added in mulch film processing with 2% ~ 20% ratio, and preferably 2%-8%, make the environmentally degradable mulch film.The environmentally degradable mulch film is under physical environment, and by the effect of light or heat or microorganism, the degraded effective constituent in degradation composition will impel the polymkeric substance long-chain in general-purpose plastics to rupture gradually, forms the oxygenatedchemicals of small molecules amount.Further photo-thermal oxidative degradation or biological degradation, will make these small molecules oxygenatedchemicalss can finally change into carbonic acid gas, water and soil ulmin.
Different degradation master batch formulas, can regulate and control the degradation time of degradative plastics goods on a large scale.
Positively effect of the present invention is as follows:
The present invention joins degradation master batch in common ground film, make common ground film have degradable characteristic, degradable Environment protection mulch film of the present invention has advantages of that not only processing is simple, production cost is low, environment friendly and pollution-free, but also has good time control property, by regulating the component concentration in product, can change the degradation time of mulch film, meet the growth demand of Different Crop, be applicable to very much the needs of agricultural planting.
The accompanying drawing explanation
Fig. 1 is the schema of degradation master batch preparation process.
Fig. 2 is the biological degradation rate of degradable Environment protection mulch film of the present invention and the graph of a relation of time.
Fig. 3 is the time control performance map of degradable Environment protection mulch film of the present invention.
Embodiment
The following examples are to describe in further detail of the present invention.
Embodiment 1 coventional type Environment protection mulch film preparation
1.1 photo-thermal biological degradation multicomponent composite component and consumption (weight percentage)
TiO 2 30
Cobalt stearate 40
Calcium stearate 3
Zinic stearas 3
Oxidation inhibitor 246 20
GW944 1
N-lauroyl glutamate 3
In above-mentioned formula, TiO 2For the anatase titanium dioxide crystalline structure, with polyoxyethylene glycol or trolamine by TiO 2Carry out coating.The chemistry of oxidation inhibitor 246 is called 2,4,6-tri-butyl-phenol.GW944 is hindered amine as light stabilizer, and chemistry is by name to be gathered-{ [6-[(1,1,3,3-tetramethyl butyl)-imino-]-1,3,5-triazine-2,4-bis-bases] [2-(2,2,6,6-tetramethyl--4-piperidyl)-inferior amino]-hexa-methylene-[4-(2,2,6,6-tetramethyl--4-piperidyl)-inferior amino] }.
1.2 coventional type degradation master batch
1.1 described Multiple components are pressed to each component weight percentage content weighing, and each component is carried out respectively to drying, then put into shearing stirrer, utilize high shear force to make each composition carry out physics fusion and chemical reaction.(as Exxon Mobil LD654, fusing point is 96 in 5% ratio, to add this mixing material the Low Density Polyethylene of low melting point to oC) in, add dual-screw pelletizer, make the coventional type degradation master batch.
1.3 coventional type Environment protection mulch film
45% LLDPE 3305+40%LLDPE7042+10%LDPE0274
3% coventional type degradation master batch
2% CaCO 3
After above-mentioned each constituent materials is fully mixed, add single screw extrusion machine (length-to-diameter ratio of forcing machine is generally 20 ~ 30), blowing out thickness is 8 microns, and width is the coventional type Environment protection mulch film of 90 centimetres.
Embodiment 2 type Environment protection mulch film preparation at a slow speed
2.1 photo-thermal biological degradation multicomponent composite component and consumption (weight percentage)---type at a slow speed
Cerium stearate 50
Calcium stearate 5
Zinic stearas 5
Antioxidant 264 20
GW944 20
In above-mentioned formula, the chemistry of antioxidant 264 is called 2,6 di tert butyl 4 methyl phenol.
2.2 type degradation master batch at a slow speed
2.1 described Multiple components are pressed to each component weight percentage content weighing, and each component is carried out respectively to drying, then put into shearing stirrer, utilize high shear force to make each composition carry out physics fusion and chemical reaction.(as Exxon Mobil LD654, fusing point is 96 in 5% ratio, to add this mixing material the Low Density Polyethylene of low melting point to oC) in, add dual-screw pelletizer, make type degradation master batch at a slow speed.
2.3 type Environment protection mulch film at a slow speed
45% LLDPE 3305+40%LLDPE7042+10%LDPE0274
3% type degradation master batch at a slow speed
2% CaCO 3
After above-mentioned each constituent materials is fully mixed, add single screw extrusion machine (length-to-diameter ratio of forcing machine is generally 20 ~ 30), blowing out thickness is 8 microns, and width is the Environment protection mulch film of type at a slow speed of 90 centimetres.
Embodiment 3 Quick-type Environment protection mulch films
3.1 photo-thermal biological degradation multicomponent composite component and consumption (weight percentage)
TiO 2 30
Cobalt stearate 40
Oxidation inhibitor BHA 10
N-lauroyl glutamate 20
In above-mentioned formula, TiO2 is the anatase titanium dioxide crystalline structure, with the coated fertilizer of organism as TiO2, as polyoxyethylene glycol, trolamine etc.The chemistry of oxidation inhibitor BHA is called butylhydroxy anisole.
3.2 Quick-type degradation master batch
3.1 described Multiple components are pressed to each component weight percentage content weighing, and each component is dry respectively, then put into shearing stirrer, utilize high shear force to make each composition carry out physics fusion and chemical reaction.(as Exxon Mobil LD654, fusing point is 96 in 25% ratio, to add this mixing material the Low Density Polyethylene of low melting point to oC) in, add dual-screw pelletizer, make the Quick-type degradation master batch.
2.3 Quick-type Environment protection mulch film
43% LLDPE 3305+40%LLDPE7042+10%LDPE0274
5% Quick-type degradation master batch
2% CaCO 3
After above-mentioned each constituent materials is fully mixed, add single screw extrusion machine (length-to-diameter ratio of forcing machine is generally 20 ~ 30), blowing out thickness is 8 microns, and width is the Quick-type Environment protection mulch film of 90 centimetres.
Embodiment 4 photo-oxidative degradation tests
To the coventional type Environment protection mulch film, type Environment protection mulch film and Quick-type Environment protection mulch film carry out the exposure test of fluorescence UV-light according to USS ASTM D5208-01 at a slow speed, light source used is the ultraviolet lamp of emission 340 nanometers, and intensity is 0.78 ± 0.02W/m 2Mm.The exposure test of fluorescence UV-light is round-robin test.The circulation of adopting is is 50 ± 3 in black standard temperature intensity oUnder C, radioactive exposure is 20 hours, then, is 40 ± 3 in black standard temperature intensity oUnder C, expose 4 hours without the irradiation condensation.Every 24 hours, measure the elongation of sample.When the elongation of 75% sample is less than 5%, by ASTM D3826-98(2002) be defined as the degraded terminal of degradative plastic film.The degradation time of each Environment protection mulch film in the exposure test of fluorescence UV-light is as shown in table 1.
Quick-type Environment protection mulch film, coventional type Environment protection mulch film and at a slow speed the type Environment protection mulch film under the condition of fluorescence UV-light exposure test defined, at 72 hours, 120 hours and 192 hours, reach respectively the degraded terminal of ASTM D3826 definition.
Elongation (%) data of different open-assembly times in the exposure test of table 1 fluorescence UV-light
The open-assembly time/hour 0 24 48 72 96 120 144 168 192
The coventional type Environment protection mulch film 490 421 345 150 61 <5
Type Environment protection mulch film at a slow speed 530 512 495 487 470 360 241 90 <5
The Quick-type Environment protection mulch film 502 290 65 <5
Embodiment 5 thermooxidative degradation tests
To the coventional type Environment protection mulch film, type Environment protection mulch film and Quick-type Environment protection mulch film be according to USS ASTM D5510-94(2001 at a slow speed) carry out the thermooxidative degradation test.Adopt the gravity convection baking oven, temperature is 70 oC.Every 3 days, measure the elongation of sample.When the elongation of 75% sample is less than 5%, by ASTM D3826-98(2002) be defined as the degraded terminal of degradative plastic film.The degradation time of each Environment protection mulch film in the exposure test of fluorescence UV-light is as shown in table 2.
Quick-type Environment protection mulch film, coventional type Environment protection mulch film and at a slow speed the type Environment protection mulch film 70 OCIn the thermal destruction test, at 18 days, 21 days and 24 days, reach respectively the degraded terminal of ASTM D3826 definition.
Table 2 sample is 70 oElongation (%) data in C thermal destruction test
In baking oven time/sky 0 3 6 9 12 15 18 21 24
The coventional type Environment protection mulch film 490 486 395 304 213 127 32 <5
Type Environment protection mulch film at a slow speed 530 534 489 402 320 232 132 40 <5
The Quick-type Environment protection mulch film 502 460 397 268 140 37 <5
Embodiment 6 molecular weight tests
To the coventional type Environment protection mulch film, type Environment protection mulch film and the sample of Quick-type Environment protection mulch film after photo-oxidative degradation and thermooxidative degradation be according to USS ASTM D6474-12 gel permeation chromatography weight-average molecular weight (Mw), number-average molecular weight (Mn) and dispersed (Mw/Mn) at a slow speed.Test condition is 1,2,4-trichlorobenzene, 140 oC.Test result is as shown in table 3.After photo-thermal oxidative degradation, poly molecular weight and molecular weight, to 5000 left and right, can be biodegradable.
Table 3 photo-thermal degraded sample
Figure 234722DEST_PATH_IMAGE001
Embodiment 7 biodegradation tests
Choose Quick-type Environment protection mulch film sample, simulation refuse landfill or compost environment, put into 70 oThe C thermal aging oven was processed 60 days.Sample after processing carries out biodegradation test according to USS ASTM D5988-03.Test-results as shown in Figure 2.
Environment protection mulch film after thermooxidative degradation, can be resolved into CO by various microorganisms under aerobic conditions 2And water.Test sample can the biological decomposition rate arrive 30% in 90 days.
The embodiment test of being exposed to the sun in 8 fields
To the coventional type Environment protection mulch film, type Environment protection mulch film and Quick-type Environment protection mulch film carry out the field test of being exposed to the sun at a slow speed.Adopting the length of sample is 5 meters (wide 80 centimetres).Sample is laid on the Hebei Suburb of Shijiazhuang at the bottom of by April.Below mulch film, be soil, the above does not plant farm crop.When the degraded breach number of every square metre of mulch film generation is greater than 1, be defined as the degradation time of mulch film.Each mulch film field be exposed to the sun the test degradation time as shown in table 3.
General farm crop plants at the beginning of by the end of April or 5 months, the be exposed to the sun implantation time of time of test and farm crop of field is identical.Most of farm crop are 50 ~ 60 days to the requirement of insulation soil moisture conservation, and the coventional type Environment protection mulch film can meet the demands.Answer light intensity and the temperature of various places different, require to extend or shorten type Environment protection mulch film or the Quick-type Environment protection mulch film at a slow speed selected of degradation time.
The table 3 field testing data of being exposed to the sun
The degradative plastic film model The coventional type Environment protection mulch film Type Environment protection mulch film at a slow speed The Quick-type Environment protection mulch film
Degradation time (my god) 57 75 33
The time control property of embodiment 9 Environment protection mulch films
Fig. 3 shows the time control technique of time control Environment protection mulch film.The degradation time of Environment protection mulch film depends on latent period and the oxidative degradation phase of mulch film.The latent period of mulch film and oxidative degradation phase are longer, and the degradation time of Environment protection mulch film is just longer.Thermo-stabilizer, photostabilizer and oxidation preventive content are higher, and the latent period of mulch film and oxidative degradation phase are longer; And oxygenant and Biostimulation agent content are larger, the latent period of mulch film and oxidative degradation phase are shorter.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.

Claims (10)

1. degradable Environment protection mulch film, it is characterized in that: this Environment protection mulch film has added weight percent in manufacturing processed be the degradation master batch of 2-20%, degradation master batch is comprised of polyethylene, polypropylene or the polystyrene of degradable environment friendly material and low density, low melting point, and wherein to account for the weight percent of degradation master batch be 2-30% to degradable environment friendly material.
2. degradable Environment protection mulch film as claimed in claim 1, it is characterized in that: degradable environment friendly material comprises oxidative degradation composition and antioxidant, the weight percent of this material is composed as follows:
Oxidative degradation composition 60-90%
Antioxidant 10-40%
Wherein, the oxidative degradation composition is octyl ferrocene, positive capryloyl ferrocene, the hendecene acyl Ferrocene, iron stearate, manganese stearate, cobalt stearate, copper stearate, cerium stearate, Lanthanum Stearate, Praseodymium Stearate, lauric acid iron, lauric acid manganese, cobalt laurate, lauric acid copper, the lauric acid cerium, the lauric acid lanthanum, the lauric acid praseodymium, iron octoate, manganese octoate, cobalt octoate, cupric octoate, cerium octoate, sad lanthanum, sad praseodymium, ferric dimethyl dithiocarbamate, the diethyldithiocar bamic acid cerium, lanthanum diethyldithiocarbamate, the diethyldithiocar bamic acid praseodymium, dibutyl dithiocaarbamate iron, the dibutyl dithiocaarbamate cerium, the dibutyl dithiocaarbamate lanthanum, the dibutyl dithiocaarbamate praseodymium, Methyl disulfide is for tertiary iron phosphate, Methyl disulfide is for Cerium monophosphate, Methyl disulfide is for lanthanum orthophosphate, Methyl disulfide is for praseodymium phosphate, diethyldithiophosphoric acid iron, the diethyldithiophosphoric acid cerium, the diethyldithiophosphoric acid lanthanum, the diethyldithiophosphoric acid praseodymium, dibutyl phosphorodithioic acid iron, dibutyl phosphorodithioic acid cerium, dibutyl phosphorodithioic acid lanthanum, dibutyl phosphorodithioic acid praseodymium, titanium dioxide, one or more in ferric oxide and manganese oxide,
Antioxidant is 1-hydroxy-3-methyl-4-isopropyl benzene, 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-4-normal-butyl phenol, 4-methylol-2, the 6-di-tert-butylphenol, butylhydroxy anisole, 2-(1-methylcyclohexyl)-4, the 6-xylenol, 2-methyl-4, the 6-dinonyl phenol, 2,4,6-tri-butyl-phenol, β-positive octadecanol ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, styrenated phenol, 4,4 '-dihydroxybiphenyl, 2,2 '-methylene bis (4-methyl-6-tert-butylphenol), 4,4 '-methylene bis (2,6 di t butyl phenol), 2,2 '-methylene bis (6-α-methylbenzyl p-cresol), 2,2 '-bis-(4-hydroxy phenyl) propane, 4,4 '-Ding fork two (3 methy 6 tert butyl phenol), 1,1 '-bis-(4-hydroxybenzene) cyclic group alkane, two [4-methyl-6-(Alpha-Methyl cyclohexyl) phenol of 2,2 ' methene, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, two [two (3 '-tertiary butyl-4 '-hydroxy phenyl) butyric acid of 3,3-] glycol ester, four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, two [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic esters of 1,6-hexanol, 2,5 di tert butyl hydroquinone, 2,5-, bis-tert-pentyl Resorcinol, triglycol is two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, the hydroquinone dibenzyl ether, 2,5,7,8-tetramethyl--2-(4 ', 8 ', 12 '-trimethylammonium tridecyl) chroman-6-alcohol acetate, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid isooctyl alcohol ester, 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 3,9 ,-bis-2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-propionyl oxygen] and-1,1-dimethyl ethane } 2,4,8,10-tetra-oxidation volutions-[5,5] undecane, the 2-tertiary butyl-6-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-4-aminomethyl phenyl acrylate, 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl acrylate, 3-aryl-benzofuranone, the amino p-cresol of 2,6-di-t-butyl-alpha, alpha-dimethyl, 6-(4-hydroxyl-3,5-di-tert-butyl amido)-2, two (the octylsulfo)-1,3,5-triazines of 4-, two (4-hydroxyl-3,5-di-t-butyl the phenoxy group)-2-n-octyl sulfo--1,3,5-triazines of 4,6-, 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 4,4 '-thiobis (2-methyl-6-tert-butylphenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol), 2,2 '-thiobis [3-(3,5-and tert-butyl-hydroxy phenyl) ethyl propionate, 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) 1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H)-triketone, isocyanuric acid three [β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl ethyl ester], 1,1 '-thiobis (2-phenol), two (3,5-di-tert-butyl-hydroxy phenyl) thioether, 3,5-di-tert-butyl-4-hydroxyl benzyl di(2-ethylhexyl)phosphate (18) ester, 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid, two (3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acids, two (3,5-di-t-butyl-4-hydroxybenzene propionyl) hydrazine, 2, two [ethyl-3-(3,5-the di-tert-butyl-hydroxy phenyl)] propionic esters of 2 '-oxalyl amido, two (benzyl hydrazides), N-(4-hydroxyphenyl) Stearyl Amine, N, N '-phenylbenzene azanol, N, N '-bis-(octadecyl azanol), the different tridecane ester of (3,5-di-t-butyl-4-hydroxyphenyl) methyl-thioacetic acid, 4,6-bis-(hot thiomethyl) ortho-cresol, the different suffering of tricresyl phosphite (or last of the ten Heavenly stems) ester, phosphorous acid benzene two isodecyl esters, isooctyl diphenyl phosphite, diphosphorous acid tetramethylolmethane distearyl alcohol ester, tricresyl phosphite (octadecyl ester), phosphorous acid ester three (nonylphenol), tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, the hot fat of two (2, the 4-di-t-butyl bibenzyl) phosphorous acid of 2-, four (2,4-di-tert-butylphenols)-4,4 '-xenyl diphosphites, thio-2 acid stearyl alcohol ester, the two dodecane esters of thio-2 acid, thio-2 acid two lauric acid, two 14 esters of thio-2 acid, two (octadecyl) disulphide, one or more in tetramethylolmethane four (3-lauryl thiopropionate) and Resorcinol mono benzoate.
3. degradable Environment protection mulch film as claimed in claim 2, it is characterized in that: degradable environment friendly material also comprises biodegradation promotor, the weight percent of this material is composed as follows:
Oxidative degradation composition 20-90%
Antioxidant 5-40%
Biodegradation promotor 1-40%
Wherein, biodegradation promotor is N-lauroyl glutamate, treated starch, polylactide, poly butylene succinate, polycaprolactone or gathers (3-hydroxybutyrate ester).
4. degradable Environment protection mulch film as claimed in claim 2, it is characterized in that: degradable environment friendly material also comprises thermo-stabilizer and photostabilizer, the weight percent of this material is composed as follows:
Oxidative degradation composition 20-90%
Antioxidant 5-40%
Thermo-stabilizer 1-20%
Photostabilizer 1-20%
Wherein, thermo-stabilizer is barium stearate, calcium stearate, Zinic stearas, strontium stearate, Magnesium Stearate, barium laurate, calcium laurate, zinc laurate, Magnesium monolaurate, ricinolic acid barium, ricinolic acid calcium, zinc ricinate, barium naphthenate, calcium naphthenate, zinc naphthenate, magnesium naphthenate, 2 ethyl hexanoic acid barium, 2 ethyl hexanoic acid calcium, 2 ethyl hexanoic acid zinc, toxilic acid monoesters, hydrotalcite, zeolite or alkali formula phosphorous acid calcium aluminium;
Photostabilizer is salicylic acid, Methyl Salicylate, Whitfield's ointment-4-tertiary butyl phenyl ester, 4 tert octylplhenyl salicylate, 4,4 '-isopropylidene two-(phenol salicylate), Whitfield's ointment-2-ethylhexyl, menthyl salicylate, 4-(Whitfield's ointment)-2,2,6,6-tetramethyl piperidine alcohol ester, 2,4 dihydroxyl benzophenone, ESCALOL 567, Octabenzone, 2-hydroxyl-4-dodecyloxy benzophenone, 2-hydroxyl-4-benzyloxy benzophenone, 2 ' 2,4,4 '-tetrahydroxybenzophenone, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-bis-alpha, alpha-dimethylbenzyls) benzene a pair of horses going side by side triazole, 2,4,6-tri-(2 '-hydroxyl-4 '-n-butylphenyl)-1,3,5-triazines, 2-[4, two (2,4-the xylyl)-2-(1,3,5-triazines base) of 6-]-the 5-phenol octyloxy, sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester, three (1,2,2,6,6-pentamethyl--4-piperidyl) phosphorous acid ester, [(1-(β-ethyl)-2-2-6,6-tetramethyl--4-piperidyl) succinic acid] ester, poly--[6-[(1,1,3,3-tetramethyl butyl)-imino-]-1,3,5-triazines-2,4-bis-bases] [2-(2,2,6,6-tetramethyl--4-piperidyl)-inferior amino]-hexa-methylene-[4-(2,2,6,6-tetramethyl--4-piperidyl)-inferior amino] }, poly--{ [6-(morpholine-4-yl)-1,3,4-triazine-2,4-bis-bases] [2-(2,2,6,6-tetramethyl--4-piperidyl)-inferior amino]-hexa-methylene-[4-(2,2,6,6-tetramethyl--4-piperidyl)-inferior amino] }, 1,2-bis-(3,3,5,5-tetramethyl-piperazine-2-ketone-1-yl) ethane, 1,1 ', 1 "-{ 1,3, 5-triazine-2,4,6-tri-bases three [(cyclohexyl imino-)-2,1-second two bases] } three [3, 3,5,5-tetramethyl-piperazinones or 1,1 ', 1 "-{ 1,3,5-triazines-2,4,6-tri-bases three [(cyclohexyl imino-)-2,1-second two bases] } three [3,3,4,5,5-pentamethyl-piperazinones.
5. degradable Environment protection mulch film as claimed in claim 4, it is characterized in that: degradable environment friendly material also comprises biodegradation promotor, the weight percent of this material is composed as follows:
Oxidative degradation composition 10-90%
Antioxidant 5-30%
Thermo-stabilizer 1-20%
Photostabilizer 1-20%
Biodegradation promotor 1-30%
Wherein, biodegradation promotor is N-lauroyl glutamate, treated starch, polylactide, poly butylene succinate, polycaprolactone or gathers (3-hydroxybutyrate ester).
6. degradable Environment protection mulch film as claimed in claim 5, it is characterized in that: the weight percent of environment-friendly materials consists of: oxidative degradation composition and biodegradation promotor total amount are 70% ~ 80%, the total amount of thermo-stabilizer, photostabilizer and antioxidant is 20% ~ 30%, the weight percentage of this kind environment-friendly materials in mulch film is 0.4% ~ 1%, degradative plastic film is coventional type, and the time of degraded is 40-60 days.
7. degradable Environment protection mulch film as claimed in claim 5, it is characterized in that: the weight percent of environment-friendly materials consists of: oxidative degradation composition and biodegradation promotor total amount are 40% ~ 60%, the total amount of thermo-stabilizer, photostabilizer and antioxidant is 40% ~ 60%, the weight percentage of this kind environment-friendly materials in mulch film is 0.4% ~ 1%, degradative plastic film is slow type, and the time of degraded is greater than 60 days.
8. degradable Environment protection mulch film as claimed in claim 5, it is characterized in that: the weight percent of environment-friendly materials consists of: oxidative degradation composition and biodegradation promotor total amount are 80% ~ 90%, the total amount of thermo-stabilizer, photostabilizer and antioxidant is 10% ~ 20%, the weight percentage of this kind environment-friendly materials in mulch film is 0.4% ~ 1%, degradative plastic film is Quick-type, and the time of degraded is 10-40 days.
9. as the preparation method of the described degradable Environment protection mulch film of claim 1-8 any one claim, it is characterized in that: the method comprises the following steps:
(1) at first by proportioning, take the various components of degradable environment-friendly material, and be dried respectively;
(2) then each component is joined to shearing stirrer, the rotating speed of shear mixer is greater than 500rpm, so that each component is disperseed fully and mixed;
The component that (3) then will be stirred joins in polyethylene, polypropylene or the polystyrene of low density, low melting point, and fully mixes, and the weight percent that makes degradable environment friendly material account for degradation master batch is 2-30%;
(4) compound is joined in twin screw extruder, carry out granulation, extruder discharging mouth temperature is lower than 130 oC, forcing machine revolution are 400-800 rev/min;
(5) degradation master batch out enters tank cooling afterwards from forcing machine, natural air drying then, and pelletizing, can make degradation master batch;
(6) degradation master batch is joined and produce in mulching film raw material, the weight percent of degradation master batch is 2-20%, fully mixes, and then adds in single screw extrusion machine, regulates thickness and width, can produce degradable Environment protection mulch film.
10. preparation method as claimed in claim 9 is characterized in that: in step (6), to add the weight percent content in mulch film be 2-8% to degradation master batch.
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