The content of the invention
In order to solve the problems such as time control property difference of processed complex existing for existing degradative plastic film, cost height, degradation time,The present invention proposes a kind of degradable Environment protection mulch film and its manufacture method.
The present invention adopts the following technical scheme that：
The degradable environment friendly material of the present invention includes oxidative degradation composition and antioxidant, the percentage by weight of the materialComposition is as follows:
Oxidative degradation composition 60-90%
Antioxidant 10-40%
Wherein, oxidative degradation composition is octyl ferrocene, positive caprylyl ferrocene, hendecene acyl Ferrocene, tristearinSour iron, manganese stearate, cobaltous octadecanate, copper stearate, cerium stearate, Lanthanum Stearate, Praseodymium Stearate, laurate iron, laurate manganese,Cobalt laurate, laurate copper, laurate cerium, laurate lanthanum, laurate praseodymium, iron octoate, manganese octoate, cobalt octoate, cupric octoate, octanoic acidCerium, sad lanthanum, sad praseodymium, ferric dimethyl dithiocarbamate, diethyldithiocar bamic acid cerium, diethyl-dithio ammoniaBase formic acid lanthanum, diethyldithiocar bamic acid praseodymium, dibutyl dithiocaarbamate iron, dibutyl dithiocaarbamateCerium, dibutyl dithiocaarbamate lanthanum, dibutyl dithiocaarbamate praseodymium, DMDS are for ferric phosphate, dimethyl twoD2EHDTPA cerium, DMDS are for lanthanum orthophosphate, DMDS for praseodymium phosphate, diethyldithioposphoric acid iron, diethyl twoD2EHDTPA cerium, diethyldithioposphoric acid lanthanum, diethyldithioposphoric acid praseodymium, dibutyl dithio ferric phosphate, dibutyl twoIn D2EHDTPA cerium, dibutyl dithio lanthanum orthophosphate, dibutyl dithio praseodymium phosphate, titanium dioxide, iron oxide and manganese oxideIt is one or more of；
Antioxidant is 1- hydroxy-3-methyl -4- cumenes, 2,6 di tert butyl 4 methyl phenol, bis- tertiary fourths of 2,6-Base -4- normal-butyls phenol, 4- methylol -2,6- di-tert-butylphenols, butylhydroxy anisole, 2- (1- methylcyclohexyls) -4,6- xylenols, 2 methyl 4,6 dinonyl phenol, 2,4,6- tri-butyl-phenols, β-(4- hydroxyl -3,5- di-t-butylsPhenyl) the positive octadecanol ester of propionic acid, styrenated phenol, 4,4 '-dihydroxybiphenyl, 2,2 '-methylene bis (4- methyl-6-tert-butylsBase phenol), 4,4 '-methylene bis(2,6-di-butyl phenol), 2,2 '-methylene bis (6- α-methylbenzyls paracresol), 2,2 '-it is bis-(4- hydroxy phenyls) propane, 4,4 '-fourth fork double (3 methy 6 tert butyl phenol), 1,1 '-bis- (4- hydroxy benzenes) ring group alkane, 2,2 ' methenes double [4- methyl -6- (Alpha-Methyl cyclohexyl) phenol, (3,5- di-t-butyl -4- hydroxyls of 1,3,5- trimethyls -2,4,6- threeBase benzyl) benzene, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, double [double (3 '-tert-butyl groups -4 '-hydroxyl of 3,3-Base phenyl) butyric acid] glycol ester, four [β-(3 ', 5 '-di-t-butyl -4 '-hydroxy phenyl) propionic acid] pentaerythritol esters, 1,6- oneselfAlcohol is double, and [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic ester, 2,5 di tert butyl hydroquinone, the tertiary pentyls of 2,5- bis- are to benzeneDiphenol, triethylene glycol double -3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester, hydroquinone dibenzyl ether, 2,5,7,8- tetra-Methyl -2- (4 ', 8 ', 12 '-trimethyltridecvl) benzodihydropyran -6- alcohol acetates, β-(3,5- di-t-butyl -4- hydroxylsBase phenyl) propionic acid isooctanol ester, 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 3,9 ,-two { 2- [3- (the tertiary fourths of 3-Base -4- hydroxy-5-methyl bases phenyl)-propionyl oxygen] -1,1- dimethyl ethanes } oxidations of 2,4,8,10- tetra- loop coil-[5,5] hendecane,The 2- tert-butyl groups -6- (the 2- hydroxyl -3- tert-butyl group -5- aminomethyl phenyls) -4- aminomethyl phenyls acrylate, 2- [1- (2- hydroxyls -3,5-Di-tert-pentyl-phenyl) ethyl] -4,6- di-tert-pentyl-phenyls acrylate, 3- aryl-benzofuranone, 2,6- di-t-butyls-α -Double (the octylsulfo) -1,3,5- triazines of dimethylamino-p-cresol, 6- (4- hydroxyl -3,5- di-tert-butyls amido) -2,4-, 4,6-Double (4- hydroxyl -3,5- di-t-butyls phenoxy group) -2- n-octylthio -1,3,5- triazines, 4,4 '-thiobis (the 6- tert-butyl groups -3-Methylphenol), 4,4 '-thiobis (2- methyl-6-tert-butylphenols), 2,2 '-thiobis (4- methyl-6-tert-butylphenols),2,2 '-thiobis [3- (3,5- and tert-butyl-hydroxy phenyl) ethyl propionate, (the 4- tert-butyl group -3- hydroxyls -2,6- of 1,3,5- tri-Dimethyl benzyl) 1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls)Guanamine, 4,6- (1H, 3H, 5H)-the triketone, [β-(3,5- di-tert-butyl-hydroxy phenyls) propiono second of isocyanuric acid threeEster], 1,1 '-thiobis (2- phenol), double (3,5- di-tert-butyl-hydroxy phenyls) thioethers, 3,5- di-t-butyl -4- hydroxyl benzylsBase di(2-ethylhexyl)phosphate (18) ester, 3,5- di-tert-butyl-4-hydroxyl benzyls diethyl phosphate, double (3,5- di-tert-butyl-4-hydroxyl benzylsDouble [ethyl -3- (the bis- tertiary fourths of 3,5- of diethyl phosphate, double (3,5- di-t-butyl -4- hydroxy benzenes propionyl) hydrazines, 2,2 '-oxalyl amidoBase -4- hydroxy phenyls)] propionic ester, double (benzyl hydrazides), N- (4- hydroxyphenyls) Stearyl Amine, N, N '-diphenyl azanol, N, N ' -Two (octadecyl hydroxylamines), (3,5- di-t-butyl -4- hydroxyphenyls) different tridecane ester of methyl-thioacetic acid, (Xin Liujia of 4,6- bis-Base) orthoresol, different pungent (or last of the ten Heavenly stems) ester of phosphorous acid three, the isodecyl ester of phosphorous acid benzene two, isooctyl diphenyl phosphite, diphosphorous acid season pentaTetrol distearyl alcohol ester, phosphorous acid three (octadecyl ester), phosphite ester three (nonyl phenol), (the 2,4- di-tert-butyls of phosphorous acid threeBase) ester, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, double (2,6- di-t-butyl -4- aminomethyl phenyls) seasons pentaTetrol diphosphites, 2- double (2,4- di-t-butyls bibenzyl) misery fat of phosphorous, four (2,4- di-tert-butylphenols) -4,4 '-biphenylIt is the double dodecane ester of base diphosphites, thio-2 acid octadecyl, thio-2 acid, thiodipropionic acid dilauryl cinnamic acid, thioDipropionic acid double 14 esters, two (octadecyl) disulphide, pentaerythrite four (3- lauryl thiopropionates) and 1,3- benzene twoOne or more in phenol mono benzoate.
The environment-friendly materials of the present invention also include biodegradation promotor, and the percentage by weight composition of the material is as follows:
Oxidative degradation composition 20-90%
Antioxidant 5-40%
Biodegradation promotor 1-40%
Wherein, biodegradation promotor is N- lauroyl glutamates, modified starch, polylactide, poly-succinic fourth twoAlcohol ester, polycaprolactone or poly- (3-hydroxybutyrate ester).
The degradable environment friendly material of the present invention also includes heat stabilizer and light stabilizer, the percentage by weight group of the materialInto as follows:
Oxidative degradation composition 20-90%
Antioxidant 5-40%
Heat stabilizer 1-20%
Light stabilizer 1-20%
Wherein, heat stabilizer be barium stearate, calcium stearate, zinc stearate, strontium stearate, magnesium stearate, barium laurate,Calcium laurate, zinc laurate, Magnesium dilaurate, castor oil acid barium, castor oil acid calcium, zinc ricinate, barium naphthanate, aphthenic acidsCalcium, zinc naphthenate, magnesium naphthenate, 2 ethyl hexanoic acid barium, 2 ethyl hexanoic acid calcium, 2 ethyl hexanoic acid zinc, maleic mono-ester, neatlyStone, zeolite or alkali formula Arizona bacilli aluminium；
Light stabilizer is septichen, Methyl Salicylate, salicylic acid -4- tert-butyl groups phenyl ester, salicylic acid -4-Octyl octylphenyl, 4,4 '-isopropylidene two-（Phenol salicylate）, salicylic acid -2- ethylhexyls, menthyl salicylate, 4- (waterPoplar acid) -2,2,6,6- tetramethyl piperidines alcohol ester, 2,4 dihydroxyl benzophenone, ESCALOL 567,2- hydroxylsBase -4- oxy-octyl benzophenones, 2- hydroxyl -4- dodecyloxy benzophenones, 2- hydroxyl -4- behzyloxybenzophenones, 2 '2,4,4 '-tetrahydroxybenzophenone, 2- (2 '-hydroxyl -5 '-aminomethyl phenyl) BTA, 2- (2 '-hydroxyl -3 ', 5 '-two tertiary fourthsBase phenyl) -5- chlorinated benzotriazoles, 2- (2 '-hydroxyl-the 3 '-tert-butyl group -5 '-aminomethyl phenyl) -5- chlorobenzotriazoles, 2- (2 ' -Hydroxyl -3 ', 5 '-two bis (alpha, alpha-dimethylbenzyl) bases) benzene a pair of horses going side by side triazole, 2,4,6- tri- (2 '-hydroxyl -4 '-n-butylphenyl) -1,3,5- threePiperazine, 2- [double (2,4- the xylyls) -2- (cyanuro 1,3,5) of 4,6-] -5- phenol octyloxies, (2,2,6,6- tetra- of decanedioic acid twoMethyl -4- piperidyls) ester, three (1,2,2,6,6- pentamethyl -4- piperidyls) phosphite esters, [(1- (β-ethyl) -2-2-6,6-Tetramethyl -4- piperidyls) succinic acid] ester, it is poly- [6- [(1,1,3,3- tetramethyl butyls)-imino group] -1,3,5- triazine -2,4- diyls] [2- (2,2,6,6- tetramethyl -4- piperidyls)-secondary amino]-hexa-methylene-[4- (2,2,6,6- tetramethyl -4- piperazinesPiperidinyl)-secondary amino], poly- { [6- (morpholine -4- bases) -1,3,4- triazine -2,4- diyls] [2- (2,2,6,6- tetramethyl -4- piperazinesPiperidinyl)-secondary amino]-hexa-methylene-[4- (2,2,6,6- tetramethyl -4- piperidyls)-secondary amino], (3,3,5,5- of 1,2- bis-Tetramethyl piperazine -2- ketone -1- bases) ethane, 1,1 ', 1 "-bases three of 1,3,5- triazines -2,4,6- three [(cyclohexylimino) -2,1- second diyl] } three [3,3,5,5- tetramethyls piperazinones or 1,1 ', 1 "-{ [(cyclohexyl is sub- for the bases three of 1,3,5- triazines -2,4,6- threeAmino) -2,1- second diyl] three [3,3,4,5,5- pentamethyl piperazinones.
The degradable environment friendly material of the present invention also includes biodegradation promotor, and the percentage by weight composition of the material is such asUnder:
Oxidative degradation composition 10-90%
Antioxidant 5-30%
Heat stabilizer 1-20%
Light stabilizer 1-20%
Biodegradation promotor 1-30%
Wherein, biodegradation promotor is N- lauroyl glutamates, modified starch, polylactide, poly-succinic fourth twoAlcohol ester, polycaprolactone or poly- (3-hydroxybutyrate ester).
The degradable Environment protection mulch film of the present invention, it is 2- that the Environment protection mulch film adds percentage by weight in the fabrication process20% degradation master batch, degradation master batch be by degradable environment friendly material as described above and low-density, low melting point polyethylene,Polypropylene or polystyrene composition, the percentage by weight that wherein degradable environment friendly material accounts for degradation master batch is 2-30%.
The degradable Environment protection mulch film of the present invention, the percentage by weight composition of environment-friendly materials are：Oxidative degradation composition and lifeThing degradation of promoter total amount is 70% ~ 80%, and the total amount of heat stabilizer, light stabilizer and antioxidant is 20% ~ 30%, this kind of ringIt is 0.4% ~ 1% to protect percetage by weight of the material in mulch film, and degradative plastic film is plain edition, and mulch film is in April to crop growth in JulyThe time that phase starts degraded is 40 days ~ 60 days.
The Environment protection mulch film of the present invention, the percentage by weight composition of environment-friendly materials are：Oxidative degradation composition and biodegradable rushIt is 40% ~ 60% to enter agent total amount, and the total amount of heat stabilizer, light stabilizer and antioxidant is 40% ~ 60%, and this kind of environment-friendly materials existPercetage by weight in mulch film is 0.4% ~ 1%, and degradative plastic film is slow type, and mulch film starts to drop in April to September crop growth phaseThe time of solution is more than 60 days.
The degradable Environment protection mulch film of the present invention, the percentage by weight composition of environment-friendly materials are：Oxidative degradation composition and lifeThing degradation of promoter total amount is 80% ~ 90%, and the total amount of heat stabilizer, light stabilizer and antioxidant is 10% ~ 20%, this kind of ringIt is 0.4% ~ 1% to protect percetage by weight of the material in mulch film, and degradative plastic film is Quick-type, and mulch film is in April to September crop growthThe time that phase starts degraded is 10 days ~ 40 days.
When the total amount of heat stabilizer composition, light stabilizer composition and antioxidant composition is 10% ~ 50%, degradative plasticsProlongation of latency, degraded are slow；When oxidative degradation composition and biodegradation promotor composition total amount are 50% ~ 90%, degraded modelingThe incubation period of material prolongs short, and degraded is quick.
The preparation process of degradative plastic film comprises the following steps：
Prepare each component for weighing degradable environment friendly material by matching first, and each component is separately dried, Ran HoufangEnter shearing mixer, each composition is carried out physics fusion and chemical reaction using high shear force.The rotating speed of shear mixer shouldMore than 500rpm, each component is fully disperseed and mixed.Then, the mixing material directly can be added in 2% ~ 30% ratioThe low density polyethylene (LDPE) of low melting point（Such as Exxon Mobil LD654, fusing point 96oC）In, add dual-screw pelletizer, systemInto degradation master batch.Dual-screw pelletizer uses metering feeding, each component is had identical time of fusion in dual-screw-stem machine, producesThe degradation master batch of uniform quality, it is ensured that the quality of degradative plastic film.Band Horizontal stirring oar in feeding body, to prevent material frame bridge.It is doubleScrew pelletizer screw diameter is 35.6mm, and spiral groove depth 6mm, screw slenderness ratio 40, screw element is with mandrel using graduallyThe spline that bursts at the seams couples, modular construction.Eight sections of modular construction cylinder point, first paragraph cylinder is feed cylinder.Feeding section usesDeep screw channel large pitch screw element, conveyed in favor of the material of feeding section.4th section of cylinder is that nature is vented cylinder, deviates from fillerAfter component is heated and the former gas entrained into, increase the stability of material.7th section of cylinder is vacuum exhaust cylinder, to sloughLow molecular weight volatile component and moisture.8th section of cylinder is extrusion cylinder.Remaining cylinder, including second segment, the 3rd section, the 5th section and8th section of cylinder is cylinder of remaining silent.During granulation, the maximum temperature of cylinder does not exceed 150oC, the discharging opening temperature of the 8th section of cylinderDegree should be less than 130oC.Relatively low prilling temperature, particularly discharging opening temperature are controlled, journey of the component in cylinder internal oxidition can be reducedDegree, to ensure the quality of degradation master batch.Extruder revolution is 400 ~ 800 revs/min.The discharging opening and temperature lowering water of 8th section of cylinderThe distance of groove should be less than 30cm.Tank cooling is immediately entered after master batch extrusion, is then air-dried with natural wind, pelletizing.
Above-mentioned degradation master batch is added in mulch film processing with 2% ~ 20% ratio, preferably 2%-8%, environmentally degradable is madeFilm.Environmentally degradable mulch film is under natural environment, and by the effect of light or heat or microorganism, the degraded in degradation composition is effectiveComposition will promote the polymer long-chain in general-purpose plastics to be gradually broken, and form the oxygenatedchemicals of small-molecular-weight.Further lightThermal oxidative degradation or biodegradation, these small molecule oxygenatedchemicals will be enable to be eventually converted into carbon dioxide, water and humicMatter.
Different degradation master batch formulas, the degradation time of degradative plastics product can be regulated and controled on a large scale.
The positive effect of the present invention is as follows：
Degradation master batch is added in common ground film by the present invention, common ground film is had degradable characteristic, of the inventionDegradable Environment protection mulch film not only has the advantages of processing is simple, production cost is low, environment friendly and pollution-free, but also with goodTime control property, by adjusting the constituent content in product, thus it is possible to vary the degradation time of mulch film, meet the growth need of Different CropAsk, be especially suitable for the needs of agricultural planting.