CN1611531A - Starch-based biodegradable film material and its production method - Google Patents
Starch-based biodegradable film material and its production method Download PDFInfo
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Abstract
The invention relates to a kind of starch-group biodegradation agricultural mulching film production technology. In the technology, make natural starch act on plasticizer in order to produce plasticity starch; then make the plasticity starch blend with polythene, grafted monomer, and initiating agent, and in double screw extruder, manufacture starch-group biodegradation granule by reactivity extrusion; then make the granule have blow molding to agricultural mulching film. In mulching film, the plasticity starch content is 42-80wt%, and the content of polythene and polythene grafted copolymer is 20-58%. Biodegradation ability of the mulching film is controllable, and the mulching film can burst apart to 2-4cm2 fragments in 3-6 months, so it can be basically dissolved by soil after one year.
Description
Technical field
The present invention relates to a kind of starch-base biodegradation thin-film material, especially agricultural mulching and production method thereof.This starch-base biodegradation thin-film material is to be main raw material with starch, make plasticity-starch by plasticization and modification, under the effect of reactive solubilizing agent, make the starch-base biodegradation pellet with polyolefin blend, again with this pellet blowing film forming, especially agricultural mulching.Agricultural mulching of the present invention has good biodegradability, and can regulate and control according to being suitable for the different of region, temperature and soil humidity degraded inductive phase, is to solve the optimal material of soil white pollution.In addition, the present invention also can be used to produce light packaging film material, as: agricultural byproducts, clothes, packing films such as daily necessities.With after abandon occurring in nature and equally easily dissolved by environment.
Background technology
China is large agricultural country, and the consumption of agricultural film ranks first in the world.According to relevant agricultural sector: 2002, the membrane covering area of China is above 1.2 hundred million mu, the consumption of mulch film is up to 500,000 tons, and the application of mulch film has been brought into play great effect to the volume increase of China farm crop, is called " White Revolution " by the vast farmers reputation once.In the last few years, because the non-degradable of mulch film, life-time service remained in the soil, made soil compaction, and crop growth is obstructed, and has a strong impact on output.For this reason, many knowledgeable people that are engaged in degradable material research have dropped into a large amount of energy and financial resources and have done many work for the white pollution problems that solves agricultural mulching.Mainly contain the following aspects: (1) photodegradation film promptly adds a certain amount of photodegradable aid in mulch film.(2) starch filled type Biodegradable mulch.(3) optically and biologically degrading mulch film promptly adds a certain amount of photodegradable aid in starch filled type Biodegradable mulch.This three series products was all tested in the land for growing field crops, did not all obtain satisfactory result.So far fail large scale application.Its reason is: the mechanism of degradation of photodegradation film is to lean on photodegradable aid under the effect of sunlight, resolves into free radical, causes the polyethylene chain break by free radical again, makes membrane degradation.Degradation process is controlled by weather quality and solar radiation intensity.Weather is good, and solar radiation is strong, and mulch film breaks too early, influences crop growth, and overcast and rainy many, can not degrade as scheduled again, especially is embedded in not degraded in the soil.Starch filled type Biodegradable mulch or optically and biologically degrading mulch film, because starch is without plastics processing, the filling of starch is few, and intensity is low, microorganism can only be destroyed starch ingredients, remaining most of plastic fraction still can not be degraded, as for optically and biologically degrading, and the same existence problem identical with photodegradation film.In addition, also there is a common problem in above-mentioned three kinds of mulch films, and price is higher than pure plastic film, and agricultural is difficult to accept.
The present invention is directed to above-mentioned three kinds of existing problems of degraded agricultural mulching, earlier native starch is prepared into plasticity-starch, utilize reaction to extrude principle, with plasticity-starch and polyethylene, grafted monomer, initiator, the plasticizing blend generates polyethylene graft copolymer simultaneously in twin screw extruder, polyethylene graft copolymer can make plasticity-starch and polyethylene form even co-mixing system as solubilizing agent, under the starch content condition with higher, make blend have better mechanical property and degradation property.
Summary of the invention
The production method that the purpose of this invention is to provide a kind of starch-base biodegradation thin-film material, comprise plasticity-starch, polyethylene, grafted monomer and radical initiator can make polyethylene be blended into compound under the action of evocating with under the temperature of monomer generation graft copolymerization, then this compound is made film, wherein plasticity-starch: polyethylene: grafted monomer: radical initiator weight ratio=40～80: 18～54: 1～3.5: 0.1～0.5.
Wherein plasticity-starch is by using secondary plasticizer and softening agent at 70-110 ℃ native starch, obtain by combination treatment under preferred 80-100 ℃ the temperature, wherein the content of secondary plasticizer is 2～4% of amount of starch in the plasticity-starch, the content of softening agent is 20～40% of amount of starch, and optimum quantity is 25～35%.
Wherein secondary plasticizer for example is selected from the lipid acid and the salt thereof of whiteruss, solid paraffin, 12～18 carbon, the low-molecular-weight wax of relative molecular mass 500～2000, or their mixture.
Softening agent for example is selected from ethylene glycol, tirethylene glycol, propylene glycol, glycerol, sorbyl alcohol, acetate, sorbic ester, ethyl Sorbic Acid ether, polyvinyl alcohol (polymerization degree 200～1000,100% hydrolysis), or their mixture.
Plasticity-starch preferably obtains by the following method: (particle diameter is 60～100mm with native starch, water content 11～13%), as W-Gum, yam starch, tapioca (flour), sweet potato starch, the mixture of any one or they in rice starch and the wheat starch, be good wherein with straight chain content higher W-Gum and yam starch, by a certain percentage with secondary plasticizer, as whiteruss, solid paraffin, the lipid acid of 12～18 carbon and salt thereof, the height that in the low-molecular-weight wax of relative molecular mass 500～2000 one or both and two or more compound join together with air extractor stirs in the machine, under negative pressure state (60Kpa～80Kpa), (120～200r/min) 5～8min, temperature is controlled at 80～100 ℃ to high-speed stirring.And then add a certain amount of softening agent, and as: ethylene glycol, tirethylene glycol, propylene glycol, glycerol, sorbyl alcohol, acetate, sorbic ester, ethyl Sorbic Acid ether, one or both in the polyvinyl alcohol (polymerization degree 200～1000,100% hydrolysis) or two or more compound.Under above-mentioned identical processing condition, behind continuation high-speed stirring 6～10min, just can make plasticity-starch.The content of secondary plasticizer is 2～4% of starch quality in the plasticity-starch, and the content of softening agent is 20～40% of amount of starch, and optimum quantity is 25～35%.Water content is reduced to 3～5% by ative starch 11～13% in the plasticity-starch.
Wherein polyethylene is a new LDPE (film grade), linear low density polyethylene, very low density polyethylene etc., or their mixture.Polyethylene most preferably is the blend of new LDPE (film grade) and linear low density polyethylene, and the ratio of the two is preferably 10～30: 8～24.
Grafted monomer for example is selected from one or both or the two or more compound in vinylformic acid, esters of acrylic acid (as methyl acrylate), methacrylic acid, methyl acrylic ester (as methyl methacrylate), vinyl cyanide, the maleic anhydride.
Radical initiator for example is selected from organo-peroxide and inorganic peroxide, and azo-compound etc. preferentially are selected from hydrogen peroxide, dibenzoyl peroxide, dicumyl peroxide, the special butyl ester of peroxidation base formic acid, Diisopropyl azodicarboxylate, or their mixture.
A kind of preferred manufacturing procedure of thin-film material of the present invention for example comprises by a certain percentage with plasticity-starch and polyethylene, preferred new LDPE (film grade) (LDPE) and linear low density polyethylene (LLDPE), grafted monomer, as vinylformic acid, esters of acrylic acid, methacrylic acid, methyl acrylic ester, vinyl cyanide, in the maleic anhydride one or both or two or more compound, radical initiator, as hydrogen peroxide, dibenzoyl peroxide, dicumyl peroxide, in special butyl ester of peroxidation base formic acid and the Diisopropyl azodicarboxylate any one or mixture, joining height stirs in the machine, (temperature must not above 40 ℃) mixes under the room temperature, and the quality proportioning of each component is: plasticity-starch: LDPE: LLDPE: grafted monomer: radical initiator=40～80: 10～30: 8～24: 1～3.5: 0.1～0.5.With the mixture length-to-diameter ratio is 1: 44～48,65 types or 75 type twin screw extruders with displacement devices carry out reactive extruding pelletization, each Heating Zone Temperature of screw rod is controlled between 110 ℃～140 ℃, screw speed is 120～160r/min, use inflation film manufacturing machine then, with the blow temperatures that is controlled at 140～160 ℃, 1.5: 1～2.5～1 blow-up ratio is blow molded into thin-film material with this pellet.
The blowing preparation method blows with the inflation film manufacturing machine of common blowing plastics film to form.Just blow temperatures is hanged down 10～15 ℃ than the pure new LDPE (film grade) and the pure low density linear polyethylene of same proportioning, and blow-up ratio is smaller, and general blow-up ratio is 1.5: 1～2.5: 1.
The invention still further relates to the thin-film material that obtains with aforesaid method.
The invention still further relates to above-mentioned thin-film material at agricultural mulching, light packaging film material, as: agricultural byproducts, clothes, the purposes in the fields such as the packing film of daily necessities.
The present invention compares with existing preparation starch-based degradable plastics method, its technological innovation part, mainly contain 2 points: the first is made plasticity-starch with starch earlier, by changing the phase structure of starch, reduce its second-order transition temperature, thereby improve the processing characteristics of starch, self intensity and with poly consistency.It two is to adopt the twin screw reactive extrusion technology, in the blend extrusion, make polyethylene under action of evocating with monomer generation graft copolymerization, the graft copolymer that generates makes plasticity-starch become homogeneous system with polyethylene blend as solubilizing agent, forms homogeneous phase phase structure.
Native starch is the double-stranded natural polymer of having of a kind of partial crystallization, contain in the molecule many form hydrogen bond-the OH group, because molecular chain is interior and molecule interchain hydrogen bond action, make starch be double-spiral structure, and easily absorb airborne water, water content is 11～13% in the starch usually.The rigidity of native starch particles is bigger, is difficult for fragmentation, and decomposition temperature is lower than melt temperature, does not have thermoplasticity, can't process in plastic processing machinery, decomposes before fusion.Want to make native starch to have thermoplasticity, must change the intramolecule structure, hydrogen bond in the saboteur, make crystalline duplex conformation transition become random conformation, make macromole become unordered shape ball of string shape structure, thereby reduce the second-order transition temperature of starch and melt temperature and be transformed into plasticity-, be convenient to processing by plasticity-not.
The present invention is in preparation plasticity-starch, the secondary plasticizer that is added all is a non-polar compound, under condition of heating and stirring, they are in a liquid state, and can fully be inserted between the starch chain, has the effect of peeling off, increase intermolecular distance, reduce intermolecular Van der Waals force, the polarity hydroxyl in the molecular chain is had shielding effect, starch molecular chain is moved easily, be convenient to processing.Softening agent is that polarity polyol and native starch have analog structure, form that can the hydrogen chain is inserted in the starch molecular chain, substitute original hydrogen chain in the starch molecular chain, make starch duplex conformation be converted into random conformation, make starch molecular chain be ball of string shape structure, native starch is converted into plasticity-starch.Meanwhile, under the negative pressure heated condition, most of combination water is discharged from the starch, helps plasticity-starch and polyethylene or polyethylene graft copolymer and mutually combines.Plasticity-starch and polyethylene blend are to utilize the extrusion reaction principle, with plasticity-starch, new LDPE (film grade), linear low density polyethylene, grafted monomer and radical initiator, after mixing by a certain percentage, join in the twin screw extruder, under fusion and high shear force state, initiator at first resolves into free radical, free radical initiation grafting monomer, and then be grafted on polyethylene and the starch molecular chain.Wherein graft reaction mainly occurs in the new LDPE (film grade) molecular chain on the tertiary carbon.The graft copolymer that generates under the twin screw high shear, makes the two form uniform co-mixing system as polyethylene and plasticity-starch solubilizing agent, generates equal phase structure, thereby improves the mechanical property of blend.Polyethylene graft copolymer can quicken poly Degradation owing to introduce oxygen containing polar group in the molecular chain, makes mulch film have good degradation property.
During reaction was extruded, the consumption of initiator and grafted monomer was the key that influences material mechanical performance and degradation property.Consumption is too much, and material mechanical performance is poor, and degradation property is good; And very few, then do not have the reaction solubilizing effect, polyethylene and plasticity-starch do not form homogeneous system, have obvious phase interface between the two.The intensity of same starch filled amount of influence and material.The degradation rate of mulch film is to realize by the consumption of control initiator and grafted monomer.
The present invention is aspect the blowing of starch-base biodegradation mulch film, used blown film equipment is common plastics blown film equipment, be in the material owing to contain a large amount of plasticity-starch, melt temperature is lower than pure polyethylene, blow temperatures and blow-up ratio also should be low, general blow temperatures is controlled at 140～160 ℃, and blow-up ratio is 1.5: 1～2.5～1 to be advisable.
The plasticity-starch content is 42～80wt% in the mulch film of the present invention, and the content of polyethylene and polyethylene graft copolymer is 20～58wt%.The biodegradability of mulch film is controlled, and mulch film can break down into 2～4cm in 3～6 months
2Fragment.Basically can be dissolved by soil after 1 year.This invention is compared with present production starch-based degradable plastics technology, the starch content height, and biological degradation is dissolved, and degraded is controlled inductive phase, and production technique is simple, cost is low, is 80～90% of pure polyethylene ground film cost.
Embodiment
Embodiment 1
Take by weighing industrial yam starch 72kg, 1.5kg whiteruss, 1.5kg stearic acid, 1kg relative molecular mass 1000～1500 low-molecular polyethylene waxs, join in the homogenizer that air extractor is housed, start off-gas pump and stirrer, 90～95 ℃ of controlled temperature, machine internal pressure 60Kpa～70Kpa, rotating speed 180r/min stir after 5 minutes, closing off-gas pump makes and returns to normal pressure in the stirrer, add the 15kg glycerol again, 10kg acetate sorbitol ester, the 5kg polymerization degree 300～400, the polyvinyl alcohol of 100% hydrolysis is reset off-gas pump.Under the aforesaid operations condition, continuation is got material after stirring 8min, makes to have certain elastic granule shape plasticity-yam starch, and water-content is reduced to about 3.5% in the plasticity-starch.
Get 50kg plasticity-yam starch and 20kgLDPE, 15kg LLDPE, the 1kg maleic anhydride, 0.5kg methyl acrylate and 0.15kg dicumyl peroxide, in height stirred machine, low speed (60r/min) stirred 5 minutes (to be no more than 40 ℃) under the normal temperature.
With 65 type length-to-diameter ratios 1: 44 twin screw extruder with gas barrier, extrusion temperature is controlled at 110 ℃～140 ℃ with above-mentioned compound, and extruding pelletization is used the pellet blown film, and the blown film temperature is 150～160 ℃.The blowing mulch film is in the shop film test of area, Atushi, Xinjiang, and mulch film begins to burst apart after 4 months, is broken into 3～4cm after 6 months
2Fragment.Can only see tiny filament after 1 year.
Embodiment 2
Get 50kg plasticity-yam starch and 25kgLDPE that embodiment 1 makes, 20kgLLDPE, 2.5kg vinylformic acid, 0.5kg methyl acrylate, 1kg maleic anhydride, 0.2kg dibenzoyl peroxide, press embodiment 1 same schedule of operation and processing condition, make pellet, the blowing mulch film, began in 4 months to burst apart in the shop film test of area, Atushi, Xinjiang with this mulch film, be broken into 4～6cm after 6 months
2Fragment.Can only see 0.2cm * 0.6cm bar after 1 year, not influence crop growth.
Embodiment 3
Take by weighing industrial W-Gum 75kg, the 2kg solid paraffin, the 1kg Magnesium Stearate, the 1kg whiteruss, join in the homogenizer that air extractor is housed, start off-gas pump and stirrer, 80～90 ℃ of controlled temperature, machine internal pressure 50Kpa～60Kpa, rotating speed 180r/min stir after 4 minutes, closing off-gas pump makes and returns to normal pressure in the stirrer, add 5kg ethylene glycol again, 10kg glycerol, the 10kg Sorbic Acid and the 4kg polymerization degree 400～600, the polyvinyl alcohol of 100% hydrolysis is reset off-gas pump and stirrer.Under the aforesaid operations condition, continuation is got material after stirring 10min, makes to have certain elastic granule shape plasticity-W-Gum, and water content is reduced to about 2～3% in the plasticity-starch.
Get 50kg plasticity-W-Gum and 25kg LDPE, 10kgLLDPE, the 1kg maleic anhydride, 1kg methyl methacrylate and 0.2kg Diisopropyl azodicarboxylate, press embodiment 1 same schedule of operation and processing condition, produce the starch-base biodegradation pellet earlier, be blow molded into mulch film again, land for growing field crops shop film test result and embodiment 1 degradation effect are basic identical.
Embodiment 4
Get 50kg plasticity-W-Gum and 30kg LDPE that embodiment 3 makes, 10kg LLDPE, 1.5kg maleic anhydride, 0.5kg methyl acrylate, 0.15kg the special butyl ester of peroxidation phenylformic acid is pressed embodiment 1 same schedule of operation and processing condition, produces the starch-base biodegradation pellet earlier, be blow molded into mulch film again, land for growing field crops shop film test result and embodiment 2 degradation effects are basic identical.
Embodiment 5
Take by weighing industrial W-Gum 75kg, the 2kg solid paraffin, the 1kg Magnesium Stearate, the 1kg whiteruss, join in the homogenizer that air extractor is housed, start off-gas pump and stirrer, 80～90 ℃ of controlled temperature, machine internal pressure 50Kpa～60Kpa, rotating speed 180r/min stir after 4 minutes, closing off-gas pump makes and returns to normal pressure in the stirrer, add 5kg ethylene glycol again, 10kg glycerol, the 10kg Sorbic Acid and the 4kg polymerization degree 400～600, the polyvinyl alcohol of 100% hydrolysis is reset off-gas pump and stirrer.Under the aforesaid operations condition, continuation is got material after stirring 10min, makes to have certain elastic granule shape plasticity-W-Gum, and water content is reduced to about 2～3% in the plasticity-starch.
Get 50kg plasticity-W-Gum and 30kg LDPE, 5kg LLDPE, 1kg maleic anhydride, 1kg methyl methacrylate and 0.2kg Diisopropyl azodicarboxylate, press embodiment 1 same schedule of operation and processing condition, produce the starch-base biodegradation pellet earlier, be blow molded into packaging film again.
Claims (9)
1, a kind of production method of starch-base biodegradation thin-film material, comprise with plasticity-starch, polyethylene, grafted monomer and radical initiator make polyethylene under the initiator effect can with the temperature of monomer generation graft copolymerization under be blended into compound, then this compound is made film, wherein plasticity-starch: polyethylene: grafted monomer: radical initiator weight ratio=40～80: 18～54: 1～3.5: 0.1～0.5.
2, according to the production method of claim 1, wherein plasticity-starch is by using secondary plasticizer and softening agent at 70-110 ℃ native starch, obtain by combination treatment under preferred 80-100 ℃ the temperature, wherein the content of secondary plasticizer is 2～4% of amount of starch in the plasticity-starch, the content of softening agent is 20～40% of amount of starch, and optimum quantity is 25～35%.
3, according to the production method of claim 2, wherein secondary plasticizer is selected from the lipid acid and the salt thereof of whiteruss, solid paraffin, 12～18 carbon, the low-molecular-weight wax of relative molecular weight 500～2000, or their mixture; Softening agent is selected from ethylene glycol, tirethylene glycol, propylene glycol, glycerol, sorbyl alcohol, acetate, sorbic ester, ethyl Sorbic Acid ether, polyvinyl alcohol (polymerization degree 200～1000,100% hydrolysis), or their mixture.
4, production method according to claim 1, wherein plasticity-starch obtains by the following method: with native starch, as W-Gum, yam starch, tapioca (flour), sweet potato starch, the mixture of any one or they in rice starch and the wheat starch, be good wherein with straight chain content higher W-Gum and yam starch, by a certain percentage with secondary plasticizer, as whiteruss, solid paraffin, the lipid acid of 12～18 carbon and salt thereof, the height that in the low-molecular-weight wax of relative molecular mass 500～2000 one or both and two or more compound join together with air extractor stirs in the machine, under negative pressure state, high-speed stirring 5～8min, temperature is controlled at 80～100 ℃; And then add a certain amount of softening agent, and as: ethylene glycol, tirethylene glycol, propylene glycol, glycerol, sorbyl alcohol, acetate, sorbic ester, ethyl Sorbic Acid ether, one or both in the polyvinyl alcohol (polymerization degree 200～1000,100% hydrolysis) or two or more compound; Under above-mentioned identical processing condition, behind continuation high-speed stirring 6～10min, just can make plasticity-starch; The content of secondary plasticizer is 2～4% of starch quality in the plasticity-starch, and the content of softening agent is 20～40% of amount of starch, and optimum quantity is 25～35%.Water content is reduced to 3～5% by ative starch 11～13% in the plasticity-starch.
5, according to the production method of claim 1, wherein polyethylene is the blend of new LDPE (film grade) and linear low density polyethylene, and the ratio of the two is 10～30: 8～24.
6, according to the production method of claim 1, wherein grafted monomer is selected from one or both or the two or more compound in vinylformic acid, esters of acrylic acid, methacrylic acid, methyl acrylic ester, vinyl cyanide, the maleic anhydride.
7, according to the production method of claim 1, wherein radical initiator is selected from hydrogen peroxide, dibenzoyl peroxide, dicumyl peroxide, the special butyl ester of peroxidation base formic acid, Diisopropyl azodicarboxylate, or their mixture.
8, the thin-film material that obtains by each the method for claim 1-7.
9, the thin-film material of claim 8 is at the preparation agricultural mulching, and the usefulness that reaches in the light packaging film material is coated with.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402567C (en) * | 2006-07-03 | 2008-07-16 | 浙江工业大学 | Preparation method of graft starch |
| CN101831097A (en) * | 2010-04-09 | 2010-09-15 | 常州百利基生物材料科技有限公司 | Biodegradable mulching film |
| CN103570976A (en) * | 2013-10-16 | 2014-02-12 | 池州市大恒生化有限公司 | Master batches |
| CN103739922A (en) * | 2013-12-18 | 2014-04-23 | 戴骏超 | Environment-friendly garbage bag and preparation method thereof by film blowing |
| CN105001492A (en) * | 2015-07-23 | 2015-10-28 | 安徽德琳环保发展（集团）有限公司 | Low-density polyethylene degradable mulching film modified by carrying cross-linked starch through nanometer active carbon and preparing method of low-density polyethylene degradable mulching film |
| CN105175848A (en) * | 2015-07-23 | 2015-12-23 | 安徽德琳环保发展（集团）有限公司 | Low-density polyethylene degradable film modified by nano polygorskite loaded crosslinked starch and preparation method for low-density polyethylene degradable film |
| CN106366358A (en) * | 2016-08-31 | 2017-02-01 | 迁安市隆赓塑料制品有限公司 | Multifunctional polyethylene photo-biodegradable mulching film |
| CN109517224A (en) * | 2018-09-10 | 2019-03-26 | 天津大学 | Biodegradable adhesive tape film |
| CN112358657A (en) * | 2020-11-26 | 2021-02-12 | 重庆和泰润佳股份有限公司 | Non-air-permeable biodegradable film and preparation method thereof |
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2003
- 2003-10-29 CN CN 200310102295 patent/CN1284820C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402567C (en) * | 2006-07-03 | 2008-07-16 | 浙江工业大学 | Preparation method of graft starch |
| CN101831097A (en) * | 2010-04-09 | 2010-09-15 | 常州百利基生物材料科技有限公司 | Biodegradable mulching film |
| CN103570976A (en) * | 2013-10-16 | 2014-02-12 | 池州市大恒生化有限公司 | Master batches |
| CN103739922A (en) * | 2013-12-18 | 2014-04-23 | 戴骏超 | Environment-friendly garbage bag and preparation method thereof by film blowing |
| CN105001492A (en) * | 2015-07-23 | 2015-10-28 | 安徽德琳环保发展（集团）有限公司 | Low-density polyethylene degradable mulching film modified by carrying cross-linked starch through nanometer active carbon and preparing method of low-density polyethylene degradable mulching film |
| CN105175848A (en) * | 2015-07-23 | 2015-12-23 | 安徽德琳环保发展（集团）有限公司 | Low-density polyethylene degradable film modified by nano polygorskite loaded crosslinked starch and preparation method for low-density polyethylene degradable film |
| CN106366358A (en) * | 2016-08-31 | 2017-02-01 | 迁安市隆赓塑料制品有限公司 | Multifunctional polyethylene photo-biodegradable mulching film |
| CN109517224A (en) * | 2018-09-10 | 2019-03-26 | 天津大学 | Biodegradable adhesive tape film |
| CN112358657A (en) * | 2020-11-26 | 2021-02-12 | 重庆和泰润佳股份有限公司 | Non-air-permeable biodegradable film and preparation method thereof |
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| CN1284820C (en) | 2006-11-15 |
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