CN1927930A - Preparation method of sunlight photocatalysis degradation agricultural thin film - Google Patents
Preparation method of sunlight photocatalysis degradation agricultural thin film Download PDFInfo
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- CN1927930A CN1927930A CN 200610116366 CN200610116366A CN1927930A CN 1927930 A CN1927930 A CN 1927930A CN 200610116366 CN200610116366 CN 200610116366 CN 200610116366 A CN200610116366 A CN 200610116366A CN 1927930 A CN1927930 A CN 1927930A
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- 230000015556 catabolic process Effects 0.000 title claims abstract description 65
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 65
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000007146 photocatalysis Methods 0.000 title claims description 45
- 239000010409 thin film Substances 0.000 title claims description 38
- 239000011941 photocatalyst Substances 0.000 claims abstract description 64
- 239000004698 Polyethylene Substances 0.000 claims abstract description 28
- 229920000573 polyethylene Polymers 0.000 claims abstract description 28
- -1 polyethylene Polymers 0.000 claims abstract description 26
- 239000010408 film Substances 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 206010070834 Sensitisation Diseases 0.000 claims description 19
- 230000008313 sensitization Effects 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 10
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000009775 high-speed stirring Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 4
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 4
- 229940043267 rhodamine b Drugs 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YCUVUDODLRLVIC-VPHDGDOJSA-N sudan black b Chemical compound C1=CC(=C23)NC(C)(C)NC2=CC=CC3=C1\N=N\C(C1=CC=CC=C11)=CC=C1\N=N\C1=CC=CC=C1 YCUVUDODLRLVIC-VPHDGDOJSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 239000003504 photosensitizing agent Substances 0.000 abstract description 3
- 229920013716 polyethylene resin Polymers 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 19
- 229920001684 low density polyethylene Polymers 0.000 description 18
- 239000004702 low-density polyethylene Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 238000001782 photodegradation Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920005615 natural polymer Polymers 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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Abstract
The present invention relates to preparation process of sunlight catalyzed degradable farm film. Organic photosensitizer sensitized nanometer TiO2 as the catalyst is mixed polyethylene resin in a double screw extruder to prepare photocatalytic polyethylene agglomerate containing photocatalyst in 20-40 wt%. The polyethylene agglomerate is then mixed with polyethylene resin and blown to prepare the sunlight catalyzed degradable farm film of 8-40 micron thickness and with photocatalyst content of 0.1-10 wt%. The sunlight catalyzed degradable farm film has simple preparation process, low cost, high efficiency photocatalytic degradation in controllable degradation rate, and effectively lowered harm to environment.
Description
Technical field
The present invention relates to a kind of preparation method of sunlight photocatalysis degradation agricultural thin film, belong to chemical field.
Background technology
The application of agricultural film has greatly promoted China's Agricultural Development.Meanwhile, also brought serious pollution problem to soil.Polyethylene molecule symmetry is stable, and intensity is good, is difficult to degraded under field conditions (factors).The polyethylene film that remains in the soil is difficult to reclaim, and soil tilth, air permeability are produced detrimentally affect, and long-term accumulation causes crop yield to descend.The degradation problem that solves polyethylene agricultural film has become the task of top priority.
Existing degradation technique mainly contains photodegradation technology, biodegradation technique, light/bio-degradable technology etc.The photodegradation technology is to point to introduce light enhanced sensitivity group in the macromolecular material or add photosensitive material, makes it cause photochemical reaction after absorbing solar ultraviolet light, thereby makes macromolecular chain be broken into micromolecular method.Its problem mainly is that degradation efficiency is low, and speed is very slow, and can not degrade fully, and the small molecules photodegradation product of formation can produce serious secondary pollution problem.Biodegradation technique mainly is divided into part biological degradation technique and complete biodegradable technology.The part biological degradation technique is that the method by natural polymer and superpolymer blend or copolymerization realizes.In these class plastics, have only the natural polymer subdivision wherein can be by microbiological degradation, residual superpolymer goods still exist with a kind of structure of low strength porous form, and its degradation time is still very long, and the small molecules organic product can cause secondary pollution to soil and groundwater resource.What the complete biodegradable technology then adopted is the material of natural polymer or similar natural polymer minor structure, not common versatility plastics, the production cost height, plastics performance is poor, range of application is narrow, store with the process of using in also can be degraded by microorganism attack such as bacterium.Light/bio-degradable technology has biological degradation and photodegradative performance simultaneously, and it mainly adopts the addition type technology, introduces functional agents such as microbiological culture media, photosensitizers, autoxidator simultaneously, realizes its degradation function.The subject matter of this technology is that light is not ideal enough with biological combination, equally also is difficult to reach the purpose of degraded fully.
Nano photo catalyzed oxidation is a novel pollution treatment technology.After the ultraviolet ray of nano-photocatalyst in absorbing sunlight, can produce hydroxyl free radical and superoxide radical with water that is adsorbed on the surface and oxygen effect, have stronger redox ability, shown photocatalysis performance efficiently at aspects such as degradable organic pollutant, purification water and airs.But because the restriction of this body structure of nano-photocatalyst can only utilize UV-light, and UV-light only accounts for 4% of solar spectrum, this has just limited this technology and has used in practice.Utilize the organic photosensitive agent with the nano-photocatalyst sensitization, the photoresponse wavelength spread that can make photocatalyst is applied to the degraded of macromolecular material to visible region, has very high learning value and economic worth, has a high potential.
Reported among the Chinese patent CN1405214A and utilized the TiO2/ organic dye to be photocatalyst, miscible with plastics in tetrahydrofuran (THF), be added drop-wise to its dried film forming on the polyfluortetraethylene plate then, make the method for Photocatalytic Activity for Degradation plastics.The main drawback of this method is the poor operability in scale operation, is not suitable for industrialization promotion.Chinese patent CN1587309A discloses the preparation method of a kind of photodegradation nano TiO 2-polyethylene composite plastic, this method is earlier the nano TiO 2 powder to be carried out surface modification, make master batch with polyethylene blend then, and then will contain the master batch and the blend of polyethylene raw material of nano TiO 2, adopt the mixing photodegradation nano TiO 2-polyethylene composite plastic that makes of mixing roll.
The main drawback of this method is: the photodegradable plastics that makes is excessive to the dependency of UV-light, and the degradation efficiency under sunlight is lower; With the photodegradable plastics that this method makes, its degradation rate is not had a controllability, is difficult to satisfy the needs of different field.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of novel sunlight photocatalysis degradation agricultural thin film, the nano-photo catalytic polyethylene agricultural film of this method preparation can effectively be degraded under solar light irradiation, and degradation rate is controlled.
The preparation method of a kind of sunlight photocatalysis degradation agricultural thin film of the present invention is characterized in that adopting the nano-TiO of organic photosensitive agent sensitization
2Be photocatalyst, in twin screw extruder,, make and contain sensitization TiO with the polyvinyl resin blend
2The photochemical catalysis polyethylene master batch of photocatalyst, this master batch again with polyvinyl resin blend blown film, make sunlight photocatalysis degradation agricultural thin film; Its preparation process and step are as follows:
(a) the organic photosensitive agent is dissolved in the solution that is made into 0.001~0.005g/ml in the solvent, it is added drop-wise to the nano-TiO of high-speed stirring
2Aqueous dispersions in, drip to finish the back and continue to stir 30~90min, filter then, wash, drying, make the nano-TiO of organic photosensitive agent sensitization
2Photocatalyst; The organic photosensitive agent is any in rhodamine B, eosin, phthalocyanine blue, methylene blue or the Sudan black B; Solvent is any in water, ethanol or the acetone;
(b) with the nano-TiO of the above-mentioned organic photosensitive agent sensitization that makes
2Photocatalyst is placed in the twin screw extruder and the ldpe resin blend, makes and contains sensitization TiO
2The photochemical catalysis polyethylene master batch of catalyzer; This master batch again with polyvinyl resin blend blown film, make dog sunlight photocatalysis degradation agricultural thin film; With the polyvinyl resin of master batch blend be in ldpe resin or the linear low density polyethylene resin any, perhaps this both hybrid resin, the proportioning of hybrid resin is: ldpe resin: linear low density polyethylene resin=1: 1~4: 1.
Above-mentioned nano-TiO
2Be any of titanium ore type or rutile-type, perhaps this mixing crystal formation of two kinds, its particle diameter is 5~100nm; The photocatalyst TiO of described photochemical catalysis ethene master batch
2Content be 20~40wt%; The photocatalyst TiO of goods film
2Content be 0.1~10wt%; The thickness of film is 8~40 μ m.
Its melting index of above-mentioned ldpe resin MI is 0.1~2g/10min.
Characteristics of the present invention are: the sunlight photocatalysis polyethylene agricultural film that (1) utilizes the present invention to prepare, and technology is simple, cost is low, can effectively degrade under solar light irradiation, and degradation rate is controlled; (2) the sunlight photocatalysis polyethylene agricultural film that utilizes the present invention to prepare, dependency to UV-light reduces greatly, under solar light irradiation, can catalyzed polyethylene agricultural film generation efficient degradation react, under similarity condition, the degradation efficiency that does not add the film of organic photosensitizers than adding nano TiO 2 improves 1~3 times, improves more than 10 times than the degradation efficiency of pure polyethylene film; (3) cost of the present invention is lower, and technology is simple.
Embodiment
After now specific embodiments of the invention being described in.
The technical process of the embodiment of the invention is as follows:
1, adopt the organic photosensitive agent to nano-TiO
2Carry out surface sensitizing and handle, the photocatalyst of preparation organic photosensitive agent sensitization.
2, the photocatalyst of organic photosensitive agent sensitization and polyvinyl resin blend granulation in twin screw extruder, making photocatalyst content is 20~40wt% photochemical catalysis polyethylene master batch, again with polyvinyl resin blend blown film, make the sunlight photocatalysis degradation agricultural thin film that photocatalyst content is 0.1~10wt%, film thickness is 8~40 μ m.
Among the embodiment, LDPE represents new LDPE (film grade), and LLDPE represents linear low density polyethylene.
Embodiment 1
Rhodamine B is dissolved in ethanol, is made into the solution of 0.001g/ml, be added drop-wise to the nano-TiO of high-speed stirring
2In the aqueous dispersions of (particle diameter is 15nm, Detitanium-ore-type), dropwise the back and continue to stir 30min, filter then, wash, drying, make the nano-TiO of rhodamine B sensitization
2Photocatalyst.The blend granulation in twin screw extruder with photocatalyst and LDPE resin (MI=1.0g/10min), obtaining photocatalyst content is the photochemical catalysis polyethylene master batch of 20wt%, with LDPE resin (MI=1.0g/10min) blend blown film, make the controlled sunlight photocatalysis degradation agricultural thin film of degradation rate that photocatalyst content is respectively 0.5wt%, 1wt%, 2wt% again.
The thickness of the sunlight photocatalysis degradation agricultural thin film that makes is about 10 μ m, and it is cut into 5 * 5cm
2Square sample carry out sunlight photocatalysis degradation test.Studies show that under the room temperature, behind solar light irradiation 300h, photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 0.5wt% reduces by 30.5%, molecular weight reduces by 61.5%; Photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 1wt% reduces by 33.7%, and molecular weight reduces by 65.8%; Photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 2wt% reduces by 37.1%, and molecular weight reduces by 69.2%.
Embodiment 2
Eosin is dissolved in ethanol, is made into the solution of 0.002g/ml, be added drop-wise to the nano-TiO of high-speed stirring
2In the alcohol dispersion liquid of (particle diameter is 50nm, Detitanium-ore-type), dropwise the back and continue to stir 45min, filter then, wash, drying, make the nano-TiO of eosin sensitization
2Photocatalyst.The blend granulation in twin screw extruder with photocatalyst and LDPE resin (MI=2.0g/10min), obtaining photocatalyst content is the photochemical catalysis polyethylene master batch of 30wt%, with LDPE resin (MI=2.0g/10min) blend blown film, make the controlled sunlight photocatalysis degradation agricultural thin film of degradation rate that photocatalyst content is respectively 0.5wt%, 1wt%, 2wt% again.
The thickness of the sunlight photocatalysis degradation agricultural thin film that makes is about 20 μ m, and it is cut into 5 * 5cm
2Square sample carry out sunlight photocatalysis degradation test.Studies show that under the room temperature, behind solar light irradiation 300h, photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 0.5wt% reduces by 35.9%, molecular weight reduces by 64.7%; Photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 1wt% reduces by 38.2%, and molecular weight reduces by 69.2%; Photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 2wt% reduces by 41.1%, and molecular weight reduces by 75.6%.
Embodiment 3
Phthalocyanine blue is dissolved in ethanol, is made into the solution of 0.003g/ml, be added drop-wise to the nano-TiO of high-speed stirring
2In the alcohol dispersion liquid of (particle diameter is 25nm, Detitanium-ore-type), dropwise the back and continue to stir 60min, filter then, wash, drying, make the nano-TiO of phthalocyanine blue sensitization
2Photocatalyst.The blend granulation in twin screw extruder with photocatalyst and LDPE resin (MI=2.5g/10min), obtaining photocatalyst content is the photochemical catalysis polyethylene master batch of 30wt%, with LDPE resin (MI=2.5g/10min) blend blown film, make the controlled sunlight photocatalysis degradation agricultural thin film of degradation rate that photocatalyst content is respectively 0.5wt%, 1wt%, 2wt% again.
The thickness of the sunlight photocatalysis degradation agricultural thin film that makes is about 25 μ m, and it is cut into 5 * 5cm
2Square sample carry out sunlight photocatalysis degradation test.Studies show that under the room temperature, behind solar light irradiation 300h, photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 0.5wt% reduces by 31.7%, molecular weight reduces by 56.2%; Photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 1wt% reduces by 34.2%, and molecular weight reduces by 59.7%; Photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 2wt% reduces by 36.7%, and molecular weight reduces by 64.8%.
Embodiment 4
Methylene blue is dissolved in acetone, is made into the solution of 0.004g/ml, be added drop-wise to the nano-TiO of high-speed stirring
2In the alcohol dispersion liquid of (particle diameter is 75nm, Detitanium-ore-type), dropwise the back and continue to stir 75min, filter then, wash, drying, make the nano-TiO of methylene blue sensitization
2Photocatalyst.The blend granulation in twin screw extruder with photocatalyst and LDPE resin (MI=3.0g/10min), obtaining photocatalyst content is the photochemical catalysis polyethylene master batch of 30wt%, with LDPE resin (MI=3.0g/10min) blend blown film, make the controlled sunlight photocatalysis degradation agricultural thin film of degradation rate that photocatalyst content is respectively 0.5wt%, 1wt%, 2wt% again.
The thickness of the sunlight photocatalysis degradation agricultural thin film that makes is about 25 μ m, and it is cut into 5 * 5cm
2Square sample carry out sunlight photocatalysis degradation test.Studies show that under the room temperature, behind solar light irradiation 300h, photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 0.5wt% reduces by 28.9%, molecular weight reduces by 53.1%; Photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 1wt% reduces by 30.7%, and molecular weight reduces by 56.2%; Photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 2wt% reduces by 32.4%, and molecular weight reduces by 59.5%.
Embodiment 5
Sudan black B is dissolved in acetone, is made into the solution of 0.005g/ml, be added drop-wise to the nano-TiO of high-speed stirring
2In the alcohol dispersion liquid of (particle diameter is 25nm, anatase octahedrite and the crystal formation that mixes of rutile), dropwise the back and continue to stir 90min, filter then, wash, drying, make the nano-TiO of Sudan black B sensitization
2Photocatalyst.The blend granulation in twin screw extruder with photocatalyst and LDPE resin (MI=1.5g/10min), obtaining photocatalyst content is the photochemical catalysis polyethylene master batch of 30wt%, (wherein the content of LDPE resin is 50% with the hybrid resin of LDPE (MI=1.5g/10min) and LLDPE (MI=2g/10min) again, the content of LLDPE resin is 50%) the blend blown film, make the controlled sunlight photocatalysis degradation agricultural thin film of degradation rate that photocatalyst content is respectively 0.5wt%, 1wt%, 2wt%.
The thickness of the sunlight photocatalysis degradation agricultural thin film that makes is 30 μ m, and it is cut into 5 * 5cm
2Square sample carry out photocatalytic degradation test.Studies show that under the room temperature, behind solar light irradiation 300h, photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 0.5wt% reduces by 27.7%, molecular weight reduces by 58.1%; Photocatalyst content be that 1wt% sunlight photocatalysis degradation agricultural thin film weight reduces by 30.3%, molecular weight reduces by 62.4%; Photocatalyst content is that the sunlight photocatalysis degradation agricultural thin film weight of 2wt% reduces by 34.1%, and molecular weight reduces by 66.7%.
Below be comparative experimental example:
Comparative Examples 1
Make the polyethylene agricultural film that does not contain nano-photocatalyst with LDPE resin (MI=1g/10min) blown film, film thickness 10 μ m.Under the room temperature, this agricultural film is behind solar light irradiation 300h, and weight reduces by 2.5%, and molecular weight reduces by 15.6%.
Comparative Examples 2
(wherein the content of LDPE resin is 90wt% with the hybrid resin of LDPE (MI=1.5g/10min) and LLDPE (MI=1g/10min), the content of LLDPE resin is 10wt%) blown film makes the polyethylene agricultural film that does not contain nano-photocatalyst, film thickness 20 μ m.Under the room temperature, this agricultural film is behind solar light irradiation 300h, and weight reduces by 2.7%, and molecular weight reduces by 17.3%.
Comparative Examples 3
With LDPE resin (MI=2g/10min) and not photoactivated nano-TiO
2Photocatalyst is blend in twin screw extruder, making photocatalyst content is the photochemical catalysis polyethylene master batch of 20wt%, with LDPE resin (MI=2g/10min) blend blown film, make the polyethylene agricultural film that photocatalyst content is 1wt%, film thickness 30 μ m again.Under the room temperature, this agricultural film is behind solar light irradiation 300h, and weight reduces by 16.1%, and molecular weight reduces by 42.7%.
More than test shows, the agricultural film that the nano TiO 2 that uses organic photosensitive agent sensitization makes as photocatalyst and polyvinyl resin blend blown film, under solar light irradiation photocatalytic degradation efficiently can take place, can reduce the harm that discarded agricultural film causes environment so effectively.
Claims (3)
1. the preparation method of a sunlight photocatalysis degradation agricultural thin film is characterized in that adopting the nano-TiO of organic photosensitive agent sensitization
2Be photocatalyst, in twin screw extruder,, make and contain sensitization TiO with the polyvinyl resin blend
2The photochemical catalysis polyethylene master batch of photocatalyst, this master batch again with polyvinyl resin blend blown film, make sunlight photocatalysis degradation agricultural thin film; Its preparation process and step are as follows:
(a) the organic photosensitive agent is dissolved in the solution that is made into 0.001~0.005g/ml in the solvent, it is added drop-wise to the nano-TiO of high-speed stirring
2Aqueous dispersions in, drip to finish the back and continue to stir 30~90min, filter then, wash, drying, make the nano-TiO of organic photosensitive agent sensitization
2Photocatalyst; The organic photosensitive agent is any in rhodamine B, eosin, phthalocyanine blue, methylene blue or the Sudan black B; Solvent is any in water, ethanol or the acetone;
(b) with the nano-TiO of the above-mentioned organic photosensitive agent sensitization that makes
2Photocatalyst is placed in the twin screw extruder and the ldpe resin blend, makes and contains sensitization TiO
2The photochemical catalysis polyethylene master batch of catalyzer; This master batch again with polyvinyl resin blend blown film, make sunlight photocatalysis degradation agricultural thin film; With the polyvinyl resin of master batch blend be in ldpe resin or the linear low density polyethylene resin any, perhaps this both hybrid resin, the proportioning of hybrid resin is: ldpe resin: linear low density polyethylene resin=1: 1~4: 1.
2. the preparation method of a kind of sunlight photocatalysis degradation agricultural thin film as claimed in claim 1 is characterized in that described nano-TiO
2Be any of Detitanium-ore-type or rutile-type, perhaps this mixing crystal formation of two kinds, its particle diameter is 5~100nm; The photocatalyst TiO of described photochemical catalysis ethene master batch
2Content be 20~40wt%; The photocatalyst TiO of goods film
2Content be 0.1~10wt%; The thickness of film is 8~40 μ m.
3. the preparation method of a kind of sunlight photocatalysis degradation agricultural thin film as claimed in claim 1 is characterized in that its melting index of described ldpe resin MI is 0.1~2g/10min.
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101402757B (en) * | 2008-10-27 | 2011-04-13 | 江南大学 | Process for producing nano-freshness retaining packaging material |
US20140157663A1 (en) * | 2011-10-31 | 2014-06-12 | Ultrabatch S.R.L. | Laminar body for making greenhouse roofs and methods of greenhouse cultivation |
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2006
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CN101402757B (en) * | 2008-10-27 | 2011-04-13 | 江南大学 | Process for producing nano-freshness retaining packaging material |
US20140157663A1 (en) * | 2011-10-31 | 2014-06-12 | Ultrabatch S.R.L. | Laminar body for making greenhouse roofs and methods of greenhouse cultivation |
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CN107383536A (en) * | 2017-08-05 | 2017-11-24 | 福建师范大学 | The preparation method and device of a kind of photocatalysis film |
CN107383536B (en) * | 2017-08-05 | 2020-10-30 | 福建师范大学 | Preparation method and device of photocatalytic film |
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CN108970645A (en) * | 2018-07-26 | 2018-12-11 | 中原工学院 | Three screw rod legal systems are ready for use on the method and its application for administering the film of black and odorous water |
CN113245345A (en) * | 2021-04-30 | 2021-08-13 | 大连海事大学 | Method for degrading agricultural reflective film by using quantum dot photocatalytic material |
CN113245345B (en) * | 2021-04-30 | 2022-06-17 | 大连海事大学 | Method for degrading agricultural reflective film by using quantum dot photocatalytic material |
CN113105660A (en) * | 2021-05-25 | 2021-07-13 | 广东天原新材料有限公司 | Preparation method of photocatalytic polyethylene film for sewage treatment |
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