CN1857903A - Method for preparing nano light catalytic agriculture film - Google Patents
Method for preparing nano light catalytic agriculture film Download PDFInfo
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- CN1857903A CN1857903A CN 200610026959 CN200610026959A CN1857903A CN 1857903 A CN1857903 A CN 1857903A CN 200610026959 CN200610026959 CN 200610026959 CN 200610026959 A CN200610026959 A CN 200610026959A CN 1857903 A CN1857903 A CN 1857903A
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Abstract
The present invention relates to preparation process of nanometer catalytic agricultural polyethylene film with controllable degradation rate under sunlight, and belongs to the field of nanometer composite polymer material technology. Surface modified nanometer TiO2 as photocatalyst is first mixed with polyethylene in a double screw extruder to prepare photocatalytic polyethylene agglomerate with modified photocatalyst content of 20-40 wt%, the photocatalytic polyethylene agglomerate is then mixed with polyethylene resin and the mixture is prepared into nanometer photocatalytic agricultural polyethylene film of 8-40 micron thickness and with photocatalyst content of 0.5-2.0 wt%. The nanometer photocatalytic agricultural polyethylene film may be degraded effectively under sunlight in controllable degradation rate, resulting in lowered environmental pollution.
Description
Technical field
The present invention relates to the preparation method of the controlled nano-photo catalytic polyethylene agricultural film of degradation rate under a kind of sunshine, belong to nano particle composite high-molecular material technology 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, aeration are produced harmful effect, and long-term accumulation causes crop yield to descend.Become the task of top priority so solve the degradation problem of polyethylene agricultural film.
Existing degradation technique mainly contains light degradation technology, biodegradation technique, light/bio-degradable technology etc.
The light degradation 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 slow, and can not degrade fully, and the little molecule light degradation product of formation can produce the secondary pollution problem.
Biodegradation technique mainly is divided into part biological degraded and complete biodegradable technology.The part biological degradation technique is that the method by natural polymer and high polymer blend or copolymerization realizes.In these class plastics, have only natural polymer subdivision wherein to be decomposed by microorganism, residual high polymer still exists with a kind of structure of low-intensity porous form, and its degradation time is still very long, and small organic molecule can cause secondary pollution to soil and groundwater resources.What the complete biodegradable technology then adopted is the material of natural polymer or similar natural polymer minor structure, it is not common general plastic, the production cost height, plastics performance is poor, range of application is narrow, store with the process of using in also can be produced unfavorable factor by microorganism attack such as bacterium.
Light/bio-degradable technology has biodegradation and photodegradative performance simultaneously, and it mainly adopts the addition type technology, introduces function additives such as microbiological culture media, sensitising agent, 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 sunshine, can produce hydroxyl free radical and superoxide radical with water that is adsorbed on the surface and oxygen effect, they have very strong redox ability, have shown photocatalysis performance efficiently at aspects such as degradable organic pollutant, purification water and airs.Utilize nano-photocatalyst photocatalysis performance efficiently, be applied to the degraded of macromolecular material, have very high learning value and economic worth.
Reported among the Chinese patent CN1405214A and utilized TiO
2/ organic dyestuff is a photochemical catalyst, and is miscible in oxolane with plastics, is added drop-wise to its dried film forming on the polyfluortetraethylene plate then, makes the method for Photocatalytic Activity for Degradation plastics.The major defect of this method is the poor operability in large-scale production, is not suitable for industrialization promotion.Chinese patent CN1587309A discloses a kind of light degradation nano-TiO
2The preparation method of-polyethylene composite plastic, this method are earlier with nano-TiO
2Powder carries out surface modification, makes master batch with polyethylene blend then, and then will contain nano-TiO
2Master batch and the blend of polyethylene raw material, adopt the mixing light degradation nano-TiO that makes of mixing roll
2-polyethylene composite plastic.The major defect of this method is: the photodegradable plastics that makes is excessive to the dependence of ultraviolet light, and the degradation efficiency under sunshine 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.
Some scholars think that nano-photocatalyst can pass through doping vario-property, with significantly improving light-catalysed efficient behind some metallic ion-doping modification, dependence to ultraviolet light can reduce greatly, can the reaction of catalyzed polyethylene agricultural film generation efficient degradation under solar light irradiation.
Summary of the invention
The preparation method who the purpose of this invention is to provide the controlled nano-photo catalytic agricultural film of degradation rate under a kind of sunshine.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 invention provides a kind of preparation method of nano-photo catalytic agricultural film, it is characterized in that having following technical process and step:
Employing is through the nano-TiO of surface modification treatment
2Be photochemical catalyst, modification is treated to metal ion mixing or nonmetal doping; The metal ion mixing element is platinum, iron, cerium; The nonmetal doping element is a nitrogen; The content of doped chemical is 0.5～4.0wt%; Nano-TiO after at first modification being mixed
2Photochemical catalyst is incorporated in blend in double screw extruder in the polyvinyl resin, makes photocatalysis polyethylene master batch; The content of modified light catalyst is 20～40wt%; And then with polyvinyl resin blend blown film; Make the nano-photo catalytic polyethylene agricultural film; Film thickness is 8～40 μ m; The content of photochemical catalyst is 0.5～2.0wt% in the control polyethylene film.
In the inventive method, described polyvinyl resin is the hybrid resin of ldpe resin or low density polyethylene (LDPE) and LLDPE; The low density polyethylene (LDPE) in the hybrid resin and the weight ratio of LLDPE are 1: 1～4: 1; The melt index of low density polyethylene (LDPE) is 1～3g/10min; The melt index of LLDPE is 0.1～2.0g/10min.
Described nano-TiO
2Be any one or two kinds of mixing crystal formation of Detitanium-ore-type, rutile-type, its particle diameter is 5～100nm.
The inventive method technology is simple, cost is low, and the nano-photo catalytic polyethylene agricultural film that makes need not recycling after using and discarding in agricultural, under sunshine photocatalytic degradation efficiently can take place, degradation rate is controlled, can effectively reduce the harm that discarded agricultural film causes environment.
The specific embodiment
After now embodiments of the invention being described in.
Embodiment 1
The nano-TiO that adopts the modification of surface doping platinum to handle
2Be photochemical catalyst; Earlier chloroplatinic acid and citric acid are made into mol ratio and are 1: 6 solution, adding particle diameter again is the anatase type nano TiO of 15nm
2Dispersed with stirring is even, uses UV-irradiation after 5 hours then, and filtration, washing, drying obtain the nanometer Pt/TiO of modification
2Photochemical catalyst; Wherein the Pt constituent content is 2.0wt%.With the photochemical catalyst after the modification and ldpe resin (melt index=1.0g/10min) blend granulation in double screw extruder, the weight proportion of photochemical catalyst and ldpe resin is 20: 100; The photocatalysis polyethylene master batch that makes again with ldpe resin blend blown film, make the nano-photo catalytic polyethylene agricultural film, film thickness is 10 μ m; Adopt the photocatalysis polyethylene master batch and the ldpe resin blend blown film of different amounts, make nanometer Pt/TiO
2Photochemical catalyst content is respectively the nanometer Pt/TiO of 0.5wt%, 1wt%, 2wt%
2Polyethylene agricultural film.
The nanometer Pt/TiO that makes
2Photocatalysis polyethylene agricultural film thickness is 10 μ m, and it is cut into 5 * 5cm
2Square sample carry out photocatalytic degradation test.Test shows that under the room temperature, after 240 hours, photochemical catalyst content is the nanometer Pt/TiO of 0.5wt% through solar light irradiation
2-polyethylene agricultural film weight reduces by 28.7%, and molecular weight reduces by 58.5%; Photochemical catalyst content is the nanometer Pt/TiO of 1wt%
2-polyethylene agricultural film weight reduces by 32.4%, and molecular weight reduces by 63.1%; Photochemical catalyst content is the nanometer Pt/TiO of 2wt%
2-polyethylene agricultural film weight reduces by 35.1%, and molecular weight reduces by 68.8%.
Embodiment 2
The nano-TiO that adopts the modification of surface doping iron to handle
2Be photochemical catalyst; Earlier with a certain amount of Fe (NO
3)
39H
2O is dissolved in the hot water, stirs, and adds the anatase type nano TiO of 70nm
2, ultrasonic dispersion 40 minutes places 100 ℃ of baking oven bakings 24 hours then, takes out back porphyrize in mortar, fuses 1 hour in 500 ℃ of Muffle furnaces subsequently, again through porphyrize, makes the nanometer Fe/TiO of modification
2Photochemical catalyst, wherein iron content is 3.0wt%.With the photochemical catalyst after the modification and ldpe resin (melt index=2.0g/10min) blend granulation in double screw extruder, photochemical catalyst and ldpe resin weight proportion are 25: 100; The photocatalysis polyethylene master batch that makes again with ldpe resin blend blown film, make the nano-photo catalytic polyethylene agricultural film, film thickness is 20 μ m; Adopt the photocatalysis polyethylene master batch and the ldpe resin blend blown film of different amounts, make nanometer Fe/TiO
2Photochemical catalyst content is respectively nanometer Fe/TiO of 0.5wt%, 1.0wt%, 2.0wt%
2-polyethylene agricultural film.
Nanometer Fe/the TiO that makes
2Photocatalysis polyethylene agricultural film thickness is 20 μ m, and it is cut into 5 * 5cm
2Square sample carry out photocatalytic degradation test.Test shows that under the room temperature, after 240 hours, photochemical catalyst content is nanometer Fe/TiO of 0.5wt% through solar light irradiation
2-polyethylene agricultural film weight reduces by 22.5%, and molecular weight reduces by 50.1%; Photochemical catalyst content is nanometer Fe/TiO of 1.0wt%
2-polyethylene agricultural film weight reduces by 25.7%, and molecular weight reduces by 55.3%; Photochemical catalyst content is nanometer Fe/TiO of 2.0wt%
2-polyethylene agricultural film weight reduces by 28.4%, and molecular weight reduces by 58.7%.
Embodiment 3
Adopt the nano-TiO of the cerium modified processing of surface doping
2Be photochemical catalyst; Be the anatase of 75nm and the nano-TiO of rutile mixing crystal formation with particle diameter earlier
2Added in the distilled water in ultrasonic disperser vibration 20 minutes, and added cerous sulfate solution again, reaction temperature is 60 ℃, and in 3 hours reaction time, then after filtration, washing, drying, again after 600 ℃ of calcinings, porphyrize makes the nano Ce/TiO of modification
2Photochemical catalyst, wherein Ce elements content is 4.0wt%.With the photochemical catalyst after the modification and ldpe resin (melt index=3g/10min) blend granulation in double screw extruder, photochemical catalyst and ldpe resin weight proportion are 30: 100; The photocatalysis polyethylene master batch that makes again with ldpe resin blend blown film, make the nano-photo catalytic polyethylene agricultural film, film thickness is 25 μ m; Adopt the photocatalysis polyethylene master batch and the ldpe resin blend blown film of different amounts, make nano Ce/TiO
2Photochemical catalyst content is respectively nano Ce/TiO of 0.5wt%, 1.0wt%, 2.0wt%
2Polyethylene agricultural film.
Nano Ce/the TiO that makes
2Photocatalysis polyethylene agricultural film thickness is 25 μ m, and it is cut into 5 * 5cm
2Square sample carry out photocatalytic degradation test.Test shows that under the room temperature, after 240 hours, photochemical catalyst content is nano Ce/TiO of 0.5wt% through solar light irradiation
2-polyethylene agricultural film weight reduces by 18.9%, and molecular weight reduces by 43.1%; Photochemical catalyst content is nano Ce/TiO of 1.0wt%
2-polyethylene agricultural film weight reduces by 20.6%, and molecular weight reduces by 46.2%; Photochemical catalyst content is nano Ce/TiO of 2wt%
2-polyethylene agricultural film weight reduces by 22.7%, and molecular weight reduces by 49.3%.
Embodiment 4
The nano-TiO that adopts the modification of surface doping nitrogen to handle
2Be photochemical catalyst; With particle diameter is the anatase type nano TiO of 15nm
2Pack in the high temperature process furnances, the mist of feeding ammonia and argon gas is treated to be heated to 450 ℃ after air-flow steadily, reacts 3 hours, obtains modified TiO
2-XN
XPhotochemical catalyst, wherein the N constituent content is 0.5wt%.With the photochemical catalyst after the modification and ldpe resin (melt index=1.5g/10min) blend granulation in double screw extruder, photochemical catalyst and ldpe resin weight proportion are 35: 100; The photocatalysis polyethylene master batch that makes again with ldpe resin (melt index=1.5g/10min) and LLDPE (and the hybrid resin blend blown film of melt index=1g/10min), film thickness is 30 μ m; The weight proportion of low density polyethylene (LDPE) and LLDPE is 90: 10.Adopt the photocatalysis polyethylene master batch and the above-mentioned hybrid resin blend blown film of different amounts, make nano-TiO
2-XN
XPhotochemical catalyst content is respectively the nano-TiO of 0.5wt%, 1.0wt%, 2.0wt%
2-XN
X-polyethylene agricultural film.
The nano-TiO that makes
2-XN
XPhotocatalysis polyethylene agricultural film thickness is 30 μ m, and it is cut into 5 * 5cm
2Square sample carry out photocatalytic degradation test.Test shows that under the room temperature, after 240 hours, photochemical catalyst content is the nano-TiO of 0.5wt% through solar light irradiation
2-XN
X-polyethylene agricultural film weight reduces by 25.7%, and molecular weight reduces by 53.1%; Photochemical catalyst content is the nano-TiO of 1.0wt%
2-XN
X-polyethylene agricultural film weight reduces by 28.6%, and molecular weight reduces by 55.9%; Photochemical catalyst content is the nano-TiO of 2wt%
2-XN
X-polyethylene agricultural film weight reduces by 31.8%, and molecular weight reduces by 59.8%.
Some comparative experimental example of frequently using and doing are listed in following in order to oppose:
Comparative Examples 1
(melt index=2g/10min) blown film makes the polyethylene agricultural film that does not contain nano-photocatalyst, and film thickness is 10 μ m with ldpe resin.Under the room temperature, after 240 hours, weight reduces by 2.6% to this agricultural film through solar light irradiation, and molecular weight reduces by 25.7%.
Comparative Examples 2
Mixed resinous (both weight proportions are 90: 10) blend blown film with ldpe resin and LLDPE makes the polyethylene agricultural film that does not contain nano-photocatalyst, film thickness 30 μ m.Under the room temperature, after 240 hours, weight reduces by 2.7% to this agricultural film through solar light irradiation, and molecular weight reduces by 26.8%.
Comparative Examples 3
With the ldpe resin (nano-TiO of melt index=2g/10min) and non-modified
2Photochemical catalyst is blend in double screw extruder, making photochemical catalyst content is the photocatalysis polyethylene master batch of 25wt%, and then with ldpe resin blend blown film, make the polyethylene agricultural film that photochemical catalyst content is 1.0wt%, film thickness 10 μ m.Under the room temperature, after 240 hours, weight reduces by 15.2% to this agricultural film through solar light irradiation, and molecular weight reduces by 43.5%.
More than test shows, through the nano-TiO of modification processing
2The photocatalytic degradation of more efficient can take place in the nano-photo catalytic polyethylene agricultural film that photochemical catalyst and polyvinyl resin blend blown film make under solar light irradiation, can reduce the harm that discarded agricultural film causes environment so effectively.
Claims (3)
1. the preparation method of a nano-photo catalytic agricultural film is characterized in that having following technical process and step:
Employing is through the nano-TiO of surface modification treatment
2Be photochemical catalyst, modification is treated to metal ion mixing or nonmetal doping; The metal ion mixing element is platinum, iron, cerium; The nonmetal doping element is a nitrogen; The content of doped chemical is 0.5～4.0wt%; Nano-TiO after at first modification being mixed
2Photochemical catalyst adds in the polyvinyl resin, by the double screw extruder blend, makes photocatalysis polyethylene master batch; The content of modified light catalyst is 20～40wt%; And then with polyvinyl resin blend blown film; Make the nano-photo catalytic polyethylene agricultural film; Film thickness is 8～40 μ m; The content of photochemical catalyst is 0.5～2.0wt% in the control polyethylene film.
2. the preparation method of a kind of nano-photo catalytic agricultural film as claimed in claim 1 is characterized in that described polyvinyl resin is the hybrid resin of ldpe resin or low density polyethylene (LDPE) and LLDPE; The low density polyethylene (LDPE) in the hybrid resin and the weight ratio of LLDPE are 1: 1～4: 1; The melt index of low density polyethylene (LDPE) is 1～3g/10min; The melt index of LLDPE is 0.1～2.0g/10min.
3. the preparation method of a kind of nano-photo catalytic agricultural film as claimed in claim 1 is characterized in that described nano-TiO
2Be any one or two kinds of mixing crystal formation of Detitanium-ore-type, rutile-type, its particle diameter is 5～100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610026959 CN1857903A (en) | 2006-05-26 | 2006-05-26 | Method for preparing nano light catalytic agriculture film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610026959 CN1857903A (en) | 2006-05-26 | 2006-05-26 | Method for preparing nano light catalytic agriculture film |
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| CN1857903A true CN1857903A (en) | 2006-11-08 |
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ID=37296878
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012002933A1 (en) * | 2010-06-29 | 2012-01-05 | Empire Technology Development Llc | Coating materials for bisphenol a-containing polymers |
| CN102634094A (en) * | 2012-03-31 | 2012-08-15 | 许昌学院 | Optical and thermal-oxidative dual-degradation plastic thin film and manufacturing method thereof |
| CN102719004A (en) * | 2012-06-21 | 2012-10-10 | 莱阳子西莱环保科技有限公司 | Nanosize TiO2 photocatalysis degradable agricultural plastic film and preparation method thereof |
| CN111424368A (en) * | 2020-03-20 | 2020-07-17 | 赵梓权 | Method for producing nonwoven fabric, and protective product |
| CN117659546A (en) * | 2023-12-08 | 2024-03-08 | 潍坊华南环保科技有限公司 | Ecological degradable mulching film and preparation method thereof |
-
2006
- 2006-05-26 CN CN 200610026959 patent/CN1857903A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012002933A1 (en) * | 2010-06-29 | 2012-01-05 | Empire Technology Development Llc | Coating materials for bisphenol a-containing polymers |
| CN102634094A (en) * | 2012-03-31 | 2012-08-15 | 许昌学院 | Optical and thermal-oxidative dual-degradation plastic thin film and manufacturing method thereof |
| CN102719004A (en) * | 2012-06-21 | 2012-10-10 | 莱阳子西莱环保科技有限公司 | Nanosize TiO2 photocatalysis degradable agricultural plastic film and preparation method thereof |
| CN111424368A (en) * | 2020-03-20 | 2020-07-17 | 赵梓权 | Method for producing nonwoven fabric, and protective product |
| CN117659546A (en) * | 2023-12-08 | 2024-03-08 | 潍坊华南环保科技有限公司 | Ecological degradable mulching film and preparation method thereof |
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