CN101367971B - Preparation method for ultraviolet light degradable polythene or polypropylene film - Google Patents
Preparation method for ultraviolet light degradable polythene or polypropylene film Download PDFInfo
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- CN101367971B CN101367971B CN2008101972359A CN200810197235A CN101367971B CN 101367971 B CN101367971 B CN 101367971B CN 2008101972359 A CN2008101972359 A CN 2008101972359A CN 200810197235 A CN200810197235 A CN 200810197235A CN 101367971 B CN101367971 B CN 101367971B
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- manganese oxide
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- polypropylene
- ultraviolet light
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Abstract
The invention pertains to the technical field agricultural film preparation, particularly relating to a method for preparing ultraviolet light degradable polyethylene or polypropylene film. Manganese oxide or the boracic load body powder body and polyethylene or polypropylene masterbatch are mixed and dissolved in cyclohexane to prepare solution; the solution is evenly dripped on a polytetrafluor ethylene plate, tiled evenly, and taken off after being dried by natural wind, and finally, the desired ultraviolet light photocatalyzed polyethylene film is achieved. The method has the advantages that the process is simple and the raw materials are cheap; the prepared polyethylene or polypropylene film is degraded for 300 hours under ultraviolet light, the weight of the film prepared by the method is reduced by about 5 times compared with the common polyethylene or polypropylene film (with the same thickness and weight, not including the mineral applied by the invention) degraded under ultraviolet light; the total amount of volatile organic substance is reduced by about one third, and secondary pollution is avoided. The degradation reaction can be conducted in natural environment and the degradation is rapid. Therefore, the method has very high use value and a bright prospect of application.
Description
Technical field
The invention belongs to material chemistry technical field, be specifically related to a kind of preparation method of polyethylene or polypropylene screen of ultraviolet light degradable.
Technical background
The main component of agricultural mulching is polyethylene or polypropylene (PE or PP), is one of plastics of present turnout maximum in the world.The use of plastic sheeting for farm use helps crop growth, improves crop yield.Yet the increase of plastic sheeting for farm use usage quantity and refractory organics thereof make in the soil residual film and fragment thereof increase, and cause soil compaction, permeability variation, cause crop production reduction, and its difficult property that reclaims causes it to discard at occurring in nature, and is very big to ecotope harm.The main path that addresses this problem has: the landfill of residual film, burning, recovery and reuse, and preceding two kinds of methods not only exhaust the people and drain the treasury but also can cause secondary pollution; The recovery and reuse method of residual film makes and reclaims the residual film in back by the common production of refining again secondary film, and this regeneration membrane all is far from physical strength still is light transmitting property and can compares with former film, and result of use is very poor, and the cost that reclaims refining again is also very high.Facts have proved, can not cause film user's attention to this way to manage of residual film, residual film reclaims difficulty; In addition, the film fragment that is dissipated in the farmland still can't reclaim.Will thoroughly solve the pollution of residual film in the soil and fragment the like waste thereof, should be its fundamental way to use degradable plastic sheeting for farm use (comprising photodegradation film, Biodegradable film and light/Biodegradable film).
Photodegradation film generally can be divided into copoly type and addition type two class films.The former is the film that forms with after carbon monoxide or carbonyl monomer and ethene or other olefinic monomer copolymerization.These copolymer molecules are owing to contain chromophoric group and weak bond such as carbonyl on polymer chain.The latter is meant the polymeric film that adds the additive formation with photosensitization in copolymerization is synthetic.In the practical application of photodegradation film, exist how to select having high reactivity, stable, the problem of catalyzer and photosensitizers cheaply.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of polyethylene or polypropylene screen of ultraviolet light degradable is to solve the degraded of agricultural mulching fragments such as present polyethylene or polypropylene screen.The present invention is added to manganese oxide and boracic load thereof in poly-second (third) the alkene master batch to be prepared into ultraviolet light degradable polythene or polypropylene screen, and its degradation rate is fast, non-secondary pollution, is fit to apply aborning.
The present invention is achieved in that
A kind of polyethylene of ultraviolet light degradable or the preparation method of polypropylene screen, its step is as follows:
(1) with 277g MnCl
24H
2After O is dissolved in the 1907ml deionization, add 893ml36%HAc, continue under the vigorous stirring, adding concentration with the speed of 200ml/min is 0.4mol/L KMnO
4Solution, after reaction finished, directly suction filtration got mineral precipitation, with mineral precipitation deionized water repetitive scrubbing, dry down for 60 ℃, the 100 order analyses of milling sieve the manganese oxide powder;
(2) with 277gMnCl
24H
2After O is dissolved in the 1907ml deionized water, add 893ml36%HAc, continue under the vigorous stirring, adding concentration with the speed of 200ml/min is the KMnO of 0.4mol/L
4Solution (containing 0.75mol/L boric acid), after reaction finished, directly suction filtration got mineral precipitation, with this mineral precipitation deionized water repetitive scrubbing, dry down for 60 ℃, the 100 order analyses of milling sieve manganese oxide boracic load powder;
(3) polyethylene or polypropylene are dissolved in the cyclohexane solution, add manganese oxide or manganese oxide boracic load powder then, stir 3h, manganese oxide or manganese oxide boracic load powder are uniformly dispersed in described cyclohexane solution, press mass ratio, manganese oxide or manganese oxide boracic load powder: polyethylene or polypropylene: hexanaphthene=1:20～60:300～800; Obtain polyethylene or polypropylene suspension solution;
(4) polyethylene that step (3) is obtained or polypropylene suspension solution evenly drip on polyfluortetraethylene plate, and the power effect of relying on for support evenly is tiled on this plate, opens behind the natural air drying, promptly make the polyethylene of ultraviolet light degradable or poly-
The alkene film.
More detailed technical scheme is as described in " embodiment ".
Effect of the present invention is: manganese oxide mineral and boracic load thereof have advantages such as activity is high, with low cost, utilize ultraviolet light degradable polythene or polypropylene screen that the present invention prepares, have that technology is simple, cost is low, degradable characteristics under UV-light, and degradation rate is fast.In identical UV-irradiation in the time, polyethylene or polypropylene screen by the present invention's preparation, its quality reduces about 5 times than the common polythene that does not contain associated minerals or the polypropylene screen of condition of equivalent thickness and equal quality in the quality of degraded gained under the similarity condition, and non-secondary pollution.
Description of drawings
Fig. 1: load manganese oxide or boracic load polyethylene film UV-irradiation rate of weight loss graphic representation.(b:0.4wt% is c:1.0wt%) with the rate of weight loss of PE-boracic manganese oxide (d:0.4wt%) film with UV-irradiation for Fig. 1 PE (a), PE-manganese oxide.
Fig. 2: load manganese oxide or boracic load polypropylene film UV-irradiation rate of weight loss graphic representation.Among the figure: PS (a), PS-manganese oxide (b:0.4wt%) and PS-boracic manganese oxide (c:0.4wt%) film are with the rate of weight loss of UV-irradiation.
Embodiment
Embodiment 1:
1, manganese oxide powder preparing:
Synthesizing of manganese oxide: with 277g MnCl
24H
2After O is dissolved in the 1907ml deionization, add 893ml36%HAc, continue under the vigorous stirring, with the speed adding KMnO of 200ml/min
4Solution is (with 177g KMnO
4Be dissolved in the 2800ml water), after reaction finished, directly suction filtration got mineral precipitation, the precipitate with deionized water repetitive scrubbing, 60 ℃ of oven dry down, 100 mesh sieves of milling get the manganese oxide powder.
2, degradable polyethylene membrane prepare:
1.0g polyethylene masterbatch is dissolved in the hexanaphthene of 50ml, adds 0.004g manganese oxide powder.Stir 3h, manganese oxide is uniformly dispersed in solution, with the solution of this about 20ml, evenly drip on tetrafluoroethylene, the power effect of relying on for support evenly is tiled on this plate, takes off behind the natural air drying, makes the degradable polyethylene film.With the 20W ultraviolet lamp is light source, has compared film and common polythene film (except that not adding the oxidation manganese mineral, other the operates same present embodiment) situation with its quality of light application time, molecular weight, surface adsorption species and generation secondary pollution.Experiment shows that the common polythene film is behind UV-irradiation 300h, and quality minimizing value is 4%.And the vinyon that adopts present embodiment to prepare, because the effect of manganese oxide, its quality minimizing value brings up to 10% behind the UV-irradiation 300h; Infrared spectra behind the polyethylene film ultraviolet lighting 300h of present embodiment preparation shows that film light has produced the material (see figure 1) that contains carbonyl in a large number after shining.
Embodiment 2:
1, the preparation of manganese oxide powder such as embodiment 1.
2, preparation degradable polyethylene film:
1.0g polyethylene masterbatch is dissolved in the hexanaphthene of 50ml, adds 0.01g manganese oxide powder.Stir 3h, manganese oxide is uniformly dispersed in solution, with the solution of this about 20ml, evenly drip on tetrafluoroethylene, the power effect of relying on for support evenly is tiled on this plate, takes off behind the natural air drying, makes the degradable polyethylene film.With the 20W ultraviolet lamp is light source, has compared the film of this law preparation and common polythene film (except that not adding the mineral, other the operates same this law) situation with its quality of light application time, surface group.Experiment shows that the common polythene film is behind UV-irradiation 300h, and quality minimizing value is 4%.And the vinyon that adopts present method to prepare, because the effect of manganese oxide, behind the UV-irradiation 300h, its quality minimizing value brings up to 16%; Infrared spectra behind the polyethylene film UV-irradiation 300h of present embodiment preparation shows that film light has produced the material (see figure 1) that contains carbonyl in a large number after shining.
Embodiment 3:
1, preparation manganese oxide boracic load powder:
Synthesizing of manganese oxide boracic load: with 277g MnCl
24H
2After O is dissolved in the 1907ml deionization, add 893ml36%HAc, continue under the vigorous stirring, be added to the KMnO that contains 0.75mol/L boric acid with the speed of 200ml/min
4Solution (177g KMnO
4Be dissolved in the 2800ml water), after reaction finished, directly suction filtration got mineral precipitation, the precipitate with deionized water repetitive scrubbing, 60C oven dry down, 100 mesh sieves of milling get manganese oxide boracic load powder.
2, preparation degradable polyethylene film:
1.0g polyethylene masterbatch is dissolved in the hexanaphthene of 50ml, adds 0.004g manganese oxide boracic load powder.Stir 3h, powder is uniformly dispersed in solution, with the solution of this about 20ml, evenly drip on tetrafluoroethylene, the power effect of relying on for support evenly is tiled on this plate, takes off behind the natural air drying, makes the degradable polyethylene film.With the 20W ultraviolet lamp is light source, has compared the film of this law preparation and common polythene film (except that not adding the mineral, other the operates same this law) situation with its quality of light application time, surface group.Experiment shows that the common polythene film is behind UV-irradiation 300h, and quality minimizing value is 4%.And the degradable polyethylene plastics film that adopts present method to prepare, because the effect of manganese oxide boracic load, behind the UV-irradiation 300h, its quality minimizing value brings up to 19%; Infrared spectra behind the polyethylene film ultraviolet lighting 300h of present embodiment preparation shows that film light has produced the material (see figure 1) that contains carbonyl in a large number after shining.
Example 4:
1, the preparation of manganese oxide powder such as embodiment 1.
2, preparation degradable polypropylene film:
The 1.0g polypropylene masterbatch is dissolved in the hexanaphthene of 50ml, adds 0.004g manganese oxide powder again.Stir 3h, manganese oxide is uniformly dispersed in solution, with the solution of this about 20ml, evenly drip on tetrafluoroethylene, the power effect of relying on for support evenly is tiled on this plate, takes off behind the natural air drying, makes the degradable polypropylene film.With the 20W ultraviolet lamp is light source, has compared the film and common polythene film (except that not adding the mineral, other the operates same this law) situation with its quality of light application time, molecular weight, surface adsorption species and generation secondary pollution of this law preparation.Experiment shows that ordinary polypropylene film is behind UV-irradiation 300h, and quality minimizing value is 3%.And the polypropylene film that adopts present method to prepare, because the effect of manganese oxide, behind the UV-irradiation 300h, its quality minimizing value brings up to 12%; Infrared spectra behind the polypropylene film ultraviolet lighting 300h of present embodiment preparation shows that film light has produced the material (see figure 2) that contains carbonyl in a large number after shining.
Embodiment 5:
1, manganese oxide boracic load powder preparing such as embodiment 3
2, preparation degradable polypropylene film:
The 1.0g polypropylene masterbatch is dissolved in the hexanaphthene of 50ml, adds 0.004g manganese oxide boracic load powder.Stir 3h, powder is uniformly dispersed in solution, with the solution of this about 20ml, drip on tetrafluoroethylene uniformly, the power effect of relying on for support evenly is tiled on this plate, takes off behind the natural air drying, makes the degradable polypropylene film.With the 20W ultraviolet lamp is light source, has compared the film of this law preparation and ordinary polypropylene film (except that not adding the mineral, other the operates same this law) situation with its quality of light application time, surface group.Experiment shows that ordinary polypropylene film is behind UV-irradiation 300h, and quality minimizing value is 3%.And the photodegradation polyacrylic film that adopts present method to prepare, because the effect of manganese oxide boracic load, behind the UV-irradiation 300h, its quality minimizing value brings up to 21%; Infrared spectra behind the polypropylene film ultraviolet lighting 300h of present embodiment preparation shows that film light has produced the material (see figure 2) that contains carbonyl in a large number after shining.
Claims (1)
1. the preparation method of the polyethylene of a ultraviolet light degradable or polypropylene screen, its step as
(1) 277g MnCl24H20 is dissolved in the 1907ml deionized water after, add 893ml 36%HAc, continue under the vigorous stirring, speed adding concentration with 200ml/min is the KMnO4 solution of 0.4mol/L, after reaction finished, directly suction filtration got mineral precipitation, with mineral precipitation deionized water repetitive scrubbing, 60 ℃ of down oven dry, the 100 order analyses of milling sieve the manganese oxide powder;
(2) 277g MnCl24H2O is dissolved in the 1907ml deionized water after, add 893ml 36%HAc, continue under the vigorous stirring, adding the concentration that contains 0.75mol/L boric acid with the speed of 200ml/min is the KMnO4 solution of 0.4mol/L, after reaction finished, directly suction filtration got mineral precipitation, with this mineral precipitation deionized water repetitive scrubbing, 60 ℃ of down oven dry, the 100 order analyses of milling sieve manganese oxide boracic load powder;
(3) polyethylene or polypropylene are dissolved in the cyclohexane solution, add manganese oxide or manganese oxide boracic load powder then, stir 3h, manganese oxide or manganese oxide boracic load powder are uniformly dispersed in described cyclohexane solution, press mass ratio, manganese oxide or manganese oxide boracic load powder: polyethylene or polypropylene: hexanaphthene is 1: 20～60: 300～800; Obtain polyethylene or polypropylene suspension solution;
(4) polyethylene that step (3) is obtained or polypropylene suspension solution evenly drip on polyfluortetraethylene plate, and the power effect of relying on for support evenly is tiled on this plate, opens behind the natural air drying, promptly makes the polyethylene or the polypropylene screen of ultraviolet light degradable.
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| CN103316712B (en) * | 2013-06-26 | 2014-11-26 | 天津工业大学 | Polypropylene catalytic film for dye degradation and preparation method thereof |
| CN105815855A (en) * | 2016-05-21 | 2016-08-03 | 苏州泽谦纺织有限公司 | Environment-friendly and degradable mosquito-preventing fabric |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405213A (en) * | 2002-11-08 | 2003-03-26 | 清华大学 | Method for preparing ultravoilet catalytic degraded plastic using titanium dioxide as catalyst |
| CN1468895A (en) * | 2002-07-18 | 2004-01-21 | 青岛海洋大学 | Degradable plastic film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1468895A (en) * | 2002-07-18 | 2004-01-21 | 青岛海洋大学 | Degradable plastic film |
| CN1405213A (en) * | 2002-11-08 | 2003-03-26 | 清华大学 | Method for preparing ultravoilet catalytic degraded plastic using titanium dioxide as catalyst |
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Effective date of registration: 20130114 Address after: 11 groups of Wang Yingzhen Su Jia Qiao Cun 445409 Hubei city of Lichuan Province Patentee after: Lichuan Wuzhou Animal Husbandry Co., Ltd. Address before: 430070 Wuhan, Hongshan Province, lion street, No. 1 District, No. Patentee before: Huazhong Agricultural University |
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Granted publication date: 20110420 Termination date: 20171013 |