CN103012928A - Thermal oxidation-biological double degradation plastic film and preparation method thereof - Google Patents
Thermal oxidation-biological double degradation plastic film and preparation method thereof Download PDFInfo
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- CN103012928A CN103012928A CN2012105268559A CN201210526855A CN103012928A CN 103012928 A CN103012928 A CN 103012928A CN 2012105268559 A CN2012105268559 A CN 2012105268559A CN 201210526855 A CN201210526855 A CN 201210526855A CN 103012928 A CN103012928 A CN 103012928A
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Abstract
The invention relates to a thermal oxidation-biological double degradation plastic film and a preparation method thereof. The plastic film comprises a transition metal carboxylate thermal oxidation degradation accelerant and a clay bioactivator, so that the plastic film can accumulate heat in the composting process and can be completely degraded under the action of microorganisms after being discarded. The plastic film is prepared by two steps of pelleting and film blowing. The plastic film is prepared by the following steps: mixing transition metal carboxylate, bioactivator, polyethylene micropowder and oxidized polyethylene wax uniformly according to the ratio; melting, extruding and pelleting; mixing the particles and polyolefin uniformly according to the ratio; and performing blow molding to obtain the thermal oxidation-biological double degradation plastic film. The method has a simple process; the raw materials are cheap and readily available; and production can be performed by the universal plastic film production equipment. The plastic film has excellent mechanical property, can meet the using requirements of daily life and the agricultural field, can be spontaneously degraded in the composting environment, does not need additional energy, is not limited by conditions such as illumination, and is a practical, environment-friendly and degradable plastic film.
Description
Technical field
The present invention relates to a kind of plastics film and manufacture method thereof that degraded can occur in physical environment, be specially
A kind of hot oxygen-biological double degradation plastic film and manufacture method thereof,It belongs to chemical field mainly for the manufacture of series product such as wrapping material, disposable plastic articles for use, agricultural mulchings.
Background technology
As everyone knows, along with the quickening of social rhythm, the application of plastics in people's daily life is more and more extensive, indispensable article in the life that become a reality.Yet the polyolefins plastic construction is highly stable, hard degradation under field conditions (factors), and the use of a large amount of plastics, especially Phthalates has also caused serious pollution to ecotope when offering convenience to people.
The effective ways that reduce the waste plastic pollution are to use degradable plastics.The degradable plastics of research and development mainly contains two kinds at present: biodegradable plastic and photodegradable plastics.The biodegradable plastic that the materials processing by readily biodegradables such as starch, Mierocrystalline celluloses forms has been reported in Chinese patent " full starch-type biodegradable plastic " (200310111110.7), " full degradable additive and full degradable plastic products " (98114170.6) etc., although these class plastics can be by complete biodegradable, have mostly that production technology content is high, expensive, bad mechanical strength and heat-resisting a, shortcoming such as water tolerance is weak.Chinese patent " controllable light/biodegradation plastic material " (200910023271.8), " photodegradation nano-TiO
2The preparation method of-polyethylene composite plastic " (200410060618.3) etc. reported the photodegradable plastics that can issue in sunlight or UV-irradiation third contact of a total solar or lunar eclipse oxidative degradation; these class plastics generally only have the initial stage after discarded to expose in the sun; along with the continuous accumulation of rubbish; gradually by other article landfill; thus lost the photodegradation chance, in addition buried at the very start, can not be by sufficient illumination degrading; therefore, there is the incomplete problem of degraded in this class photodegradable plastics.
After plastics are discarded, landfill, gathering along with Other Waste, can constantly produce heat in the process of compost, if can utilize the heat of these accumulations, promote the plastics thermooxidizing, in the polymkeric substance long-chain, introduce a large amount of oxy radicals, promote the polymeric long splitting of chain, thereby cause follow-up microbiological deterioration, the degradable possibility that provides of plastics will be provided.If in composite plastic, add biologically active agent simultaneously, with the effectively biological degradation of boosting composite plastic.
The present invention is with thermooxidative degradation promotor and biologically active agent and polyolefin base material blend, adopt general polyolefin film blow moulding equipment and technique, prepared a kind of NEW TYPE OF COMPOSITE polyolefin film, it can either be by effective thermal-oxidative degradation, and resistates also is proved effectively biological degradation.
Summary of the invention
The present invention is directed to polyolefins plastics chemical stability strong, hard degradation under the natural condition, the use of a large amount of disposable plastics has brought serious pollution to environment; After common photodegradable plastics film goes out of use, be exposed on the limited time under the irradiate light, palliating degradation degree is limited, and photodegradation resistates molecular weight is still higher, can not satisfy the requirement of microbiological deterioration, belongs to incompletion degradable plastics; Biodegradable plastic film production technology content is high, and is expensive, and bad mechanical strength and heat-resisting, water tolerance are weak etc., have limited the problems such as its environment for use.A kind of hot oxygen-biological double degradation plastic film and manufacture method thereof are provided.
The technical scheme that the present invention takes the problem that will solve is: with thermooxidative degradation promotor and biologically active agent and polyolefin master batch blend, adopt general polyolefin film blow moulding equipment and method, prepare a kind of hot oxygen-biological double degradation plastic film.These goods are after discarding, can utilize the heat that accumulates in the garbage compost process, impel the metal ion in the hot oxygen promotor to form the free radical with strong oxidation capacity by single electron transfer, the attack polymer carbon, promote polyolefinic oxidative degradation, make the oxy radicals such as a large amount of carbonyl of introducing in the polymkeric substance and hydroxyl, for the biological degradation of resistates provides can be by the carbon source of microbial assimilation.In addition, clay class biologically active agent contains abundant trace element as a kind of mineral substance, be seen as natural microbiological culture media, make the plastics film surface microorganism that more easily grows, can improve the biological degradation efficient of plastics film, thereby reach final degradable purpose.Simultaneously, the interpolation of clay also is conducive to improve the mechanical property of general degradable plastic product, can satisfy the requirement that daily life is used.
The present invention is a kind of hot oxygen-biological double degradation plastic film, this plastics film is to contain thermal-oxidative degradation promotor, biologically active agent, polyethylene micropowder and polyethylene oxidized petroleum waves in the polyolefin film, oxidative degradation under the effect of the heat that not only can in composting process, accumulate after it is discarded, and the degraded resistates can be engulfed by microorganism, finally degradable by microorganism.
The mass percent of hot oxygen-biological double degradation plastic film of the present invention consists of: thermal-oxidative degradation promotor 0.5%-1.5%, biologically active agent 0.5%-1.5%, polyethylene micropowder 0.5%-1.5%, polyethylene oxidized petroleum waves 2%-6%, surplus is polyolefine, and wherein thermal-oxidative degradation promotor and biologically active agent total mass content are 1%-3%.
Hot oxygen of the present invention-biological double degradation plastic film preferred mass per-cent consists of: thermal-oxidative degradation promotor 1%, biologically active agent 1%, polyethylene micropowder 1%, polyethylene oxidized petroleum waves 4%, surplus are polyolefine.
In the technical solution of the present invention, described polyolefine refers to polyethylene, polypropylene, polystyrene, wherein one or several combinations.
In the technical solution of the present invention, described thermal-oxidative degradation promotor refers to the transition metal carboxylate salt.
In the technical solution of the present invention, described transition metal carboxylate salt is one or several combinations in carboxylic acid molysite, manganese carboxylate salt, the carboxylic acid calcium salt.
In the technical solution of the present invention, described biologically active agent refers to the clay quasi-mineral.
The making method of hot oxygen-biological double degradation plastic film of the present invention, carry out according to following two step process:
1) prepares hot oxygen-bio-degradable master batch:, thermal-oxidative degradation promotor, biologically active agent, polyolefine micropowder and oxidized polyethlene wax are mixed in proportion, again through melt extruding granulation by claim 2 or 3 described quality of material per-cents;
2) prepare hot oxygen-biological double degradation plastic film: according to thermal-oxidative degradation promotor and biologically active agent total amount for the ratio of the 1%-3% of this plastics total mass with step 1) in the pellet and the polyolefine that make mix, then make hot oxygen-biological double degradation plastic film through the blowing operation.
It is this area multipurpose plants that the present invention prepares the two devices that fall master batch of above-mentioned hot oxygen-biology, such as Double-screw forcing machine, homogenizer, Banbury mixer etc.The device that the present invention prepares above-mentioned hot oxygen-biological double degradation plastic film is the general plastics film blow moulding machine of the art.
Advantage of the present invention is:
(1) this hot oxygen-biological double degradation plastic film main body still is polyolefine, does not add the materials such as starch, Mierocrystalline cellulose, and the satisfactory mechanical property of product can satisfy the basic demand that use in the fields such as daily life and agricultural;
(2) equipment for preparing this hot oxygen-biological double degradation plastic film is multipurpose plant in this area, and production technology is ripe, does not therefore additionally increase production cost;
(3) this hot oxygen-biological double degradation plastic film not only can oxidative degradation under heat energy promotes, and can utilize the mineral element that self contains, make the plastics film surface microorganism that more easily grows, thereby improve the biological degradation efficient of plastics film thermal destruction resistates, thereby reach finally degradable;
(4) this hot oxygen-biological double degradation plastic film can spontaneous degraded in the compost environment after discarded, and not needing additionally provides other energy, and is not subjected to the restriction of the condition such as illumination, has widely using value.
Description of drawings
Fig. 1 is the hot oxygen-biological double degradation plastic film pictorial diagram of embodiment 1 preparation;
Fig. 2-1 is the hot oxygen-biological double degradation plastic film of embodiment 1 preparation and the common hot oxygen of sealed polyethylene plastic
Mechanical property-fracture tensile strength the variation diagram in 30 days of degrading;
Fig. 2-2 is the hot oxygen-biological double degradation plastic film of embodiment 1 preparation and the common hot oxygen of sealed polyethylene plastic
Mechanical property-elongation at break the variation diagram in 30 days of degrading;
Fig. 3-1 is the infrared spectra in the hot oxygen-biological double degradation plastic film thermal-oxidative degradation 30 days of embodiment 1 preparation
Variation diagram;
Fig. 3-2 is the infrared spectra variation diagram in the common sealed polyethylene plastic thermal-oxidative degradation 30 days;
Fig. 4 is the hot oxygen-biological double degradation plastic film of embodiment 1 preparation and common polyethylene film thermal-oxidative degradation carbonyl index comparison diagram after 30 days.
Fig. 5 for real be the hot oxygen-biological double degradation plastic film of example 1 preparation and the biological degradation rate comparison diagram of the common resistates of polyethylene film thermal-oxidative degradation after 30 days.
Embodiment
Further specify hot oxygen of the present invention-biological double degradation plastic film composition, preparation and property below by embodiment.
Hot oxygen-biological double degradation plastic film mass percent consists of the value of appointing in the following ranges among the embodiment: biologically active agent 0.5%-1.5%, thermal-oxidative degradation promotor 0.5%-1.5%, polyolefine micropowder 0.5%-1.5%, polyethylene oxidized petroleum waves 2%-6%, the surplus polyolefine, wherein biologically active agent and thermal-oxidative degradation promotor total amount are 1%-3%.Described polyolefine is to choose any one kind of them in polyethylene, polypropylene and polystyrene or several combinations; Described biologically active agent is selected from the clay quasi-mineral; Described thermal-oxidative degradation promotor is selected from the transition metal carboxylate salt.Therefore content of the present invention is not subjected to the restriction of embodiment.
Hot oxygen-biological double degradation plastic film preparation and property test
1, prepare hot oxygen-bio-degradable master batch: kaolin (Solution on Chemical Reagents in Shanghai company of Chinese Medicine group), manganese carboxylate salt (friend of Gaomi City, Shandong Province and auxiliary agent company limited), polyethylene micropowder (the desirable plastics of Jiangyin Science and Technology Ltd.), oxidized polyethlene wax (Jiangyin City, Jiangsu turns round and look at Shandong wind and synthesizes chemical industry company limited) etc. are in mass ratio for the ratio of 1:1:1:4 mixes in homogenizer, then melting in the Double-screw forcing machine, extruding pelletization.
2, prepare hot oxygen-biological double degradation plastic film: with the degradation master batch that obtains in above-mentioned 1 and linear low density polyethylene particle (Sinopec Central Plains petrochemical complex limited liability company) in mass ratio for the ratio of 7:93 mixes, Blown Film in the plastics film blow moulding machine then.The thickness of gained film is 25 ± 5 μ m, and the quality percentage composition of thermal-oxidative degradation promotor and biologically active agent is 1%.Finished film is seen Fig. 1.
3, the simulation thermal-oxidative degradation of the above-mentioned film that makes experiment: plastics film clip 10 * 10 cm sizes that make are placed in the baking oven, and design temperature is 70 ° of C.After the thermal treatment 8 days, the performance loss of laminated film machinery is serious, and the polyethylene film mechanical property is without considerable change.Fracture tensile strength changes sees Fig. 2-1, and elongation at break changes sees Fig. 2-2.Detect film at 1712cm by Fourier infrared spectrograph
-1Strong carbonyl absorption peak appears in the place, and the prolongation of intensity heat treatment time strengthens gradually, sees Fig. 3-1; And Fourier infrared spectrum figure sees Fig. 3-2 without considerable change before and after the common sealed polyethylene plastic thermal treatment.In order better to characterize polyolefinic degree of oxidation, the carbonyl index calculation result in laminated film and the polyethylene film thermal treatment 30 days, as shown in Figure 4.Laminated film thermal-oxidative degradation 30 rear carbonyl indexes reach 120 %, and the carbonyl index of polyethylene film is about zero.
4, the resistates of thermal-oxidative degradation after 30 days of the above-mentioned film that makes, press the measuring method of the final aerobic biodegradability ability of material in the GBT 19276.2-2003 aqueous medium, biological degradation 60 days, its biological degradation rate can reach 24%, and the biological degradation rate under common sealed polyethylene plastic the same terms only is 6%, sees Fig. 5.
Claims (8)
1. hot oxygen-biological double degradation plastic film, it is characterized in that, this plastics film is to contain thermal-oxidative degradation promotor, biologically active agent, polyethylene micropowder and polyethylene oxidized petroleum waves in the polyolefin film, oxidative degradation under the effect of the heat that not only can in composting process, accumulate after it is discarded, and the degraded resistates can be engulfed by microorganism, finally degradable by microorganism.
2. hot oxygen-biological double degradation plastic film according to claim 1, it is characterized in that, its mass percent consists of: thermal-oxidative degradation promotor 0.5%-1.5%, biologically active agent 0.5%-1.5%, polyethylene micropowder 0.5%-1.5%, polyethylene oxidized petroleum waves 2%-6%, surplus is polyolefine, and wherein thermal-oxidative degradation promotor and biologically active agent total mass content are 1%-3%.
3. hot oxygen-biological double degradation plastic film according to claim 1 is characterized in that, its mass percent consists of: thermal-oxidative degradation promotor 1%, biologically active agent 1%, polyethylene micropowder 1%, polyethylene oxidized petroleum waves 4%, surplus are polyolefine.
4. each described hot oxygen-biological double degradation plastic film is characterized in that according to claim 1-3, and described polyolefine refers to polyethylene, polypropylene, polystyrene, wherein one or several combinations.
5. each described hot oxygen-biological double degradation plastic film is characterized in that according to claim 1-3, and described thermal-oxidative degradation promotor refers to the transition metal carboxylate salt.
6. hot oxygen-biological double degradation plastic film according to claim 5 is characterized in that, described transition metal carboxylate salt is one or several combinations in carboxylic acid molysite, manganese carboxylate salt, the carboxylic acid calcium salt.
7. each described hot oxygen-biological double degradation plastic film is characterized in that according to claim 1-3, and described biologically active agent refers to the clay quasi-mineral.
8. such as the making method of the described hot oxygen-biological double degradation plastic film of claim 1-3, it is characterized in that carrying out according to following two step process:
1) prepares hot oxygen-bio-degradable master batch:, thermal-oxidative degradation promotor, biologically active agent, polyolefine micropowder and oxidized polyethlene wax are mixed in proportion, again through melt extruding granulation by claim 2 or 3 described quality of material per-cents;
2) prepare hot oxygen-biological double degradation plastic film: according to thermal-oxidative degradation promotor and biologically active agent total amount for the ratio of the 1%-3% of this plastics total mass with step 1) in the pellet and the polyolefine that make mix, then make hot oxygen-biological double degradation plastic film through the blowing operation.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277346A (en) * | 2014-09-30 | 2015-01-14 | 苏州博利迈新材料科技有限公司 | Agricultural film with high light transmission and preparation method of agricultural film |
| CN106009207A (en) * | 2016-08-12 | 2016-10-12 | 安徽中杰信息科技有限公司 | Method for producing environmentally digestible plastic by using clay as filling material |
| CN107163369A (en) * | 2017-06-29 | 2017-09-15 | 吉林省农业科学院 | Peanut Special-purpose double-action unifies degradative plastic film |
| CN108137875A (en) * | 2015-08-26 | 2018-06-08 | 塞拉尼斯伊娃高性能聚合物公司 | It is used to form the polymer composition and its compound of melt extrusion film |
| CN109577100A (en) * | 2018-12-18 | 2019-04-05 | 广州泽田餐饮用品实业有限公司 | It is a kind of can photooxidation droping polyethylene leaching membrane paper and the preparation method and application thereof |
| CN110467736A (en) * | 2019-09-18 | 2019-11-19 | 枣阳市东航塑编彩印有限公司 | A kind of biodegradable plastics woven bag production technology |
| CN114058087A (en) * | 2020-08-05 | 2022-02-18 | 纳米及先进材料研发院有限公司 | Master batch composition of environmentally degradable plastic and application thereof |
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| CN101665625A (en) * | 2008-09-03 | 2010-03-10 | 王丽红 | Plastic degrading composition, use of same and plastic and product containing same |
| CN102180617A (en) * | 2010-12-17 | 2011-09-14 | 东莞市川森环保塑料有限公司 | Biodegradable stone paper |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277346A (en) * | 2014-09-30 | 2015-01-14 | 苏州博利迈新材料科技有限公司 | Agricultural film with high light transmission and preparation method of agricultural film |
| CN108137875A (en) * | 2015-08-26 | 2018-06-08 | 塞拉尼斯伊娃高性能聚合物公司 | It is used to form the polymer composition and its compound of melt extrusion film |
| CN108137875B (en) * | 2015-08-26 | 2021-04-27 | 塞拉尼斯伊娃高性能聚合物公司 | Polymer compositions and composites thereof for forming melt-extruded films |
| CN106009207A (en) * | 2016-08-12 | 2016-10-12 | 安徽中杰信息科技有限公司 | Method for producing environmentally digestible plastic by using clay as filling material |
| CN107163369A (en) * | 2017-06-29 | 2017-09-15 | 吉林省农业科学院 | Peanut Special-purpose double-action unifies degradative plastic film |
| CN109577100A (en) * | 2018-12-18 | 2019-04-05 | 广州泽田餐饮用品实业有限公司 | It is a kind of can photooxidation droping polyethylene leaching membrane paper and the preparation method and application thereof |
| CN109577100B (en) * | 2018-12-18 | 2021-08-24 | 广州泽田餐饮用品实业有限公司 | Photooxygenically degradable polyethylene coated paper and preparation method and application thereof |
| CN110467736A (en) * | 2019-09-18 | 2019-11-19 | 枣阳市东航塑编彩印有限公司 | A kind of biodegradable plastics woven bag production technology |
| CN110467736B (en) * | 2019-09-18 | 2021-12-07 | 枣阳市东航塑编彩印有限公司 | Biodegradable plastic woven bag production process |
| CN114058087A (en) * | 2020-08-05 | 2022-02-18 | 纳米及先进材料研发院有限公司 | Master batch composition of environmentally degradable plastic and application thereof |
| CN114058087B (en) * | 2020-08-05 | 2023-03-24 | 纳米及先进材料研发院有限公司 | Master batch composition of environmentally degradable plastic and application thereof |
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Application publication date: 20130403 |