CN1309145A - Fully degradable multifunctional film - Google Patents
Fully degradable multifunctional film Download PDFInfo
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- CN1309145A CN1309145A CN 00113989 CN00113989A CN1309145A CN 1309145 A CN1309145 A CN 1309145A CN 00113989 CN00113989 CN 00113989 CN 00113989 A CN00113989 A CN 00113989A CN 1309145 A CN1309145 A CN 1309145A
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Abstract
A full-degradable multifunctional film is prepared from superfine modified coal powder, assistant, biodegradation promoter, optical degrading agent, basic resin through mixing at 50-70 deg.C, high-speed stirring for 10-25 min, cooling, extruding out, granulating, and blowing film. Its advantages are controllable degradation speed, low cost and multiple functions including providing fertilizer, herbiciding, sterilizing and increasing yield of crops.
Description
The present invention relates to fully degradable multifunctional film, be specially adapted to do agricultural film.
China's film-mulching cultivation technique is to introduce from Japan in 1978, through experiment and demonstration, is applied rapidly in China.Nineteen eighty-three, the agricultural film area coverage reached 943.7 ten thousand mu, leapt to the No. 1 in the world.Nineteen ninety reaches 5,000 ten thousand mu, and this technology range of application covers from initial vegetables, peanut, cotton, develops into cash crop, as more than 10 fields such as sugar material, tobacco, grains, has obtained positive effect.Since 1984, in order to alleviate the cost of peasant's membrane covering, many manufacturers have manufactured experimently than conventional thinner ultra-thin mulch film, to reducing use cost, enlarge usable floor area and played the effect that promotes, for the agricultural development band of China a good head, for example, China's patent of invention on August 21st, 96 disclosed " the multi-functional controlled starch plastic resin of separating ", its publication number CN1129229A, application number 95117894.6 and on December 9th, 1992 disclosed " plastic sheeting for farm use carbon black and colour batch thereof ", publication number is CN1066862A, application number 92104960.9, on the above-mentioned two patent surfaces near technology, but from fact, with the present invention bigger difference is arranged again, the former is the starch with modification, polyolefine or polyvinyl chloride resin, the light depressant prescription is a main raw material, and degradation rate was 100% in 120 days, the latter be the band look can not degrade still can complete recovery mulch film.These two kinds of mulch film usable floor areas are little, but traditional white agricultural mulching uses in a large number, caused tight person of outstanding talent " white pollution " for the Agro-ecology of China.Along with the continuous attenuate of mulch film, increase the removing of waste mulching film and the difficulty of recovery, residual film is cumulative in the soil, has influenced the growth of farm crop greatly, and makes the underproduction of Soil degradation and farm crop.Therefore, the agricultural mulching that continue to use white not degrade will pollute China farm land and bring serious disaster, and there is the cost height in agricultural mulching at present, can not degrade fully or the accurate defective of control degradation time of degradation speed.
The object of the present invention is to provide the low coloured high-fall accurately fully degradable multifunctional film of control degradation time of separating also of a kind of cost.
The technical scheme that realizes the object of the invention is to solve like this: the composition of fully degradable multifunctional film comprises 3～50 parts of microfine coals through modification, 1～3 part of processing aid, 2～20 parts of biodegradation promotor, 0～3 part of photodegradable aid, 40～94 parts of basic resins, by weight adding modified super-fine cool-ash earlier, add other compositions successively respectively for 50～70 ℃ in temperature, high-speed stirring 10～25 minutes, cooling back twin screw extruder extruding pelletization, promptly make masterbatch or PP Pipe Compound, be processed into film with blow moulding machine.
Above-mentioned said modified super-fine cool-ash is with 2～20 parts of biodegradation promotor, and coupling agent 1-4 part or rare-earth mineral 1-4 part are carried out mechanical-chemical modification with 90～95 parts of coals of≤3 millimeters on ultrafine crusher, and makes the superfine powder of particle diameter≤10 micron; Said base resin mainly comprises natural polymer, graft modified starch, Sumstar 190, microorganism synthesizing polyester, poly(lactic acid), polycaprolactone, polyvinyl alcohol, polyesterification acid amides, polyesterification ether, ethylene acrylic acid co polymer, ethene-acetate ethylene copolymer, new LDPE (film grade), linear low density polyethylene, high density polyethylene(HDPE), modified polyolefin one or more compositions wherein; The photodegradation control agent is meant the title complex and the modified super-fine cool-ash composition of transition metal, and transition metal complex mainly comprises dibutyl dithiocaarbamate iron/nickel dibutyl dithiocarbamate, and the ratio of the two is 28～30: 1～4; Biodegradation promotor is meant nitrogenous, Phosphorus compound or composition mainly comprises urea, Secondary ammonium phosphate, ammonium sulfate, primary ammonium phosphate, vitriolate of tartar, and its ratio is 2～20 parts; Processing aid mainly comprise hard ester acid, aluminium titanium composite coupler, rare-earth mineral, silane coupling agent wherein any one or two or morely use simultaneously.
The present invention compared with prior art, be by mechanical-chemical modification and photodegradation control agent with the low coal resources of cost, biodegradation promotor, co-blended such as resin and processing aid aurification technology makes seriation resin new variety, this whole degrading film has light, the biological degradation synergy, multiple degradation process takes place simultaneously, degradation time is control arbitrarily in 30～180 days, its degraded product has physiological regulatory action to plant, include 12 kinds to the plant-growth effective element, can make ground temperature increase 3～4 ℃, sterilization, getting fat, weeding, improve crop yield 20～40%, degraded product is an a kind of efficient organic composite fertilizer, there is not a difficult problem that soil is produced " white pollution ", product cost is lower than the conventional starch or the characteristics of other non-starch degradable films, by the control production technique, can make 0.08～0.014 millimeter coloured film, be widely used in farming land and approach, refuse bag, multiple products such as handbag.Technical feature of the present invention is listed as follows:
The milpa difference comparison sheet table one that grows
| Sample | Plant height (cm) | The number of sheets (sheet) | Individual plant is fresh weight (g) on the ground | Following five leaf length/width (cm) | Aerial root is given birth to (individual) | Etap | The 20cm stem is thick | Radical (individual) |
| COPO resin mulch film I | ?210 | ?11 | ????950 | ????86/11 | ????12 | Take out hero | ????25 | ????55 |
| COPO resin mulch film II | ?208 | ?11 | ????850 | ????75/12 | ????/ | Take out hero | ????23 | ????54 |
| Common ground film | ?205 | ?11 | ????900 | ????82/11 | ????12 | Take out hero | ????24 | ????45 |
| Contrast | ?135 | ?6 | ????400 | ????75/9 | ????0 | / | ????21 | ????38 |
Blank ground, COPO resin mulch film field covering with plastic film test-results
Table two
| Time | COPO resin mulch film I | COPO resin mulch film II | The common white mulch film |
| April 17 | Covering with plastic film | Covering with plastic film | Covering with plastic film |
| May 29 | Beginning has the crack | Beginning has the crack | Intact |
| June 23 | Irregular macropore (photo 1) | The hole is less relatively | Beginning has ommatidium |
| September 29 | All degradeds are seen minority 1cm fritter under the soil on the soil | All degradeds are seen minority 1cm fritter under the soil on the soil | Substantially do not become |
Performance index table three
| Longitudinal tensile strength, N | Transverse tensile strength.N | Elongation at break, % are vertically/laterally | Vertically right-angle tearing is strong, N | Laterally the right angle fracture is strong, N | Outward appearance/thickness mm | Degradation time, day |
| 3.18 | 2.34 | 454.47/780.0 | 1.2 | 1.52 | Qualified/0.010 | 30-120 |
Below in conjunction with drawings and Examples content of the present invention is described in further detail:
Accompanying drawing is a production scheme of the present invention.
Rich coal resources in China, the kind of coal is also more, and therefore, to the composition of coal, physical and chemical index is analyzed, and according to result of laboratory test raw coal is pulverized then, and its grinding particle size should reach≤3mm.
As shown in the figure, Production Flow Chart follows these steps to carry out:
1. the modified superfine of coal dust, taking by weighing 90-95 part coal dust joins in the ultrafine crusher, add 2-20 part biodegradation promotor again, mechanical-chemical modification is carried out in 1-4 part coupling agent or the superfine grinding together of 1-4 part rare-earth mineral, makes coal and biodegradation promotor with macromolecular structure, coupling agent or rare-earth mineral are together compatible, changed the functional property of coal, made it become a kind of new polymeric components, its superfine grinding coal powder size≤10 μ n.
2. take by weighing the superfine modified coal dust of 3-50 part weight, 40-94 part base resin, 1-3 part processing aid, 0-3 part photodegradation control agent is put into high-speed mixer, under the condition of temperature 50-70 ℃ or 55-65 ℃ high-speed stirring 10-25 minute or 10-15 minute, cool to room temperature then, the granulation of co-blended aurification just obtains whole degrading film masterbatch or PP Pipe Compound in forcing machine, adopts conventional film blowing processing units to be processed into many merits whole degrading film.
3. because the coal resources in China scope distributes wider, the coal kind of each department and composition and physical and chemical index are incomplete same, for the above-mentioned photodegradation control agent and the use of biodegradation promotor, look various places coal kind difference, two kinds of degradation agentss can add simultaneously, also can singly add light control agent falls singly add biodegradation promotor or two kinds do not add, its effect also can reach accurate degradation speed.
Embodiment 1:
Get 95 parts in the fine coal of granularity≤3mm, add 3.5 parts in urea, 1.5 parts of aluminium titanium composite couplers carry out mechanical-chemical modification on ultrafine crusher, and make the modified super-fine cool-ash body of granularity≤10 μ m.Get above-mentioned through 20 parts of modified super-fine cool-ash bodies, 10 parts of ethene-acetate ethylene copolymer resin, 35 parts of linear low density polyethylenes, 23 parts of new LDPE (film grade)s, 10 parts of high density polyethylene(HDPE)s, 2 parts of stearic acid are added in the high-speed mixer, mix in high mixing machine 10 minutes under 60 ℃ of temperature, behind the cool to room temperature, blend granulation in forcing machine obtains the whole degrading film dedicated parent material, adopts conventional film blowing processing units to be processed into the high-fall getting fat mulch film of separating.
Embodiment 2:
Get 95 parts of the coal dusts of granularity≤48 μ m, add 2 parts of rare-earth minerals, 2 parts in urea, 1 part of calcium superphosphate carries out superfine grinding on ultrafine crusher, make granularity≤10 μ m.With 30 parts of above-mentioned microfine coal bodies, add in the high-speed mixer, 60 ℃ of following high-speed stirring of temperature 5 minutes, add 1 part of aluminium titanium coupling agent then, 1 part of silane coupling agent continued high-speed stirring 15 minutes, add 10 parts of starch again, 30 parts of linear low density polyethylenes, 20 parts of new LDPE (film grade)s, 6 parts of high density polyethylene(HDPE)s, 2 parts of stearic acid, 2 parts of photodegradation conditioning agents, high-speed mixing 10 minutes, behind the cool to room temperature, blend granulation in forcing machine obtains the whole degrading film PP Pipe Compound, adopts conventional film blowing processing units to be processed into the high-fall getting fat commentaries on classics light mulch film of separating of control.
Embodiment 3:
Get 90 parts of the coal dusts of granularity≤3mm, add 2 parts of stearic acid, on the ultrafine powder machine, carry out mechanical-chemical modification, and make the modified super-fine cool-ash body of granularity≤10 μ m.Get 10 parts of above-mentioned modified super-fine cool-ash bodies, 0.3 part of dibutyl dithiocaarbamate iron, 0.02 part of nickel dibutyl dithiocarbamate, 10 parts of ethene-acetate ethylene copolymer resin, 45 parts of linear low density polyethylenes, 23 parts of new LDPE (film grade)s, 10 parts of high density polyethylene(HDPE)s, be added in the high-speed mixer, under 60 ℃ of temperature, in high-speed mixer, mixed 10 minutes, behind the cool to room temperature, blend granulation in forcing machine, obtain the whole degrading film dedicated parent material, adopt conventional film blowing processing units to be processed into the high-fall getting fat handbag film of separating.
Embodiment 4
Get 90 parts of the coal dusts of granularity≤3mm, add 1.5 parts of titanate coupling agents, 2 parts of Secondary ammonium phosphates, 1 part of vitriolate of tartar carries out mechanical-chemical modification on the ultrafine powder machine, and makes the modified super-fine cool-ash body of granularity≤10 μ m.10 parts of above-mentioned modified super-fine cool-ash bodies, 10 parts of ethylene acrylic acid co polymers, 15 parts of starch, 45 parts of ethene-acetate ethylene copolymers, 20 parts of modified poly ethylenes, in high-speed mixer, under 60 ℃, in high-speed mixer, mixed 10 minutes, behind the cool to room temperature, extruding pelletization in forcing machine, obtain the whole degrading film PP Pipe Compound, adopt conventional film blowing processing units to be processed into whole degrading film.
Be not difficult to find out by the foregoing description, each embodiment is alternative starch of coal dust or the non-starch composition with modification, thereby reduced the cost of film, the modification coal dust is induced control light, biological degradation synergy as composite assistant here, multiple degradation process takes place simultaneously, contained transistion metal compound is fragrant polynuclear plane composition in the modification coal dust, and the potassium in the coal, calcium, zinc etc. are the required element of biological growth, and its amount is determined by the content of coal.As long as change the content of microfine coal, just can accurately control the degradation time of film in the prescription.Therefore, maximum contribution of the present invention just is to use the abundant in coal resource to add in the prescription as a kind of important composition, and therefore, cost is lower, will obtain better economic and social benefit.
Claims (7)
1. fully degradable multifunctional film, it is characterized in that comprising 3～50 parts of microfine coals, 1～3 part of processing aid, 2～20 parts of biodegradation promotor through modification, 0～3 part of photodegradable aid, 40～94 parts of basic resins by weight adding modified super-fine cool-ash earlier, add other compositions respectively for 50～70 ℃ successively in temperature, high-speed stirring 10～25 minutes, the twin screw extruder extruding pelletization is used in the cooling back, promptly makes masterbatch or PP Pipe Compound, is processed into film with blow moulding machine.
2. fully degradable multifunctional film according to claim 1, it is characterized in that modified super-fine cool-ash is to carry out mechanical-chemical modification with 2-20 part biodegradation promotor, 1-4 part coupling agent or 1-4 part rare-earth mineral and 90～95 parts of coal dusts that are less than or equal to 3 millimeters on ultrafine crusher, and make the powder of particle diameter≤10 micron.
3. fully degradable multifunctional film according to claim 1 is characterized in that base resin comprises natural polymer, graft modified starch, Sumstar 190, microorganism synthesizing polyester, poly(lactic acid), polycaprolactone, polyvinyl alcohol, polyesterification acid amides, polyesterification ether, ethylene acrylic acid co polymer, ethene-acetate ethylene copolymer, new LDPE (film grade), linear low density polyethylene, high density polyethylene(HDPE), modified polyolefin any one or two or more compositions wherein.
4. fully degradable multifunctional film according to claim 1, it is characterized in that the photodegradation control agent is meant the title complex and the modified super-fine cool-ash composition of transition metal, the title complex of transition metal mainly comprises dibutyl dithiocaarbamate iron/nickel dibutyl dithiocarbamate, and the ratio of the two is 28～30: 1～4.
5. fully degradable multifunctional film according to claim 1 is characterized in that biodegradation promotor is meant nitrogenous, Phosphorus compound or composition, mainly comprises urea, Secondary ammonium phosphate, primary ammonium phosphate, ammonium sulfate, vitriolate of tartar, calcium superphosphate.
6. fully degradable multifunctional film according to claim 1, it is characterized in that processing aid mainly comprise hard ester acid, aluminium titanium composite coupler, rare-earth mineral, silane coupling agent wherein any one or two or morely use simultaneously.
7. according to the described multi-functional degradable film of claim, it is characterized in that this film degradation product is to contain the various plants beneficial element, and plant-growth is had the humic acid substance of regulating effect, wherein beneficial element is mainly derived from coal.
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| CN 00113989 CN1107689C (en) | 2000-11-23 | 2000-11-23 | Fully degradable multifunctional film |
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| CN 00113989 CN1107689C (en) | 2000-11-23 | 2000-11-23 | Fully degradable multifunctional film |
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| CN1309145A true CN1309145A (en) | 2001-08-22 |
| CN1107689C CN1107689C (en) | 2003-05-07 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608045B (en) * | 2009-07-10 | 2010-12-29 | 杨凌瑞丰环保科技有限公司 | Controllable light/biodegradation plastic material |
| CN101962306A (en) * | 2010-07-13 | 2011-02-02 | 北京市农林科学院 | Photodegradable mulch resin coated fertilizer and preparation method thereof |
| CN102070890A (en) * | 2010-12-23 | 2011-05-25 | 陕西科技大学 | Light degradation speed-controllable type polycaprolactone and preparation method thereof |
| CN101563405B (en) * | 2006-07-14 | 2012-08-22 | 杜邦泰吉恩胶卷美国有限公司 | Multilayer sealant film |
| CN102775750A (en) * | 2012-08-23 | 2012-11-14 | 胡建平 | Degradable multiband light conversion ground film and preparation method thereof |
| CN102177198B (en) * | 2008-10-14 | 2015-04-08 | 罗迪阿阿克土有限公司 | Biodegradable plastic and use thereof |
| CN107082945A (en) * | 2017-06-12 | 2017-08-22 | 太仓雅奥塑业有限公司 | A kind of environmentally-friendly plastic film |
| CN108260451A (en) * | 2018-01-18 | 2018-07-10 | 浙江大学 | It is a kind of can weeding Biodegradable mulch |
| CN109553941A (en) * | 2018-11-16 | 2019-04-02 | 广东众塑降解材料有限公司 | A kind of biology base full degradation chopsticks material and preparation method thereof |
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2000
- 2000-11-23 CN CN 00113989 patent/CN1107689C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101563405B (en) * | 2006-07-14 | 2012-08-22 | 杜邦泰吉恩胶卷美国有限公司 | Multilayer sealant film |
| CN102177198B (en) * | 2008-10-14 | 2015-04-08 | 罗迪阿阿克土有限公司 | Biodegradable plastic and use thereof |
| US9010338B2 (en) | 2008-10-14 | 2015-04-21 | Solvay Acetow Gmbh | Biodegradable plastic and use thereof |
| CN101608045B (en) * | 2009-07-10 | 2010-12-29 | 杨凌瑞丰环保科技有限公司 | Controllable light/biodegradation plastic material |
| CN101962306A (en) * | 2010-07-13 | 2011-02-02 | 北京市农林科学院 | Photodegradable mulch resin coated fertilizer and preparation method thereof |
| CN101962306B (en) * | 2010-07-13 | 2013-03-06 | 北京市农林科学院 | Photodegradable mulch resin coated fertilizer and preparation method thereof |
| CN102070890A (en) * | 2010-12-23 | 2011-05-25 | 陕西科技大学 | Light degradation speed-controllable type polycaprolactone and preparation method thereof |
| CN102070890B (en) * | 2010-12-23 | 2012-05-23 | 陕西科技大学 | Light degradation speed-controllable type polycaprolactone and preparation method thereof |
| CN102775750A (en) * | 2012-08-23 | 2012-11-14 | 胡建平 | Degradable multiband light conversion ground film and preparation method thereof |
| CN107082945A (en) * | 2017-06-12 | 2017-08-22 | 太仓雅奥塑业有限公司 | A kind of environmentally-friendly plastic film |
| CN108260451A (en) * | 2018-01-18 | 2018-07-10 | 浙江大学 | It is a kind of can weeding Biodegradable mulch |
| CN109553941A (en) * | 2018-11-16 | 2019-04-02 | 广东众塑降解材料有限公司 | A kind of biology base full degradation chopsticks material and preparation method thereof |
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| CN1107689C (en) | 2003-05-07 |
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