CN100447193C - Light-degradable and biodegradable nano antibacterial plastics prepared by using waste plastics and process for preparing same - Google Patents
Light-degradable and biodegradable nano antibacterial plastics prepared by using waste plastics and process for preparing same Download PDFInfo
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Abstract
The present invention relates to controllable photodegradable and biodegradable nanometer bacterium resisting plastics and a preparation method thereof, particularly to controllable photodegradable and biodegradable nanometer bacterium resisting plastics produced by utilizing waste and scrap plastics and a preparation method thereof. In the present invention, controllable photodegradable and biodegradable production and nanometer bacterium resisting production are organically combined together by utilizing the waste and scrap plastics. The present invention has the technical scheme that the controllable photodegradable and biodegradable nanometer bacterium resisting plastics produced by utilizing the waste and scrap plastics is characterized in that the controllable photodegradable and biodegradable nanometer bacterium resisting plastics is mainly prepared from waste and scrap polyethylene plastics, modified nanometer TiO2, modified starch, calcium carbonate and a photosensitizer. The present invention has the advantages that the present invention preparing the controllable photodegradable and biodegradable nanometer bacterium resisting plastics by using the waste and scrap plastics as raw materials solves the problem of environmental pollution caused by the waste and scrap plastics, fully utilizes the waste and scrap plastics to avoid wasting of resources and makes a produced new plastic product have bacterium resistance and double degradability.
Description
Affiliated technical field
The present invention relates to a kind of controlled photo-degradable and bio-degradable nano antiseptic plastic and preparation method, particularly utilize waste or used plastics will produce the waste or used plastics that utilizes that controllable light, bio-degradable, nano-antibacterial organically combine and produce controlled photo-degradable and bio-degradable nano antiseptic plastic and preparation method.
Background technology
Utilize waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic and be meant that polyethylene master batch, antibacterial matrices, biodegradable agglomerate and the organic proportioning of photodegradation master batch of utilizing waste or used plastics to make combine, thereby make the plastics of producing have two degradation properties and germ resistance.The present domestic like product that still do not have.At present the antiseptic-germicide that extensively adopts in the anti-biotic material is a silver-series antibacterial agent, meets light or very easily variable color when preserving though its bactericidal property is high, and from plastics, separate out human body unfavorable.In addition because redox reaction takes place and causes the plastics its colour changed into yellow in the activity of silver easily, though and general silver-bearing copper sterilant bacterium is lost activity, after bacterium killed, corpse can discharge deleterious component, as intracellular toxin.These problems all will be brought bad influence to the application of plastics.Domestic application number are thereby that the preparation method of 99100726.3 biodegradable plastic base material just makes itself and resin compatible make the plastics of producing have biological degradability by treated starch aspect degraded.But because starch content height wherein, in use unavoidable breed bacteria works the mischief to people health.And simple have germ resistance and reduced requirement its degradable performance.To the reclaiming and utilizing waste plastics aspect, though reduced white pollution problems, itself also may pollute.
Summary of the invention
The objective of the invention is provides a kind of waste or used plastics that utilizes to produce controlled photo-degradable and bio-degradable nano antiseptic plastic and preparation method in order to solve the problems of the technologies described above, and the present invention is to starch and nano-TiO
2Carry out modification, developed the plastics that utilize waste or used plastics to produce that biological degradation, photodegradation, nano-antibacterial are organically combined, solved waste or used plastics contaminate environment, wasting problem.
So the present invention is achieved in that the purpose of this invention is to provide and utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic and preparation method to achieve these goals.
The present invention seeks to be achieved through the following technical solutions: a kind of waste or used plastics that utilizes is produced controlled photo-degradable and bio-degradable nano antiseptic plastic, it is characterized in that it mainly is to be made of following compositions: waste polyethylene plastics, modified Nano TiO
2, treated starch, lime carbonate, photosensitizers.
The described waste or used plastics that utilizes is produced controlled photo-degradable and bio-degradable nano antiseptic plastic, and it mainly is made of by ratio of weight and the number of copies following compositions: the waste polyethylene plastics: modified Nano TiO
2: treated starch: lime carbonate: photosensitizers=100～206: 1～34: 10～91: 30～251: 1～40.
The described waste or used plastics that utilizes is produced controlled photo-degradable and bio-degradable nano antiseptic plastic, and it also comprises auxiliary agent, is by ratio of weight and the number of copies: the waste polyethylene plastics: modified Nano TiO
2: treated starch: lime carbonate: photosensitizers, auxiliary agent=100～206: 1～34: 10～91: 30～251: 1～40: 2～70.
Described auxiliary agent is to be made of compatilizer, oxidation inhibitor, and the ratio of weight and number of they and waste polyethylene plastics is: 1～40: 1～30: 100～206.
Described compatilizer is one or more among ethylene waxes, stearic acid, maleic anhydride graft POE, glycerine, the ethylene-vinyl acetate copolymer EVA.
Described photosensitizers can be one or more in dialkyldithiocarbamacompositions iron, iron stearate, ferrocene, the Zinic stearas.
A kind of described preparation method who utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, it comprises following processing step:
Waste polyethylene plastics, treated starch and the lime carbonate of getting 60-80% respectively joins and carries out uniform mixing in the mixing machine, and discharging adds granulation in the forcing machine then, gets the starch biodegradation master batch, and is standby;
Get waste polyethylene plastics, the photosensitizers of 10-20% respectively and put into Nylon Bag, tighten opening, rock, pour extruding pelletization in the forcing machine into after rocking evenly, promptly get the photodegradation master batch, standby;
Get waste polyethylene plastics, the modified Nano TiO of 10-20% respectively
2, put into Nylon Bag, tighten opening, rock, pour extruding pelletization in the forcing machine into after rocking evenly, promptly get antibacterial matrices, standby;
The above-mentioned starch biodegradation master batch for preparing, photodegradation master batch and antibacterial matrices are added the finished product that granulation is in the forcing machine.
Described treated starch prepares by following processing step: earlier starch is put into 100～120 ℃ of baking ovens, dried by the fire 1～10 hour, get 100～200 parts of starch again, put into high-speed mixer, stir for a moment, divide three times then and add 10～40 parts of vinylformic acid, reaction 10～90min adds 1～30 part of coupling agent reaction 10～60min; Add 1～26 part of glycerine, 1～31 part of urea, 1～37 part of stearic acid, 1～29 part of ethylene waxes reaction 5～60min again, 100～120 ℃ of baking ovens are put in discharging, promptly get treated starch.
Described modified Nano TiO
2Prepare by following processing step: open baking oven earlier and be preheating to 110～150 ℃; Take by weighing 100～200 parts of nano-TiOs then
2Put into baking oven baking 1～12 hour, get 0.5～35 part of titanate coupling agent 121; Coupling agent is poured into round-bottomed flask, pour round-bottomed flask into 500～1500ml dehydrated alcohol or acetone again; Put into ultrasonic cleaner, use ultrasonic dispersing 10～80 minutes earlier; Subsequently, nano titanium oxide is slowly added the round bottom beaker, the concussion of limit edged; Use ultrasonic dispersing 1～12 hour down at 50～120 ℃, concussion dispersion limit, limit solvent flashing, after dissolving was by the time volatilized fully, drying was 1～15 hour in 110～150 ℃ baking oven, promptly obtains modified Nano TiO
2
Advantage of the present invention and effect are as follows:
The present invention is that raw material has been made controlled photo-degradable and bio-degradable nano antiseptic plastic with the waste or used plastics, solved the waste or used plastics problem of environment pollution caused, waste or used plastics made full use of avoided the wasting of resources, and make the new plastic goods of producing have antibiotic and two degradation properties.Further specify beneficial effect of the present invention below by test.
We freeze our antibacterial matrices of punching adding in the substratum at beef.And introduce daily bacterium at substratum, carry out antibacterial tests.Observe in the substratum after three days and have only 2% bacterial plaque.This shows that the antibacterial matrices among the present invention has good antimicrobial property.
Find 98% the yeast of having grown in the substratum after three days, black-koji mould.And these two kinds of bacteriums requisite bacterial classification in the biological degradation just.Thereby provable the present invention has found the way that solves in the contradiction of germ resistance and biological degradability.
We introduce daily bacterium in substratum.Put into we with master batch of the present invention make plastic film.Divide two kinds of test methods, a kind ofly put into common incubator.Another kind is put in the incubator that UV-lamp is housed.Weighing plastic film after 15 days.We find that the rate of decomposition in common incubator is 10%-15%.The plastics film rate of decomposition is 20%-30% in the incubator of UV-lamp is housed.This shows that the present invention has good two degradation properties.Germ resistance and two degradation property are two outstanding effects that the present invention has.
Embodiment
Embodiment one
The present invention utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, and it is made of following compositions: waste polyethylene plastics 100g, modified Nano TiO
220g, treated starch 20g, lime carbonate 50g, ferrocene 20g, Zinic stearas 10g.
Its preparation method comprises following processing step:
Get waste polyethylene plastics 80g, treated starch 20g and lime carbonate 50g respectively and join and carry out uniform mixing in the mixing machine, discharging adds granulation in the forcing machine then, the starch biodegradation master batch, standby;
Get waste polyethylene plastics 10g, ferrocene 20g respectively, Zinic stearas 10g puts into Nylon Bag, tightens opening, rocks, and pours extruding pelletization in the forcing machine into after rocking evenly, promptly gets the photodegradation master batch, and is standby;
Get waste polyethylene plastics 10g, modified Nano TiO respectively
220g puts into Nylon Bag, tightens opening, rocks, and pours extruding pelletization in the forcing machine into after rocking evenly, promptly gets antibacterial matrices, and is standby;
The above-mentioned starch biodegradation master batch of purchasing, photodegradation master batch and antibacterial matrices are added the finished product that granulation is in the forcing machine.
Embodiment two
The present invention utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, and it is made of following compositions: waste polyethylene plastics 200g, modified Nano TiO
220g, treated starch 20g, lime carbonate 50g, ferrocene 20g, Zinic stearas 10g.
Its preparation method is with embodiment one.
Embodiment three
The present invention utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, and it is made of following compositions: waste polyethylene plastics 200g, modified Nano TiO
21g, treated starch 10g, lime carbonate 30g, ferrocene 0.4g, iron stearate 0.5g, dialkyldithiocarbamacompositions iron 0.1g.
Its preparation method is with embodiment one.
Embodiment four
The present invention utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, and it is made of following compositions: waste polyethylene plastics 100g, modified Nano TiO
230g, treated starch 90g, lime carbonate 250g, ferrocene 40g.
Its preparation method is with embodiment one.
Embodiment five
The present invention utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, and it is made of following compositions: waste polyethylene plastics 150g, modified Nano TiO
215g, treated starch 50g, lime carbonate 150g, iron stearate 20g.
Its preparation method is with embodiment one.
Embodiment six
The present invention utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, and it is made of following compositions:
Waste polyethylene plastics 150g, modified Nano TiO
215g, treated starch 50g, lime carbonate 150g, ferrocene 12g, iron stearate 10g, maleic anhydride graft POE10g, ethylene-vinyl acetate copolymer EVA10g, ethylene waxes 8g, oxidation inhibitor (1010) 12g, coupling agent 8g.
Get waste polyethylene plastics 100g; Treated starch 50g; Lime carbonate 150g; And auxiliary agent maleic anhydride graft POE 10g, ethylene-vinyl acetate copolymer EVA10g, put into high-speed mixer and react 10～60min and get final product discharging; By the forcing machine granulation, make the starch biodegradation master batch then, standby;
Get waste polyethylene plastics 30g; Iron stearate 10g; Ferrocene 12g; And auxiliary agent oxidation inhibitor 8g, ethylene waxes 5g, put into Nylon Bag, tighten opening, pour granulation in the forcing machine into after rocking evenly, make the photodegradation master batch, standby;
Get waste polyethylene plastics 20g; Nano-TiO
215g; And auxiliary agent oxidation inhibitor 4g, ethylene waxes 8g, coupling agent 3g, put into Nylon Bag, tighten opening, pour granulation in the forcing machine into after rocking evenly, make antibacterial matrices, standby;
The above-mentioned starch biodegradation master batch for preparing, photodegradation master batch and antibacterial matrices are added the finished product that granulation is in the forcing machine.
Treated starch described in the present embodiment prepares by following processing step: earlier starch is put into 100～120 ℃ of baking ovens, dried by the fire 1～10 hour, get baking back starch 100g again, put into high-speed mixer, stir for a moment, divide three times then and add 40g vinylformic acid, reaction 10～90min adds 30g coupling agent reaction 10～60min; Add 26g glycerine, 31g urea, 37g stearic acid, 29g ethylene waxes reaction 5～60min again, 100～120 ℃ of baking ovens are put in discharging, promptly get treated starch.
The described modified Nano TiO of present embodiment
2Prepare by following processing step: open baking oven earlier and be preheating to 110～150 ℃; Take by weighing the 100g nano-TiO then
2Put into baking oven baking 1～12 hour, get 35g titanate coupling agent 121 and pour round-bottomed flask into, pour round-bottomed flask into 500～1500ml dehydrated alcohol or acetone again; Put into ultrasonic cleaner, use ultrasonic dispersing 10～80 minutes earlier; Subsequently, nano titanium oxide is slowly added the round bottom beaker, the concussion of limit edged; Use ultrasonic dispersing 1～12 hour down at 50～120 ℃, concussion dispersion limit, limit solvent flashing, after dissolving was by the time volatilized fully, drying was 1～15 hour in 110～150 ℃ baking oven, promptly obtains modified Nano TiO
2
Embodiment seven
The present invention utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, and it is made of following compositions:
Waste polyethylene plastics 200g, modified Nano TiO
25g, treated starch 15g, lime carbonate 60g, ferrocene 5g, Zinic stearas 8g, dialkyldithiocarbamacompositions iron 5g, maleic anhydride graft POE5g, ethylene waxes 10g, oxidation inhibitor (1010) 20g.
Its preparation method comprises following processing step:
Get waste polyethylene plastics 140g; Treated starch 15g; Lime carbonate 60g; And auxiliary agent maleic anhydride graft POE 5g, put into high-speed mixer and react 10～60min and get final product discharging; By the forcing machine granulation, make the starch biodegradation master batch then, standby;
Get waste polyethylene plastics 20g; Zinic stearas 8g; Ferrocene 5g; Dialkyldithiocarbamacompositions iron 5g; And auxiliary agent oxidation inhibitor 5g, ethylene waxes 4g, put into Nylon Bag, tighten opening, pour granulation in the forcing machine into after rocking evenly, make the photodegradation master batch, standby;
Get waste polyethylene plastics 40g; Nano-TiO
25g; And auxiliary agent oxidation inhibitor 15g, ethylene waxes 6g, put into Nylon Bag, tighten opening, pour granulation in the forcing machine into after rocking evenly, make antibacterial matrices, standby;
The above-mentioned starch biodegradation master batch for preparing, photodegradation master batch and antibacterial matrices are added the finished product that granulation is in the forcing machine.
Treated starch described in the present embodiment prepares by following processing step: starch is put into 100～120 ℃ of baking ovens, dried by the fire 1～10 hour, get baking back starch 200g again, put into high-speed mixer, stir for a moment, divide three times then and add 10g or 30 vinylformic acid, reaction 10～90min adds 1g or 15g coupling agent reaction 10～60min; Add 1g glycerine, 1g urea, 1g stearic acid, 1g ethylene waxes reaction 5～60min again, 100～120 ℃ of baking ovens are put in discharging, promptly get treated starch.
Modified Nano TiO in the present embodiment
2Prepare by following processing step: open baking oven earlier and be preheating to 110～150 ℃; Take by weighing the 200g nano-TiO then
2Put into baking oven baking 1～12 hour, and got 0.5g or 20g titanate coupling agent 121 is poured round-bottomed flask into, pour round-bottomed flask into 500～1500ml dehydrated alcohol or acetone again; Put into ultrasonic cleaner, use ultrasonic dispersing 10～80 minutes earlier; Subsequently, nano titanium oxide is slowly added the round bottom beaker, the concussion of limit edged; Use ultrasonic dispersing 1～12 hour down at 50～120 ℃, concussion dispersion limit, limit solvent flashing, after dissolving was by the time volatilized fully, drying was 1～15 hour in 110～150 ℃ baking oven, promptly obtains modified Nano TiO
2
Embodiment eight
The present invention utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, and it is made of following compositions:
Waste polyethylene plastics 100g, modified Nano TiO
234g, treated starch 91g, lime carbonate 251g, dialkyldithiocarbamacompositions iron 40g, maleic anhydride graft POE15g, ethylene waxes 25g, oxidation inhibitor (1010) 30g.
Its preparation method is with embodiment six.
The used treated starch of present embodiment is to make by following preparation method: add entry, NaCl and W-Gum in the single port bottle, stir into uniform starch milk, regulate PH to 2-6, add mixing acid, keep pH value at 5-9, at room temperature successive reaction does not change up to pH value, washing, drying promptly get treated starch.
Embodiment nine
The present invention utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, and it is made of following compositions:
Waste polyethylene plastics 130g, modified Nano TiO
218g, treated starch 40g, lime carbonate 100g, ferrocene 20g, oxidation inhibitor (1010) 2g.
Its preparation method is with embodiment seven.
Used modified Nano TiO in the present embodiment
2Be to make: in reactor, heat high-boiling point alcohol and active additive and be controlled at 50-100 ℃, add nano-TiO gradually by following preparation method
2, and stir, to react after 2-8 hour, suction filtration, washing, drying, classification make modified Nano TiO
2This is a nano-TiO
2Conventional method of modifying.
Embodiment ten
The present invention utilizes waste or used plastics to produce controlled photo-degradable and bio-degradable nano antiseptic plastic, and it is made of following compositions:
Waste polyethylene plastics 180g, modified Nano TiO
225g, treated starch 80g, lime carbonate 160g, ferrocene 30g, oxidation inhibitor (1010) 24g, ethylene-vinyl acetate copolymer EVA10g, ethylene waxes 10g.
Its preparation method is with embodiment seven.
Claims (9)
1, a kind of controlled photo-degradable and bio-degradable nano antiseptic plastic is characterized in that it mainly is made of by ratio of weight and the number of copies following compositions:
Waste polyethylene plastics: modified Nano TiO
2: treated starch: lime carbonate: photosensitizers=100～206: 1～34: 10～91: 30～251: 1～40.
2, controlled photo-degradable and bio-degradable nano antiseptic plastic according to claim 1 is characterized in that it also comprises auxiliary agent, is by ratio of weight and the number of copies: waste polyethylene plastics: modified Nano TiO
2: treated starch: lime carbonate: photosensitizers: auxiliary agent=100～206: 1～34: 10～91: 30～251: 1～40: 2～70.
3, controlled photo-degradable and bio-degradable nano antiseptic plastic according to claim 2 is characterized in that described auxiliary agent is to be made of compatilizer, oxidation inhibitor, and the ratio of weight and number of they and waste polyethylene plastics is: 1～40: 1～30: 100～206.
4, controlled photo-degradable and bio-degradable nano antiseptic plastic according to claim 3 is characterized in that described compatilizer is one or more among ethylene waxes, stearic acid, maleic anhydride graft POE, glycerine, the ethylene-vinyl acetate copolymer EVA.
5, controlled photo-degradable and bio-degradable nano antiseptic plastic according to claim 1 is characterized in that described photosensitizers is one or more in dialkyldithiocarbamacompositions iron, iron stearate, ferrocene, the Zinic stearas.
6, controlled photo-degradable and bio-degradable nano antiseptic plastic according to claim 1 is characterized in that described modified Nano TiO
2Prepare by following processing step: open baking oven earlier and be preheating to 110～150 ℃; Take by weighing 100～200 parts of nano-TiOs then
2Put into baking oven baking 1～12 hour, get 0.5～35 part of titanate coupling agent 121 and pour round-bottomed flask into, pour round-bottomed flask into 500～1500ml dehydrated alcohol or acetone again; Put into ultrasonic cleaner, use ultrasonic dispersing 10～80 minutes earlier; Subsequently, nano titanium oxide is slowly added the round bottom beaker, the concussion of limit edged; 50～120 ℃ down with ultrasonic dispersing 1～12 hour, the limit concussion disperses the limit solvent flashing, by the time solvent evaporates fully after, in 110～150 ℃ baking oven dry 1～15 hour, promptly obtain modified Nano TiO
2
Treated starch prepares by following processing step: earlier starch is put into 100～120 ℃ of baking ovens, dried by the fire 1～10 hour, get 100～200 parts of starch again, putting into high-speed mixer stirs, divide three times then and add 10～40 parts of vinylformic acid, reaction 10～90min adds 1～30 part of coupling agent reaction 10～60min; Add 1～26 part of glycerine, 1～31 part of urea, 1～37 part of stearic acid, 1～29 part of ethylene waxes reaction 5～60min again, 100～120 ℃ of baking ovens are put in discharging, promptly get treated starch.
7, the preparation method of the described controlled photo-degradable and bio-degradable nano antiseptic plastic of a kind of claim 1, it comprises following processing step:
Waste polyethylene plastics, treated starch and the lime carbonate of getting 60-80% respectively joins and carries out uniform mixing in the mixing machine, and discharging adds granulation in the forcing machine then, gets the starch biodegradation master batch, and is standby;
Get waste polyethylene plastics, the photosensitizers of 10-20% respectively and put into Nylon Bag, tighten opening, rock, pour extruding pelletization in the forcing machine into after rocking evenly, promptly get the photodegradation master batch, standby;
Get waste polyethylene plastics, the modified Nano TiO of 10-20% respectively
2, put into Nylon Bag, tighten opening, rock, pour extruding pelletization in the forcing machine into after rocking evenly, promptly get antibacterial matrices, standby;
Granulation in the above-mentioned starch biodegradation master batch for preparing, photodegradation master batch and the antibacterial matrices adding forcing machine is got product.
8, the preparation method of controlled photo-degradable and bio-degradable nano antiseptic plastic according to claim 7, it is characterized in that described treated starch prepares by following processing step: earlier starch is put into 100～120 ℃ of baking ovens, dried by the fire 1～10 hour, get 100～200 parts of starch again, put into high-speed mixer, stir, divide three times then and add 10～40 parts of vinylformic acid, reaction 10～90min adds 1～30 part of coupling agent reaction 10～60min; Add 1～26 part of glycerine, 1～31 part of urea, 1～37 part of stearic acid, 1～29 part of ethylene waxes reaction 5～60min again, 100～120 ℃ of baking ovens are put in discharging, promptly get treated starch.
9, the preparation method of controlled photo-degradable and bio-degradable nano antiseptic plastic according to claim 7 is characterized in that described modified Nano TiO
2Prepare by following processing step: open baking oven earlier and be preheating to 110～150 ℃; Take by weighing 100～200 parts of nano-TiOs then
2Put into baking oven baking 1～12 hour, get 0.5～35 part of titanate coupling agent 121 and pour round-bottomed flask into, pour round-bottomed flask into 500～1500ml dehydrated alcohol or acetone again; Put into ultrasonic cleaner, use ultrasonic dispersing 10～80 minutes earlier; Subsequently, nano titanium oxide is slowly added the round bottom beaker, the concussion of limit edged; 50～120 ℃ down with ultrasonic dispersing 1～12 hour, the limit concussion disperses the limit solvent flashing, by the time solvent evaporates fully after, in 110～150 ℃ baking oven dry 1～15 hour, promptly obtain modified Nano TiO
2
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| CNB2005100466854A CN100447193C (en) | 2005-06-15 | 2005-06-15 | Light-degradable and biodegradable nano antibacterial plastics prepared by using waste plastics and process for preparing same |
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| CNB2005100466854A CN100447193C (en) | 2005-06-15 | 2005-06-15 | Light-degradable and biodegradable nano antibacterial plastics prepared by using waste plastics and process for preparing same |
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| CN114751089B (en) * | 2022-05-05 | 2023-02-03 | 广东正一包装股份有限公司 | Environment-friendly high-barrier packaging material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1365994A (en) * | 2001-01-18 | 2002-08-28 | 戴锡麒 | Photo- and bio-degradable antibacterial plastics |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1365994A (en) * | 2001-01-18 | 2002-08-28 | 戴锡麒 | Photo- and bio-degradable antibacterial plastics |
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