CN102702577A - Degradable rubber and plastic film with plant peel and shell, fiber, plant powder as raw materials and preparation method thereof - Google Patents
Degradable rubber and plastic film with plant peel and shell, fiber, plant powder as raw materials and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of biodegradable materials, and particularly relates to a degradable rubber and plastic film and a preparation method thereof. The degradable rubber and plastic film with plant peel and shell, fibers, plant powder as raw materials is characterized in that the film is prepared from raw materials of plant peel and shells, plant fibers, plant powder, high-molecular polymer, a compatibilizing plasticizer, and a functional additive; the weight percents of the raw materials are: 5-15% of plant peel and shells, 4-10% of plant fibers, 30-70% of plant powder, 3-7% of high-molecular polymer, 17-40% of compatibilizing plasticizers, and 1-5% of functional additives; the functional additive is any one of or a mixture of any more than two of a smell removing agent, an insect resist agent, a preservative, and a defoamer, and when any more than two of the above are mixed, the ratio is arbitrary. The degradable rubber and plastic film of the invention has rubber and plastic physical and mechanical performance, and comprehensive functions of general rubber and plastics; the degradable rubber and plastic film prepared by the method has the characteristics of low cost and biodegradability.
Description
Technical field
The invention belongs to the biodegradable material technical field, be specifically related to a kind of degradable plastic film and preparation method thereof.
Background technology
With the agricultural plants resource; Process the main raw material(s) that degradation material is used as the substituted for plastic packing articles; Make the agricultural plants material become new alternative petroleum base resource, not only make agricultural plants have new economic worth, improve the economic benefit of agriculture prodn; Minimizing is wasted (like oil) to the use of limited resources, and is to administer the environment " white pollutions that use plastic packing products to bring because of a large amount of.
Saying from the development technique of biodegradable material, is main raw material with natural macromolecular material and polymeric derivative, and producing the degradable material with superplasticity function is the main direction of current biodegradable material research.At present comparatively common has following three types:
1, filled biodegradable starch-plastics: poly research is shown, after the Vilaterm macromolecules degradation becomes molecular weight to be lower than 500 oligopolymer, can be absorbed degraded, have environmental safety preferably by the mikrobe in the soil.Therefore; With starch or degradable high polymer material, add softening agent etc. and be incorporated in the common vinyon; To reach so-called " biological slaking ", be the representative of present filled biodegradable starch-plastics, but reality in most cases; Have only starch to degrade in this type of material, and Vilaterm wherein etc. are what to be difficult to by microbiological degradation under physical environment.China just begins the research of this degradable plastics at the mid-80, and present result shows that the degradative plastics of this filled can not all degrade in physical environment, can not meet the demands on the use properties simultaneously.
2, biodegradable chemosynthesis polyester degradative plastics and mikrobe synthetic degradable polymer: wherein mikrobe synthetic degradable polymer comprises POLYACTIC ACID (PLA), gathers the hydroxyalkyl alcohol ester, gathers (beta-malic acid ester) etc., and the degradable polymer of synthetic comprises Z 150PH (PVA), POLYACTIC ACID (PLA), gathers Alpha-hydroxy acid esters class, polycaprolactone (PCL) etc.In recent years, the most active with the research and development of complete biodegradable plastics in developed country, external degradation products mainly is a complete biodegradable plastics at present, and this will be medium-term and long-term from now on industrial development direction.But this type of degradation material is comparatively complicated because of material preparation process, and tooling cost is high, causes material price expensive, lacks the comprehensive utilization to other renewable resourcess simultaneously, substituted for plastic widely aspect application market.
3, natural polymer subtype: natural macromolecular material and verivate; Like starch, Mierocrystalline cellulose, chitin, general Lu Lan etc.; But the natural polymer plastics owing to exist the direct processing difficulties of material (the general casting method film forming that adopt) more; Film has shortcomings such as weathering resistance is poor, intensity is not high, membranous instability, does not reach the practicability stage so far as yet.
Summary of the invention
The object of the present invention is to provide a kind of is degradable plastic film of raw material and preparation method thereof with plant cot, fiber, plant powder, and the degradable plastic film of this method preparation has low, the biodegradable characteristics again of cost.
For realizing above-mentioned purpose; Technical scheme of the present invention is: with plant cot, fiber, plant powder is the degradable plastic film of raw material, it is characterized in that it is formed by plant cot, vegetable fibre, plant powder, high molecular polymer, increase-volume softening agent and functional aid feedstock production; The shared weight percentage of each raw material is: plant cot 5-15%, vegetable fibre 4-10%, plant powder 30-70%, high molecular polymer 3-7%, increase-volume softening agent 17-40%, functional aid 1-5%;
Described plant cot is the mixing of any one or any more than two kinds (contain two kinds, below identical) in cotton seed hulls, chaff shell, Pericarppium arachidis hypogaeae, maize peel, green soy bean cuticle, the orange peel, and any is any proportioning when mixing more than two kinds;
Described vegetable fibre is any one or any mixing more than two kinds in sisal hemp, straw, tangerine bar, the reed rod, and any is any proportioning when mixing more than two kinds;
Described plant powder is any one or any mixing more than two kinds in Tapioca Starch, Rhizoma amorphophalli powder, sweet potato powder, potato powder, pachyrhizus dry powder, Semen Maydis grit, the dried bean dregs, and any is any proportioning when mixing more than two kinds;
Described high molecular polymer is any one or any mixing more than two kinds in rosin, shellac, guar gum, guttapercha, locust bean gum, Z 150PH, the POLYACTIC ACID, and any is any proportioning when mixing more than two kinds;
Described increase-volume softening agent is any one or any mixing more than two kinds in maleic anhydride, terepthaloyl moietie, citrate, glycerine, polyoxyethylene glycol, W 166, vanay, Triple Pressed Stearic Acid, the single stearic acid glycerine lipoprotein, and any is any proportioning when mixing more than two kinds;
Described functional aid is any one or any mixing more than two kinds in deodorant, insect-proof agent, sanitas, the skimmer, and any is any proportioning when mixing more than two kinds.
Described deodorant is the mixing of any one or two kinds in Schardinger dextrins, the L-xitix, and two kinds is any proportioning when mixing.
Described insect-proof agent is the mixing of any one or two kinds in shiu oil, the desinsection chrysanthemum, and two kinds is any proportioning when mixing.
Described sanitas is the mixing of any one or two kinds in Charantin, the pectin, and two kinds is any proportioning when mixing.
Described skimmer is the mixing of any one or two kinds in polyglycol ether, the dimethyl silicone oil, and two kinds is any proportioning when mixing.
Above-mentioned is the preparation method of the degradable plastic film of raw material with plant cot, fiber, plant powder, it is characterized in that it comprises the steps:
1) raw material is chosen: by the shared weight percentage of each raw material be: plant cot 5-15%, vegetable fibre 4-10%, plant powder 30-70%, high molecular polymer 3-7%, increase-volume softening agent 17-40%, functional aid 1-5%; Choose plant cot, vegetable fibre, plant powder, high molecular polymer, increase-volume softening agent and functional aid raw material, subsequent use;
2) raw materials pretreatment: the plant cot is placed supper micron mill, be crushed to 300 order sieving for standby; Vegetable fibre is placed fiber pulverizer, powder particle diameter to 200 order sieving for standby; Plant powder is placed supper micron mill, be crushed to 500 order sieving for standby; But the increase-volume softening agent is placed the stirred pot of temperature control, under 60-70 ℃ of temperature control, stir 3-5 minute subsequent use;
3) the increase-volume plasticising of plant cot, plant fiber material: 1. selected part increase-volume softening agent from increase-volume softening agent total amount: part increase-volume softening agent is 1 by the weight of plant cot and vegetable fibre and the part by weight of part increase-volume softening agent: 0.7-1: 1, choose; 2. will pass through fragmentation sieve pretreated plant cot, vegetable fibre, place the heat SHR high-speed mixer of interlayer of band, high speed blend under the 900rpm rotating speed, and add part increase-volume softening agent gradually; The blending reaction temperature is 100-110 ℃, and the time is 30 minutes, obtains oily gum pasty state mixture, and is subsequent use;
These process step characteristics are, can promote the abundant swelling of vegetable fibre class material through above-mentioned art breading, and reach 100 ℃ in temperature and begin a large amount of dehydrations later on; The increase-volume softening agent occupies the shared space of water molecules in the original fiber substance; " displacement " goes out the moisture in the material, can increase substantially the processability of fibre composition later on, and therefore can improve the content of fibrous matter in the integral material; Reduce material cost, increase the utilization ratio of discarded plant;
4) high-temperature high-voltage reaction: place mixing machine to mix in plant powder, high molecular polymer, remaining increase-volume softening agent; Again with its (mixture after mixing) deliver to parallel double-screw extrude extrude in the bulking machine expanded; Swelling temperature is 150-200 ℃ [pressure is generally 3～6Mpa (deciding according to expanded requirement)]; Obtain reaction mass, subsequent use;
This process step adopts the processing mode that is different from general degradable material, and its uses is food with extruding bulking machine rather than the common plastics forcing machine carries out modification, kneading, plasticizing to macromolecular materials such as starch in the plant powder; Its reason is that the screw of plastic extruder compression ratio is bigger; Shearing force is bigger in the screw rod transmission process; Temperature-sensitive materials such as starch in the plant powder have bigger destructiveness; And its mold cavity configuration makes in its airtight sleeve and the die cavity and to be difficult for forming bigger saturated vapor pressure, can not make wherein starchy material occur sloughing moisture with the mode of " flash distillation " extruding moment;
And use extrude bulking machine can be so that macromolecular material such as the starch in the plant powder and high molecular polymer together, receive from the indirect heating of machine barrel and material between two screw rods and under the stirring of screw rod and machine barrel, mixing, shearing; Temperature of charge raises, the beginning fusion, and in die cavity, push gradually; The further increasing temperature and pressure of material; Obtain boiling, make the abundant gelatinization sex change of starch in the plant powder, organize further homogenizing; The final instantaneous pressure of from nib, extruding at material discharges rapidly, and free water content sharply evaporates and dewaters.Owing to the hydrogen bond of keeping starch structure is destroyed, moisture is removed, and makes that plant powder is easier under the effect of increase-volume softening agent, combine with high molecular polymer in this technology;
5) with 4) reaction material of step gained places the compound mixing machine of the constant temperature with high, medium and low third gear; Open the compound mixing machine of constant temperature and be adjusted to low speed gear; The oily gum pasty state mixture that in this low speed gear gear, slowly adds the step 3) gained; Mixing temperature is controlled at 70-80 ℃, and mixing time is 5-10 minute; Treat oily gum pasty state mixture add finish after, regulating the compound mixing machine rotating speed of constant temperature is high gear, and the control material temperature rises to 90-120 ℃, this stage mixing time is 2-4 minute; Regulating the compound mixing machine rotating speed of constant temperature is mid ranger, and mixing temperature is controlled at 95-100 ℃, and this stage mixing time is 5-10 minute; At last low speed gear is arrived in the compound mixing machine speed setting of constant temperature, mixing temperature is reduced to below 85 ℃, progressively adds functional aid, and this stage mixing time is 5-15 minute, gets the surperficial butyrous sand shape that has a little and holds material altogether;
The above-mentioned compound mixing machine of constant temperature with high, medium and low third gear, the speed of its high gear is 2400 rev/mins, and the speed of mid ranger is 900 rev/mins, and the speed of low speed gear is 120 rev/mins;
6) treat that above-mentioned sand shape holds when expecting that temperature is reduced to below 40 ℃ altogether, it is immersed in ethanol pond soaked 30-60 minute, deviate from unnecessary oiliness increase-volume softening agent, after material surface ethanol volatilization to be obtained finishes, obtain common appearance material;
7) control the granular material that holds altogether of dry sand: will hold material altogether and send into granulation in common list/twin screw extruder, extrusion temperature is controlled at 120-160 ℃, gets pellet;
8) blowing film forming: at inflation film manufacturing machine or enterprising capable blowfilm shaping of curtain coating unit or casting film-forming, film-forming temperature is controlled at 135-180 ℃ with pellet, and obtaining with plant cot, fiber, plant powder is the degradable plastic film of raw material.
The invention has the beneficial effects as follows: utilize the agricultural plants renewable resources to be main raw material; Through screening and optimizing to natural plant material; It is function modified to adopt physics, biochemical method that screening material is implemented, and makes difference-complementary, acts synergistically, has rubber, the advanced composite material of plastics physical and mechanical properties.Degradable plastic film of the present invention has the comprehensive function of rubber, plastics physical mechanical voltinism ability and ordinary rubber, plastics; Can accomplish biological degradation through microbial process, improve the soil and by rapid absorption.Raw material resources of the present invention are abundant, with low cost; Raw material is taken from agricultural plants, and moulding process all adopts general processing units, is convenient to Industry Promotion and uses.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
With plant cot, fiber, plant powder is the preparation method of the degradable plastic film of raw material, and it comprises the steps:
1) raw material is chosen: by the shared parts by weight of each raw material be: 80 parts of cotton seed hullss, 80 parts in sisal hemp, 550 parts of potato powders, 50 parts of Z 150PH, increase-volume softening agent 220 parts of (100 parts of glycerine, 20 parts of maleic anhydrides, 100 parts of polyoxyethylene glycol (PEG-400)), 20 parts of functional aids (3 parts of dimethyl silicone oils, 1 part of shiu oil, 1 part of Charantin, 15 parts of beta-cyclodextrins); Choose raw material, subsequent use;
2) raw materials pretreatment: cotton seed hulls is placed supper micron mill, be crushed to 300 order sieving for standby; Sisal hemp is placed fiber pulverizer, powder particle diameter to 200 order sieving for standby; The dried potato piece is placed supper micron mill, be crushed to 500 order sieving for standby; With glycerine, maleic anhydride, polyoxyethylene glycol (PEG-400) but place the stirred pot of temperature control, under 65 ℃ of temperature controls, stir 4 minutes subsequent use;
3) the increase-volume plasticising of plant cot, plant fiber material: pretreated cotton seed hulls, sisal hemp are placed successively the SHR-300L high-speed mixer of being with the interlayer of heating; High speed blend under the 900rpm rotating speed; And add 150 parts increase-volume softening agent gradually, and the blending reaction temperature is 110 ℃, the time is 30 minutes; Obtain oily gum pasty state mixture, subsequent use;
4) high-temperature high-voltage reaction: place mixing machine to mix in potato powder, Z 150PH, remaining 70 parts of increase-volume softening agent; Again with its (mixture after mixing) deliver to parallel double-screw extrude extrude in the bulking machine expanded; Swelling temperature is 180 ℃ [pressure is generally 3～6Mpa (deciding according to expanded requirement)]; Obtain reaction mass, subsequent use;
5) with 4) reaction material of step gained places the compound mixing machine of the constant temperature with high, medium and low third gear; Open mixing machine and be adjusted to low speed gear; In this speed stage, slowly add the oily gum pasty state mixture of step 3) gained, mixing temperature is controlled at 75 ℃, and mixing time is 5 minutes; Treat oily gum pasty state mixture add finish after, regulating the mixing machine rotating speed is high gear, and the control material temperature rises to 110 ℃, this stage mixing time is 3 minutes; Regulate the mixing machine rotating speed this moment is mid ranger, and mixing temperature is controlled at 98 ℃, and this stage mixing time is 10 minutes; At last with the mixing machine speed setting to low speed gear, mixing temperature is reduced to below 85 ℃, progressively adds dimethyl silicone oil, shiu oil, Charantin, beta-cyclodextrin, this stage mixing time is 12 minutes, obtains the surface and has a little the butyrous sand shape and hold material altogether;
The above-mentioned compound mixing machine of constant temperature with high, medium and low third gear, the speed of its high gear is 2400 rev/mins, and the speed of mid ranger is 900 rev/mins, and the speed of low speed gear is 120 rev/mins;
6) treat that above-mentioned sand shape holds when expecting that temperature is reduced to below 40 ℃ altogether, it is immersed in ethanol pond soaked 30 minutes, deviate from unnecessary oiliness increase-volume softening agent; After material surface ethanol volatilization to be obtained finishes, obtain common appearance material;
7) control the granular material that holds altogether of dry sand, will hold material altogether and send into granulation in the common single screw extrusion machine, extrusion temperature is controlled at 140 ℃, gets pellet;
8) blowing film forming: pellet is carried out blowfilm shaping on inflation film manufacturing machine, film-forming temperature is controlled at 140 ℃, and obtaining with plant cot, fiber, plant powder is the degradable plastic film of raw material.
The advantage that adopts " mixing machine of high, medium and low third gear (promptly three kinds mixing velocity and time) " to bring: the mixing machine of certain limit speed is the preparation technology of inapplicable this material also; Because: through too much grade blend, three primary stages of having accomplished material prepn: sex change, preplasticizing reach altogether to be held: the initial stage cooperates at a high speed the sex change of atarting material under the effect of shearing force by force to material in the comparatively high temps scope in mixing machine; After rd-is accomplished, under the constant temperature material is carried out preplasticizing and handle; The formation of the common appearance system that the period of relatively low temperature reaches.The three phases of material goes forward one by one continuously; Certain controllability is arranged processing condition but process sequence does not possess reversibility; In the third gear mixing machine, can rely on the rotating speed of whisking appliance to come relevant conditions suitable such as period, temperature, and in the mixing machine of single shelves speed, can't realize above-mentioned technological process.
Employing is carried out blend, dehydration (step 3) with the increase-volume softening agent with plant cot, vegetable fibre under 100-110 ℃ of environment; Be to promote the abundant swelling of vegetable fibre class material; Can increase substantially the processability of fibre composition; Therefore and can improve the content of fibrous matter in the integral material, and reduce material cost, increase the utilization ratio of discarded plant.
For making fully sex change, the plasticising in follow-up third gear mixing machine of fiber substance and plant powder material, being total to and holding [step 5)]; Need first behavior vegetable fibre class material that enough increase-volume softening agent are provided, suitable ratio is: the part by weight of the weight of plant cot and vegetable fibre and increase-volume softening agent is 1: 0.7-1: 1 [step 3)].And the too much increase-volume softening agent of introducing thus also brings a drawback, causes that promptly follow-up blown film product surface returns oily phenomenon.Therefore need unnecessary increase-volume softening agent; Like glycerine, Ucar 35, terepthaloyl moietie etc., the common Rong Tihou at material formation sand shape removes [step 6)] with the ethanol rinsing; Consequent ethanolic soln can regularly separate through baby tower, recycle.
One, according to GB/T 1040-2006, GB/T 16578-1996 check, the tensile strength of the degradable plastic film that the detection present embodiment obtains (laterally, vertically), elongation at break (laterally, vertically), tear strength index such as table 1:
Table 1
(annotate: the NO:20090226 survey report that Hubei Province product quality supervision and inspection research institute provides is taken from above-mentioned detection).
Two, the degradable plastic film that present embodiment is got carries out biodegradable test: according to GB/T 19275-2003-8.2 check, the degradable plastic film that present embodiment gets is potential biolysis and disintegration ability assessment under microbial process.
Test strain: black mold AS 3.5487, penicillium funiculosum AS 3.3875, wooden mould AS 3.4005, ball hair shell AS 3.4254 intends mycin AS 3.2762, Pseudomonas aeruginosa AS 1.1129.
Test condition: culture temperature: 29 ± 1 ℃,
Incubation time: 2007.11.05～12.19,
Style size: 30.0mm,
Sterilising method and solution: sample is immersed in 1min in 70% ethanolic soln, 45 ℃ of following dry 4h,
Experimental technique: method A mycologic test; Method B bacteria test,
Test parameter: the range estimation outward appearance, quality change,
Test result: fungal growth experiment: riotous growth, cover whole specimen surface,
Quality change situation (fungi/bacterium): combine together with agar, sample is by fungi/degradation by bacteria,
Test result: fungi is grow prolifically on sample, covers whole specimen surface, and its growth rank reaches 5 grades, and Pseudomonas aeruginosa AS 1.1129 has raised growth at sample surfaces, and naked eyes are visible.Interpret sample can provide nutritive substance for mikrobe, is degraded by microorganisms.So the degradable plastic film that present embodiment gets has biodegradable characteristics.
(annotate: this testing data is reported NO:SHFD0071106113FD from the censorship SGS test report that degradable plastic film passed through).
Three, degradable plastic film products and marketing like product (Biodegradable starch resin) performance comparison that gets of present embodiment is seen table 2.
Table 2
(annotate: press GB/T-1040-2006, GB/T 16578-1996 test, Biodegradable starch resin parameter is from the GB prediction scheme).
Explain that the degradable plastic film that present embodiment gets has " comprehensive functions of rubber, plastics physical mechanical voltinism ability and ordinary rubber, plastics ".
Embodiment 2:
With plant cot, fiber, plant powder is the preparation method of the degradable plastic film of raw material, and it comprises the steps:
1) raw material is chosen: by the shared parts by weight of each raw material be: 50 parts of Pericarppium arachidis hypogaeaes, 50 parts on chaff shell, 100 parts of straw, 500 parts of Rhizoma amorphophalli powders, high molecular polymer 40 parts of (30 parts of guar gums, 10 parts of POLYACTIC ACIDs), increase-volume softening agent 250 parts of (30 parts of citrates, (600) 20 parts of W 166s, 200 parts of terepthaloyl moietie), 10 parts of functional aids (4 parts of polyglycol ethers (polyoxyethylene nonylphenol TX-4), 1 part of pectin, 2 parts of L-xitix, 3 parts of desinsection chrysanthemums); Choose raw material, subsequent use;
2) raw materials pretreatment: Pericarppium arachidis hypogaeae, chaff shell are placed supper micron mill, be crushed to 300 order sieving for standby; Straw is placed fiber pulverizer, powder particle diameter to 200 order sieving for standby; Dried konjaku piece is placed supper micron mill, be crushed to 500 order sieving for standby; With citrate, W 166 (600) but, terepthaloyl moietie places the stirred pot of temperature control, under 70 ℃ of temperature controls, stir 4 minutes subsequent use;
3) the increase-volume plasticising of plant cot, plant fiber material: pretreated Pericarppium arachidis hypogaeae, chaff shell, straw are placed the SHR-300L high-speed mixer of being with the interlayer of heating; High speed blend under the 900rpm rotating speed; And add 180 parts increase-volume softening agent gradually, and the blending reaction temperature is 110 ℃, the time is 30 minutes; Obtain oily gum pasty state mixture, subsequent use;
4) high-temperature high-voltage reaction: place mixing machine to mix in Rhizoma amorphophalli powder, guar gum, POLYACTIC ACID, remaining 70 parts of increase-volume softening agent; Again with its deliver to parallel double-screw extrude extrude in the bulking machine expanded; Swelling temperature is 190 ℃ [pressure is generally 3～6Mpa (deciding according to expanded requirement)]; Get reaction mass, subsequent use;
5) with 4) reaction material of step gained places the compound mixing machine of the constant temperature with high, medium and low third gear; Open mixing machine and be adjusted to low speed gear; In this speed stage, slowly add the oily gum pasty state mixture of step 3) gained, mixing temperature is controlled at 75 ℃, and mixing time is 5 minutes; Treat oily gum pasty state mixture add finish after, regulating the mixing machine rotating speed is high gear, and the control material temperature rises to 115 ℃, this stage mixing time is 2.5 minutes; Regulate the mixing machine rotating speed this moment is mid ranger, and mixing temperature is controlled at 90 ℃, and this stage mixing time is 10 minutes; At last low speed gear is arrived in the mixing machine speed setting; Mixing temperature is reduced to below 85 ℃; Progressively add polyglycol ether (polyoxyethylene nonylphenol TX-4), pectin, L-xitix, desinsection chrysanthemum, this stage mixing time is 10 minutes, gets the surperficial butyrous sand shape that has a little and holds material altogether;
The above-mentioned compound mixing machine of constant temperature with high, medium and low third gear, the speed of its high gear is 2400 rev/mins, and the speed of mid ranger is 900 rev/mins, and the speed of low speed gear is 120 rev/mins;
6) treat that above-mentioned sand shape holds when expecting that temperature is reduced to below 40 ℃ altogether, it is immersed in ethanol pond soaked 30 minutes, deviate from unnecessary oiliness increase-volume softening agent; After material surface ethanol volatilization to be obtained finishes, obtain common appearance material;
7) control the granular material that holds altogether of dry sand, will hold material altogether and send into granulation in the common single screw extrusion machine, extrusion temperature is controlled at 140 ℃, gets pellet;
8) blowing film forming: pellet is carried out blowfilm shaping on inflation film manufacturing machine, film-forming temperature is controlled at 140 ℃, and obtaining with plant cot, fiber, plant powder is the degradable plastic film of raw material.
Embodiment 3:
With plant cot, fiber, plant powder is the preparation method of the degradable plastic film of raw material, and it comprises the steps:
1) raw material is chosen: by the shared parts by weight of each raw material be: 100 parts of green soy bean cuticles, 100 parts of straw, 500 parts of Rhizoma amorphophalli powders, high molecular polymer 40 parts of (30 parts of guar gums, 10 parts of POLYACTIC ACIDs), increase-volume softening agent 250 parts of (30 parts of citrates, (600) 20 parts of W 166s, 200 parts of terepthaloyl moietie), 10 parts of functional aids (4 parts of polyglycol ethers (polyoxyethylene nonylphenol TX-4), 1 part of pectin, 2 parts of L-xitix, 3 parts of desinsection chrysanthemums); Choose plant cot, vegetable fibre, plant powder, high molecular polymer, increase-volume softening agent and functional aid raw material, subsequent use;
2) raw materials pretreatment: the green soy bean cuticle is placed supper micron mill, be crushed to 300 order sieving for standby; Straw is placed fiber pulverizer, powder particle diameter to 200 order sieving for standby; Dried konjaku piece is placed supper micron mill, be crushed to 500 order sieving for standby; With citrate, W 166 (600) but, terepthaloyl moietie places the stirred pot of temperature control, under 70 ℃ of temperature controls, stir 4 minutes subsequent use;
3) the increase-volume plasticising of plant cot, plant fiber material: pretreated green soy bean cuticle, straw are placed the SHR high-speed mixer of being with the interlayer of heating, high speed blend under the 900rpm rotating speed, and add 180 parts increase-volume softening agent gradually.The blending reaction temperature is 110 ℃, and the time is 30 minutes, gets oily gum pasty state mixture, and is subsequent use;
4) high-temperature high-voltage reaction: place mixing machine to mix in Rhizoma amorphophalli powder, guar gum, polylactic acid poly, remaining 70 parts of increase-volume softening agent; Again with its deliver to 65 type parallel double-screws extrude extrude in the bulking machine expanded; Swelling temperature is 180 ℃, gets reaction mass, and is subsequent use;
5) with 4) reaction material of step gained places the compound mixing machine of the constant temperature with high, medium and low third gear; Open mixing machine and be adjusted to low speed gear; In this speed stage, slowly add the oily gum pasty state mixture of step 3) gained, mixing temperature is controlled at 75 ℃, and mixing time is 5 minutes; Treat oily gum pasty state mixture add finish after, regulating the mixing machine rotating speed is high gear, and the control material temperature rises to 110 ℃, this stage mixing time is 4 minutes; Regulate the mixing machine rotating speed this moment is mid ranger, and mixing temperature is controlled at 95 ℃, and this stage mixing time is 10 minutes; At last low speed gear is arrived in the mixing machine speed setting; Mixing temperature is reduced to below 85 ℃; Progressively add polyglycol ether (polyoxyethylene nonylphenol TX-4), pectin, L-xitix, desinsection chrysanthemum, this stage mixing time is 10 minutes, gets the surperficial butyrous sand shape that has a little and holds material altogether;
The above-mentioned compound mixing machine of constant temperature with high, medium and low third gear, the speed of its high gear is 2400 rev/mins, and the speed of mid ranger is 900 rev/mins, and the speed of low speed gear is 120 rev/mins;
6) treat that above-mentioned sand shape holds when expecting that temperature is reduced to below 40 ℃ altogether, it is immersed in ethanol pond soaked 30 minutes, deviate from unnecessary oiliness increase-volume softening agent; After material surface ethanol volatilization to be obtained finishes, obtain common appearance material;
7) control the granular material that holds altogether of dry sand, will hold material altogether and send into granulation in the common single screw extrusion machine, extrusion temperature is controlled at 140 ℃, gets pellet;
8) blowing film forming: at the enterprising capable casting film-forming of curtain coating unit, film-forming temperature is controlled at 140 ℃ with pellet, and obtaining with plant cot, fiber, plant powder is the degradable plastic film of raw material.
Embodiment 4:
With plant cot, fiber, plant powder is the preparation method of the degradable plastic film of raw material, and it comprises the steps:
1) raw material is chosen: by the shared parts by weight of each raw material be: 100 parts of orange peel, 100 parts of straw, 500 parts of Tapioca Starchs, high molecular polymer 40 parts of (30 parts of guar gums, 10 parts of POLYACTIC ACIDs), increase-volume softening agent 250 parts of (30 parts of citrates, (600) 20 parts of W 166s, 200 parts of terepthaloyl moietie), 10 parts of functional aids (4 parts of polyglycol ethers (polyoxyethylene nonylphenol TX-4), 1 part of pectin, 2 parts of L-xitix, 3 parts of desinsection chrysanthemums); Choose raw material, subsequent use;
2) raw materials pretreatment: orange peel is placed supper micron mill, be crushed to 300 order sieving for standby; Straw is placed fiber pulverizer, powder particle diameter to 200 order sieving for standby; Dried cassava is placed supper micron mill, be crushed to 500 order sieving for standby; With citrate, W 166 (600) but, terepthaloyl moietie places the stirred pot of temperature control, under 70 ℃ of temperature controls, stir 4 minutes subsequent use;
3) the increase-volume plasticising of plant cot, plant fiber material: pretreated orange peel, straw are placed the SHR high-speed mixer of being with the interlayer of heating, high speed blend under the 900rpm rotating speed, and add 170 parts increase-volume softening agent gradually.The blending reaction temperature is 100-110 ℃, and the time is 30 minutes, gets oily gum pasty state mixture, and is subsequent use;
4) high-temperature high-voltage reaction: place mixing machine to mix in Rhizoma amorphophalli powder, guar gum, polylactic acid poly, remaining 80 parts of increase-volume softening agent; Again with its deliver to parallel double-screw extrude extrude in the bulking machine expanded; Swelling temperature is 175 ℃, gets reaction mass, and is subsequent use;
5) with 4) reaction material of step gained places the compound mixing machine of the constant temperature with high, medium and low third gear; Open mixing machine and be adjusted to low speed gear; In this speed stage, slowly add the oily gum pasty state mixture of step 3) gained, mixing temperature is controlled at 75 ℃, and mixing time is 5 minutes; Treat oily gum pasty state mixture add finish after, regulating the mixing machine rotating speed is high gear, and the control material temperature rises to 115 ℃, this stage mixing time is 2.5 minutes; Regulate the mixing machine rotating speed this moment is mid ranger, and mixing temperature is controlled at 90 ℃, and this stage mixing time is 10 minutes; At last low speed gear is arrived in the mixing machine speed setting; Mixing temperature is reduced to below 85 ℃; Progressively add polyglycol ether (polyoxyethylene nonylphenol TX-4), pectin, L-xitix, desinsection chrysanthemum, this stage mixing time is 10 minutes, gets the surperficial butyrous sand shape that has a little and holds material altogether.
The above-mentioned compound mixing machine of constant temperature with high, medium and low third gear, the speed of its high gear is 2400 rev/mins, and the speed of mid ranger is 900 rev/mins, and the speed of low speed gear is 120 rev/mins;
6) treat that above-mentioned sand shape holds when expecting that temperature is reduced to below 40 ℃ altogether, it is immersed in ethanol pond soaked 30 minutes, deviate from unnecessary oiliness increase-volume softening agent; After material surface ethanol volatilization to be obtained finishes, obtain common appearance material;
7) control the granular material that holds altogether of dry sand, will hold material altogether and send into granulation in the common single screw extrusion machine, extrusion temperature is controlled at 140 ℃, gets pellet;
8) blowing film forming: at the enterprising capable casting film-forming of curtain coating unit, film-forming temperature is controlled at 140 ℃ with pellet, and obtaining with plant cot, fiber, plant powder is the degradable plastic film of raw material.
Embodiment 5:
With plant cot, fiber, plant powder is the preparation method of the degradable plastic film of raw material, and it comprises the steps:
1) raw material is chosen: by the shared parts by weight of each raw material be: 50 parts of Pericarppium arachidis hypogaeaes, 50 parts on chaff shell, 50 parts on tangerine bar, 50 parts of reed rods, 500 parts of Rhizoma amorphophalli powders, high molecular polymer 40 parts of (30 parts of guar gums, 10 parts of POLYACTIC ACIDs), increase-volume softening agent 250 parts of (30 parts of citrates, (600) 20 parts of W 166s, 200 parts of terepthaloyl moietie), 10 parts of functional aids (4 parts of polyglycol ethers (polyoxyethylene nonylphenol TX-4), 1 part of pectin, 2 parts of L-xitix, 3 parts of desinsection chrysanthemums); Choose raw material, subsequent use;
2) raw materials pretreatment: Pericarppium arachidis hypogaeae, chaff shell are placed supper micron mill, be crushed to 300 order sieving for standby; Tangerine bar, reed rod are placed fiber pulverizer, powder particle diameter to 200 order sieving for standby; Dried konjaku piece is placed supper micron mill, be crushed to 500 order sieving for standby; With citrate, W 166 (600) but, terepthaloyl moietie places the stirred pot of temperature control, under 70 ℃ of temperature controls, stir 4 minutes subsequent use;
3) the increase-volume plasticising of plant cot, plant fiber material: pretreated Pericarppium arachidis hypogaeae, chaff shell, stalk, reed are placed the SHR high-speed mixer of being with the interlayer of heating, high speed blend under the 900rpm rotating speed, and add 180 parts increase-volume softening agent gradually.The blending reaction temperature is 110 ℃, and the time is 30 minutes, gets oily gum pasty state mixture, and is subsequent use;
4) high-temperature high-voltage reaction: place mixing machine to mix in Rhizoma amorphophalli powder, guar gum, POLYACTIC ACID, remaining 70 parts of increase-volume softening agent, again it is delivered to parallel double-screw and extrude and extrude expandedly in the bulking machine, swelling temperature is 180 ℃, reaction mass, subsequent use;
5) with 4) reaction material of step gained places the compound mixing machine of the constant temperature with high, medium and low third gear; Open mixing machine and be adjusted to low speed gear; In this speed stage, slowly add the oily gum pasty state mixture of step 3) gained, mixing temperature is controlled at 75 ℃, and mixing time is 5 minutes; Treat oily gum pasty state mixture add finish after, regulating the mixing machine rotating speed is high gear, and the control material temperature rises to 115 ℃, this stage mixing time is 2.5 minutes; Regulate the mixing machine rotating speed this moment is mid ranger, and mixing temperature is controlled at 90 ℃, and this stage mixing time is 10 minutes; At last low speed gear is arrived in the mixing machine speed setting; Mixing temperature is reduced to below 85 ℃; Progressively add polyglycol ether (polyoxyethylene nonylphenol TX-4), pectin, L-xitix, desinsection chrysanthemum, this stage mixing time is 10 minutes, gets the surperficial butyrous sand shape that has a little and holds material altogether;
The above-mentioned compound mixing machine of constant temperature with high, medium and low third gear, the speed of its high gear is 2400 rev/mins, and the speed of mid ranger is 900 rev/mins, and the speed of low speed gear is 120 rev/mins;
6) treat that above-mentioned sand shape holds when expecting that temperature is reduced to below 40 ℃ altogether, it is immersed in ethanol pond soaked 30 minutes, deviate from unnecessary oiliness increase-volume softening agent; After material surface ethanol volatilization to be obtained finishes, obtain common appearance material;
7) control the granular material that holds altogether of dry sand, will hold material altogether and send into granulation in the common single screw extrusion machine, extrusion temperature is controlled at 140 ℃, gets pellet;
8) blowing film forming: at inflation film manufacturing machine or enterprising capable blowfilm shaping of curtain coating unit or casting film-forming, film-forming temperature is controlled at 140 ℃ with pellet, and obtaining with plant cot, fiber, plant powder is the degradable plastic film of raw material.
Embodiment 6:
With plant cot, fiber, plant powder is the preparation method of the degradable plastic film of raw material, and it comprises the steps:
1) raw material is chosen: by the shared parts by weight of each raw material be: 50 parts of Pericarppium arachidis hypogaeaes, 50 parts on chaff shell, 100 parts of straw, 200 parts of Tapioca Starchs, 200 parts of sweet potato powder, 100 parts in pachyrhizus dry powder, high molecular polymer 40 parts of (30 parts of guar gums, 10 parts of POLYACTIC ACIDs), increase-volume softening agent 250 parts of (30 parts of citrates, (600) 20 parts of W 166s, 200 parts of terepthaloyl moietie), 10 parts of functional aids (4 parts of polyglycol ethers (polyoxyethylene nonylphenol TX-4), 1 part of pectin, 2 parts of L-xitix, 3 parts of desinsection chrysanthemums); Choose raw material, subsequent use;
2) raw materials pretreatment: Pericarppium arachidis hypogaeae, chaff shell are placed supper micron mill, be crushed to 300 order sieving for standby; Straw is placed fiber pulverizer, powder particle diameter to 200 order sieving for standby; Dried cassava piece, Ipomoea batatas piece, sweet potato pieces are placed supper micron mill, be crushed to 500 order sieving for standby; With citrate, W 166 (600) but, terepthaloyl moietie places the stirred pot of temperature control, under 70 ℃ of temperature controls, stir 4 minutes subsequent use;
3) the increase-volume plasticising of plant cot, plant fiber material: pretreated Pericarppium arachidis hypogaeae, chaff shell, straw are placed the SHR high-speed mixer of being with the interlayer of heating, high speed blend under the 900rpm rotating speed, and add 180 parts increase-volume softening agent gradually.The blending reaction temperature is 100-110 ℃, and the time is 30 minutes, gets oily gum pasty state mixture, and is subsequent use;
4) high-temperature high-voltage reaction: place mixing machine to mix in Tapioca Starch, sweet potato powder, tapioca flour, guar gum, polylactic acid poly, remaining 70 parts of increase-volume softening agent; Again with its deliver to parallel double-screw extrude extrude in the bulking machine expanded; Swelling temperature is 190 ℃, gets reaction mass, and is subsequent use;
5) with 4) reaction material of step gained places the compound mixing machine of the constant temperature with high, medium and low third gear; Open mixing machine and be adjusted to low speed gear; In this speed stage, slowly add the oily gum pasty state mixture of step 3) gained, mixing temperature is controlled at 75 ℃, and mixing time is 5 minutes; Treat oily gum pasty state mixture add finish after, regulating the mixing machine rotating speed is high gear, and the control material temperature rises to 115 ℃, this stage mixing time is 2.5 minutes; Regulate the mixing machine rotating speed this moment is mid ranger, and mixing temperature is controlled at 90 ℃, and this stage mixing time is 10 minutes; At last low speed gear is arrived in the mixing machine speed setting; Mixing temperature is reduced to below 85 ℃; Progressively add polyglycol ether (polyoxyethylene nonylphenol TX-4), pectin, L-xitix, desinsection chrysanthemum, this stage mixing time is 10 minutes, gets the surperficial butyrous sand shape that has a little and holds material altogether;
The above-mentioned compound mixing machine of constant temperature with high, medium and low third gear, the speed of its high gear is 2400 rev/mins, and the speed of mid ranger is 900 rev/mins, and the speed of low speed gear is 120 rev/mins;
6) treat that above-mentioned sand shape holds when expecting that temperature is reduced to below 40 ℃ altogether, it is immersed in ethanol pond soaked 30 minutes, deviate from unnecessary oiliness increase-volume softening agent; After material surface ethanol volatilization to be obtained finishes, obtain common appearance material;
7) control the granular material that holds altogether of dry sand, will hold material altogether and send into granulation in the common single screw extrusion machine, extrusion temperature is controlled at 140 ℃, gets pellet;
8) blowing film forming: at inflation film manufacturing machine or enterprising capable blowfilm shaping of curtain coating unit or casting film-forming, film-forming temperature is controlled at 140 ℃ with pellet, and obtaining with plant cot, fiber, plant powder is the degradable plastic film of raw material.
Each cited raw material of the present invention can both be realized the present invention; And the bound value of each raw material, interval value can both realize the present invention; The bound value and the interval value of processing parameter of the present invention (like temperature, time etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (6)
1. be the degradable plastic film of raw material with plant cot, fiber, plant powder, it is characterized in that it is formed by plant cot, vegetable fibre, plant powder, high molecular polymer, increase-volume softening agent and functional aid feedstock production; The shared weight percentage of each raw material is: plant cot 5-15%, vegetable fibre 4-10%, plant powder 30-70%, high molecular polymer 3-7%, increase-volume softening agent 17-40%, functional aid 1-5%;
Described plant cot is any one or any mixing more than two kinds in cotton seed hulls, chaff shell, Pericarppium arachidis hypogaeae, maize peel, green soy bean cuticle, the orange peel, and any is any proportioning when mixing more than two kinds;
Described vegetable fibre is any one or any mixing more than two kinds in sisal hemp, straw, tangerine bar, the reed rod, and any is any proportioning when mixing more than two kinds;
Described plant powder is any one or any mixing more than two kinds in Tapioca Starch, Rhizoma amorphophalli powder, sweet potato powder, potato powder, pachyrhizus dry powder, Semen Maydis grit, the dried bean dregs, and any is any proportioning when mixing more than two kinds;
Described high molecular polymer is any one or any mixing more than two kinds in rosin, shellac, guar gum, guttapercha, locust bean gum, Z 150PH, the POLYACTIC ACID, and any is any proportioning when mixing more than two kinds;
Described increase-volume softening agent is any one or any mixing more than two kinds in maleic anhydride, terepthaloyl moietie, citrate, glycerine, polyoxyethylene glycol, W 166, vanay, Triple Pressed Stearic Acid, the single stearic acid glycerine lipoprotein, and any is any proportioning when mixing more than two kinds;
Described functional aid is any one or any mixing more than two kinds in deodorant, insect-proof agent, sanitas, the skimmer, and any is any proportioning when mixing more than two kinds.
2. according to claim 1 is the degradable plastic film of raw material with plant cot, fiber, plant powder, it is characterized in that: described deodorant is the mixing of any one or two kinds in Schardinger dextrins, the L-xitix, and two kinds is any proportioning when mixing.
3. according to claim 2 is the degradable plastic film of raw material with plant cot, fiber, plant powder, it is characterized in that: described insect-proof agent is the mixing of any one or two kinds in shiu oil, the desinsection chrysanthemum, and two kinds is any proportioning when mixing.
4. according to claim 2 is the degradable plastic film of raw material with plant cot, fiber, plant powder, it is characterized in that: described sanitas is the mixing of any one or two kinds in Charantin, the pectin, and two kinds is any proportioning when mixing.
5. according to claim 2 is the degradable plastic film of raw material with plant cot, fiber, plant powder; It is characterized in that: described skimmer is the mixing of any one or two kinds in polyglycol ether, the dimethyl silicone oil, and two kinds is any proportioning when mixing.
6. as claimed in claim 1 is the preparation method of the degradable plastic film of raw material with plant cot, fiber, plant powder, it is characterized in that it comprises the steps:
1) raw material is chosen: by the shared weight percentage of each raw material be: plant cot 5-15%, vegetable fibre 4-10%, plant powder 30-70%, high molecular polymer 3-7%, increase-volume softening agent 17-40%, functional aid 1-5%; Choose plant cot, vegetable fibre, plant powder, high molecular polymer, increase-volume softening agent and functional aid raw material, subsequent use;
2) raw materials pretreatment: the plant cot is placed supper micron mill, be crushed to 300 order sieving for standby; Vegetable fibre is placed fiber pulverizer, powder particle diameter to 200 order sieving for standby; Plant powder is placed supper micron mill, be crushed to 500 order sieving for standby; But the increase-volume softening agent is placed the stirred pot of temperature control, under 60-70 ℃ of temperature control, stir 3-5 minute subsequent use;
3) the increase-volume plasticising of plant cot, plant fiber material: 1. selected part increase-volume softening agent from increase-volume softening agent total amount: part increase-volume softening agent is 1 by the weight of plant cot and vegetable fibre and the part by weight of part increase-volume softening agent: 0.7-1: 1, choose; 2. will pass through fragmentation sieve pretreated plant cot, vegetable fibre, place the heat SHR high-speed mixer of interlayer of band, high speed blend under the 900rpm rotating speed, and add part increase-volume softening agent gradually; The blending reaction temperature is 100-110 ℃, and the time is 30 minutes, obtains oily gum pasty state mixture, and is subsequent use;
4) high-temperature high-voltage reaction: place mixing machine to mix in plant powder, high molecular polymer, remaining increase-volume softening agent, again it is delivered to parallel double-screw and extrude and extrude expandedly in the bulking machine, swelling temperature is 150-200 ℃, obtains reaction mass, and is subsequent use;
5) with 4) reaction material of step gained places the compound mixing machine of the constant temperature with high, medium and low third gear; Open the compound mixing machine of constant temperature and be adjusted to low speed gear; The oily gum pasty state mixture that in this low speed gear gear, slowly adds the step 3) gained; Mixing temperature is controlled at 70-80 ℃, and mixing time is 5-10 minute; Treat oily gum pasty state mixture add finish after, regulating the compound mixing machine rotating speed of constant temperature is high gear, and the control material temperature rises to 90-120 ℃, this stage mixing time is 2-4 minute; Regulating the compound mixing machine rotating speed of constant temperature is mid ranger, and mixing temperature is controlled at 95-100 ℃, and this stage mixing time is 5-10 minute; At last low speed gear is arrived in the compound mixing machine speed setting of constant temperature, mixing temperature is reduced to below 85 ℃, progressively adds functional aid, and this stage mixing time is 5-15 minute, gets sand shape and holds material altogether;
6) treat that above-mentioned sand shape holds when expecting that temperature is reduced to below 40 ℃ altogether, it is immersed in ethanol pond soaked 30-60 minute, deviate from unnecessary oiliness increase-volume softening agent, after material surface ethanol volatilization to be obtained finishes, obtain common appearance material;
7) control the granular material that holds altogether of dry sand: will hold material altogether and send into granulation in common list/twin screw extruder, extrusion temperature is controlled at 120-160 ℃, gets pellet;
8) blowing film forming: at inflation film manufacturing machine or enterprising capable blowfilm shaping of curtain coating unit or casting film-forming, film-forming temperature is controlled at 135-180 ℃ with pellet, and obtaining with plant cot, fiber, plant powder is the degradable plastic film of raw material.7. according to claim 6 is the preparation method of the degradable plastic film of raw material with plant cot, fiber, plant powder; It is characterized in that: the said compound mixing machine of constant temperature with high, medium and low third gear; The speed of its high gear is 2400 rev/mins; The speed of mid ranger is 900 rev/mins, and the speed of low speed gear is 120 rev/mins.
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| CN102634072A (en) * | 2012-04-20 | 2012-08-15 | 桂中宇 | Degradable thermoplastic rubber membrane using agricultural plant resources as main material and preparation method of degradable thermoplastic rubber membrane |
| CN104974382A (en) * | 2015-03-29 | 2015-10-14 | 安徽松泰包装材料有限公司 | Environment-friendly packaging material used in food packaging |
| CN104987540A (en) * | 2015-07-09 | 2015-10-21 | 苏笑海 | Biomass-based thermoplastic elastic master batch and preparation method thereof |
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| CN102634072A (en) * | 2012-04-20 | 2012-08-15 | 桂中宇 | Degradable thermoplastic rubber membrane using agricultural plant resources as main material and preparation method of degradable thermoplastic rubber membrane |
| CN104974382A (en) * | 2015-03-29 | 2015-10-14 | 安徽松泰包装材料有限公司 | Environment-friendly packaging material used in food packaging |
| CN104987540A (en) * | 2015-07-09 | 2015-10-21 | 苏笑海 | Biomass-based thermoplastic elastic master batch and preparation method thereof |
| CN105714616A (en) * | 2016-01-30 | 2016-06-29 | 常州市君成机械有限公司 | Preparing method of antibacterial dampproof formaldehyde-free hat rack article shelving fiber board |
| CN106810894A (en) * | 2017-03-06 | 2017-06-09 | 合肥智慧龙图腾知识产权股份有限公司 | A kind of degradable ornament materials and preparation method thereof |
| CN107383913A (en) * | 2017-07-28 | 2017-11-24 | 南京工业大学 | The method that Wood-plastic material is prepared using bean dregs |
| CN109197283A (en) * | 2018-09-08 | 2019-01-15 | 佛山市森昂生物科技有限公司 | A kind of preparation method of degradable water conservation mulch |
| CN110358269A (en) * | 2019-07-31 | 2019-10-22 | 广东美的厨房电器制造有限公司 | Electric elements plastics composite, plastics and its preparation method and application and electric elements |
| CN112358658A (en) * | 2020-11-20 | 2021-02-12 | 山东兴泉油脂有限公司 | Biodegradable master batch based on peanut shell fibers and preparation method and application thereof |
| CN113802270A (en) * | 2021-09-06 | 2021-12-17 | 佛山市意创纺织有限公司 | Manufacturing method for degradable plant raw material non-woven fabric production |
| CN114573997A (en) * | 2022-03-04 | 2022-06-03 | 雄县鑫盛达塑料包装有限公司 | Reed-based biodegradable film and preparation method thereof |
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