CN100537661C - Preparation of biological degradation resin composite and modified special resin and product forming process - Google Patents
Preparation of biological degradation resin composite and modified special resin and product forming process Download PDFInfo
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- CN100537661C CN100537661C CNB2006100260447A CN200610026044A CN100537661C CN 100537661 C CN100537661 C CN 100537661C CN B2006100260447 A CNB2006100260447 A CN B2006100260447A CN 200610026044 A CN200610026044 A CN 200610026044A CN 100537661 C CN100537661 C CN 100537661C
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Abstract
The present invention relates to compounding of biodegradable polymer of PBS and PLA, and is compound modified biodegradable resin and its preparing and molding process. Through stuffing modification with modified starch and activated inorganic stuffing, special resin material is obtained. The special resin material may be formed in different modes and in different machines, and the product may be used in the temperature range from -20deg.c to 105deg.c and has excellent performance and 90 days biodegrading rate over 90 %.
Description
Technical field
The present invention relates to a kind of Biodegradable resin compound and resin dedicated preparation of modification and moulding process.
Background technology
China's degradable material has roughly experienced following several stages in the exploitation in 20th century:
I) 1970-1980 adds the addition type photolytic research of photosensitizers in the age in the common plastics resin
II) photodegradable plastics is used and the market development in the eighties
III) 1990-1995, two (light/biology) degradative plastics
IV) after nineteen ninety-five, market application, check and the modification of various light/articles of biodegradable plastics material.Do carrier owing to all be unable to do without in these degradable materials of applying, belong to the part degradable material with petroleum resin, remaining a large amount of polyolefine centuries non-degradable in soil, thus cause the destruction symphysis attitude second environmental pollution of Soil structure.So at the end of the nineties, some colleges and universities and R﹠D institution begin to develop Biodegradable Materials.Nowadays, can biodegradable poly(lactic acid), poly-copolyesters such as lactones, poly butylene succinate etc. newly researches and develops successfully, entered accurate batch process period, but because of the difference on expensive and certain performance of price, shortcomings such as the particular requirement of machine-shaping device and complicated process of preparation can't be accepted by market.
Summary of the invention
The objective of the invention is with prepared biological degradation composite modified resin dedicatedly, make disposable tableware, daily tourism supplies, food product pack, shopping bag, refuse bag, hair washing and wash products such as dying daily hollow bottle.It can substitute existing plastic prod, and good use properties is arranged again, can protect environment by complete biodegradable, reduces and pollutes.
Biodegradable resin of the present invention is compound and modification is resin dedicated is become to be grouped into by following weight percent: PBS (poly butylene succinate) 10-73.5%, PLA (poly(lactic acid)) 5-60%, modified starch 5-35%, activated inorganic filler 9-29.85% and interpolation auxiliary agent 0.15-1.5%;
Wherein, modified starch is 100-1000 order starch and Biodegradable resin graft modification; The activated inorganic filler is that the 1200-2000 order is through rare-earth coupling agent activatory lime carbonate and talcum powder; Add auxiliary agent and comprise lubricant paraffin and low-molecular-weight wax, promoting agent stearic acid and thermo-stabilizer calcium stearate.
Compound and modification is resin dedicated when described Biodegradable resin, is become to be grouped into by following weight percent when resin dedicated as injection moulding: PBS (poly butylene succinate) 10-40%, PLA (poly(lactic acid)) 10-60%, modified starch 30-35%, activated inorganic filler 14.75-29.5% and add auxiliary agent 0.15-0.5%.
Compound and modification is resin dedicated when described Biodegradable resin, is become to be grouped into by following weight percent when resin dedicated as blowing: PBS (poly butylene succinate) 50-60%, PLA (poly(lactic acid)) 5-10%, modified starch 15-20%, activated inorganic filler 14-29% and add auxiliary agent 1-1.5%.
Compound and modification is resin dedicated when described Biodegradable resin, is become to be grouped into by following weight percent when resin dedicated as plastic uptake: PBS (poly butylene succinate) 55-73.5%, PLA (poly(lactic acid)) 5-8.5%, modified starch 10-20%, activated inorganic filler 10-20% and add auxiliary agent 1-1.5%.
Compound and modification is resin dedicated when described Biodegradable resin, is become to be grouped into by following weight percent when resin dedicated as hollow: PBS (poly butylene succinate) 40-60%, PLA (poly(lactic acid)) 15-50%, modified starch 5-15%, activated inorganic filler 9-23.5% and add auxiliary agent 1-1.5%.
The preparation system that described various Biodegradable resin is compound and modification is resin dedicated carries out according to following step:
A. fs: preparatory technology
1. PBS, PLA are in air flow dryer dry 3-4 hour, temperature 65-75 ℃;
What 2. will prepare is all kinds of resin dedicated height stirring mixer high speed stirring 1-3 minute, and stirring at low speed 3-5 minute to stirring fully; The temperature of high-speed stirring is controlled at 60-80 ℃, and the temperature of stirring at low speed is controlled at 15-25 ℃.
B. subordinate phase: twin screw granulation process
1. temperature: 120-150 ℃ of die head 160-200 ℃, metering zone 150-190 ℃, fluxing zone 140-180 ℃, feeding section;
2. screw speed: 60-80r/min;
3. main frame electric current: 50-60A;
4. pelletizing mode: water tie rod material
5. pellet dried by the fire in 65-80 ℃ of dryer more than 2 hours, then the blowing packing.
The following describes the product forming process that various Biodegradable resins are compound and modification is resin dedicated.
(1) injection moulding resin dedicated on general injection moulding machine the forming process goods
Injection temperature be 140-185 ℃, injection pressure be during 30-90Mpa, injection moulding speed are-in fast, the cycle is 5-20 second, can be injection molded into disposable tableware (goods such as cutter, fork, spoon, cup, dish, bowl, chopsticks).
(2) blowing resin dedicated on general plastic film blowing machine forming process blown film goods
Blown film temperature: die head 130-140 ℃, threeway 125-130 ℃, 95-100 ℃ of barrel back segment, 100-110 ℃ in barrel stage casing, 110-120 ℃ of barrel leading portion;
Blow-up ratio: 1.5-2.5;
Ratio of drawing: 4-6;
Blown film thickness: 0.04-0.2mm makes goods such as packing film, food bag, refuse bag.
(3) forming process of the resin dedicated goods of plastic uptake
The first step: this resin dedicated elder generation goes out sheet material on the general-purpose plastics film-discharging machine
Slice temperature: 150-165 ℃ of die head 190-200 ℃, metering zone 185-195 ℃, fluxing zone 180-190 ℃, feeding section;
Three roll temperatures: top roll 50-60 ℃, central roll 70-80 ℃, lower roll 40-50 ℃;
Make sheet stock: thickness 0.2-1.2mm, width 450-600mm;
Second step: will go out sheet material and send general plastics sucking moulding to be machined to disposable tableware (goods such as cup, dish, bowl, dish, box).
(4) the resin dedicated machine-shaping on general blow moulding machine of hollow
Extrusion temperature 130-165 ℃, die temperature 20-50 ℃, blow-up ratio are controlled at 1.5-2.5, blowing pressure is controlled at 0.3-0.5MPa, screw speed 40-50r/min, makes the goods such as solution bottle of various moulding.
PBS among the present invention (poly-succinic acid-butanediol), PLA (poly(lactic acid)), graft starch all are the complete biodegradable resins, through the compound and resin dedicated product that produces of modification, imbed in the soil after the use, under anaerobism, water, bacterium, microorganism etc. corrode, progressively become carbonic acid gas and water, finally dissolved by environment.
The present invention with poly(lactic acid), the modification of poly-succinic acid-butanediol resin compounded after, heat resisting temperature is brought up to more than 100 ℃ by 65 ℃, 95 ℃ respectively, has strengthened rigidity simultaneously, has reduced cost.Resin dedicated flexibility of operation is strong, on existing general-purpose plastics equipment, can processing and manufacturing go out various product, its performance can compare favourably with existing plastic prod fully, use temperature is at-20 ℃ to 105 ℃, nontoxic, pollution-free, 90 days biological degradation rates〉90%, cost is low and have a practical and popularizing value.
Embodiment
Describe the present invention in detail below by preferred embodiment, but do not limit the scope of the invention.The ordinary skill of this area is according to content of the present invention, and some nonessential improvement and adjustment to the present invention has done still belong to protection scope of the present invention.
Embodiment 1: the resin dedicated A# prescription of the compound and modification injection moulding of Biodegradable resin is become to be grouped into by following weight percent: PBS 40%, PLA 10%, modified starch 30%, activated inorganic filler 19.85% and add auxiliary agent 0.15%.
Embodiment 2: the resin dedicated B# prescription of the compound and modification injection moulding of Biodegradable resin is become to be grouped into by following weight percent: PBS 25%, PLA 25%, modified starch 35%, activated inorganic filler 14.75% and add auxiliary agent 0.25%.
Embodiment 3: the resin dedicated C# prescription of the compound and modification injection moulding of Biodegradable resin is become to be grouped into by following weight percent: PBS 10%, PLA 60%, activated inorganic filler 29.5%, add auxiliary agent 0.5%.
Embodiment 4: embodiment 1～3 preparation technology that described Biodegradable resin is compound and the modification injection moulding is resin dedicated:
A. fs: preparatory technology
1. PBS, PLA are in air flow dryer dry 3-4 hour, temperature 65-75 ℃;
2. the injection moulding for preparing is resin dedicated height stirring mixer high speed stirring 1-3 minute, stirring at low speed 3-5 minute to stirring fully; The temperature of high-speed stirring is controlled at 60-80 ℃, and the temperature of stirring at low speed is controlled at 15-25 ℃.
B. subordinate phase: twin screw granulation process
1. temperature: 120-130 ℃ of 160 ℃ of die heads, metering zone 140-150 ℃, fluxing zone 130-140 ℃, feeding section;
2. screw speed: 60-80r/min;
3. main frame electric current: 50A;
4. pelletizing mode: water tie rod material
5. pellet dried by the fire in 65-80 ℃ of dryer more than 2 hours, then the blowing packing.
Embodiment 5: the resin dedicated machine-shaping on injection moulding machine of injection moulding
Compound and the resin dedicated machine-shaping on injection moulding machine of modification injection moulding of Biodegradable resin that embodiment 4 is obtained.Injection temperature 140-185 ℃, injection pressure 30-90Mpa, injection moulding speed be in-in fast, shaping cycle is 5-20 second, is injection molded into disposable tableware (goods such as cutter, fork, spoon, cup, dish, bowl, chopsticks).
Adopt the prescription of embodiment 1～3, and the complete processing of embodiment 4 and embodiment 5, the compound and modification injection moulded products of Biodegradable resin obtained.Its physicals, degradation rate, sanitary index are: fusing point 110-115 ℃, melting index 15-25g/10min, tensile strength 30-40Mpa, tensile break strength 35-45Mpa, elongation at break 80-250%, degradation rate〉90% (90 days), sanitary index belong to actual nontoxic level.
Embodiment 6: the resin dedicated A# prescription of the compound and modification blowing of Biodegradable resin is become to be grouped into by following weight percent: PBS 65%, PLA 5%, modified starch 15%, activated inorganic filler 14%, add auxiliary agent 1%.
Embodiment 7: the resin dedicated B# prescription of the compound and modification blowing of Biodegradable resin is become to be grouped into by following weight percent: PBS 65%, PLA 5%, activated inorganic filler 29%, add auxiliary agent 1%.
Embodiment 8: the resin dedicated C# prescription of the compound and modification blowing of Biodegradable resin is become to be grouped into by following weight percent: PBS 50%, PLA 10%, modified starch 20%, activated inorganic filler 18.5%, add auxiliary agent 1.5%.
Embodiment 9: embodiment 6～8 preparation technology that described Biodegradable resin is compound and modification blowing is resin dedicated:
A. fs: preparatory technology
Identical with embodiment 4.
B. subordinate phase: twin screw granulation process
1. temperature: 125-130 ℃ of 170 ℃ of die heads, metering zone 150-160 ℃, fluxing zone 135-145 ℃, feeding section;
2. screw speed: 60-80r/min;
3. main frame electric current: 55A;
4. pelletizing mode: water tie rod material
5. the granulation material dried by the fire in 65-80 ℃ of dryer more than 2 hours, then the blowing packing.
Embodiment 10: blowing resin dedicated on the general-purpose plastics inflation film manufacturing machine blowfilm shaping
Blown film temperature: die head 130-140 ℃, threeway 125-130 ℃, 95-100 ℃ of barrel back segment, 100-110 ℃ in barrel stage casing, 110-120 ℃ of barrel leading portion;
Blow-up ratio: 1.5-2.5;
Ratio of drawing: 4-6;
Blown film thickness: 0.04-0.2mm makes goods such as packing film, food bag, refuse bag.
According to the prescription of embodiment 6～8, and the technology of embodiment 9 and embodiment 10, the compound and modification blowfilm shaping goods of Biodegradable resin obtained.Its physicals, degradation rate, sanitary index are: fusing point 95-135 ℃, melting index 1-2g/10min, tensile strength be vertical/horizontal 21.3/14.8Mpa, tensile break strength 30-40Mpa, elongation at break be vertical/and horizontal 235/480%, degradation rate〉90% (90 days), sanitary index belong to actual nontoxic level.
Embodiment 11: the resin dedicated A# prescription of the compound and modification plastic uptake of Biodegradable resin is become to be grouped into by following weight percent: PBS 73.5%, modified starch 15%, activated inorganic filler 10%, add auxiliary agent 1.5%.
Embodiment 12: the resin dedicated B# prescription of the compound and modification plastic uptake of Biodegradable resin is become to be grouped into by following weight percent: PBS 63.5%, PLA 5%, modified starch 10%, activated inorganic filler 20%, add auxiliary agent 1.5%.
Embodiment 13: the resin dedicated C# prescription of the compound and modification plastic uptake of Biodegradable resin is become to be grouped into by following weight percent: PBS 55%, PLA 8.5%, modified starch 20%, activated inorganic filler 15.5%, add auxiliary agent 1%.
Embodiment 14: embodiment 11～13 preparation technology that described Biodegradable resin is compound and the modification plastic uptake is resin dedicated:
A. fs: preparatory technology
Identical with embodiment 4.
B. subordinate phase: twin screw granulation process
1. temperature: 150-160 ℃ of 200 ℃ of die heads, metering zone 180-190 ℃, fluxing zone 160-175 ℃, feeding section;
2. screw speed: 60-80r/min;
3. main frame electric current: 60A;
4. pelletizing mode: water tie rod material
5. the granulation material dried by the fire in 65-80 ℃ of dryer more than 2 hours, then the blowing packing.
Embodiment 15: the resin dedicated machine-shaping on Packing Machine of plastic uptake
Compound and the resin dedicated machine-shaping on Packing Machine of modification plastic uptake of Biodegradable resin that embodiment 14 is obtained.
The first step: this resin dedicated elder generation goes out sheet material on the general-purpose plastics film-discharging machine
Slice temperature: 190-200 ℃ on a head temperature left side, middle 180-190 ℃, right 190-200 ℃;
Extruder temperature: 150-165 ℃ of metering zone 185-195 ℃, fluxing zone 180-190 ℃, feeding section;
Three roll temperatures: top roll 50-60 ℃, central roll 70-80 ℃, lower roll 40-50 ℃;
Make sheet stock: thickness 0.2-1.2mm, width 450-600mm;
Second step: will go out sheet material and send general full-automatic or semi-automatic plastics sucking moulding to be machined to disposable tableware (goods such as cup, dish, bowl, dish, box).
According to the prescription of embodiment 11～13, and the technology of embodiment 14 and embodiment 15, the compound and modification plastics sucking moulding goods of Biodegradable resin obtained.Its physicals, degradation rate, sanitary index are: fusing point 120-130 ℃, melting index 1.5-3g/10min, tensile strength 30-40Mpa, tensile break strength 26-34Mpa, elongation at break 250-450%, degradation rate〉90% (90 days), sanitary index belong to actual nontoxic level.
Embodiment 16: the resin dedicated A# prescription of the compound and modification hollow of Biodegradable resin is become to be grouped into by following weight percent: PBS 40%, PLA 30%, modified starch 10%, activated inorganic filler 18.5%, add auxiliary agent 1.5%.
Embodiment 17: the resin dedicated B# prescription of the compound and modification hollow of Biodegradable resin is become to be grouped into by following weight percent: PBS 20%, PLA 50%, modified starch 5%, activated inorganic filler 23.5%, add auxiliary agent 1.5%.
Embodiment 18: the resin dedicated C# prescription of the compound and modification hollow of Biodegradable resin is become to be grouped into by following weight percent: PBS 60%, PLA 15%, modified starch 15%, activated inorganic filler 9%, add auxiliary agent 1%.
Embodiment 19: embodiment 16～17 preparation technology that described Biodegradable resin is compound and modification hollow is resin dedicated:
A. fs: preparatory technology
Identical with embodiment 4.
B. subordinate phase: twin screw granulation process
1. temperature: 145-160 ℃ of 195 ℃ of die heads, metering zone 180-190 ℃, fluxing zone 165-180 ℃, feeding section;
2. screw speed: 60-80r/min;
3. main frame electric current: 60A;
4. pelletizing mode: water tie rod material
5. pellet dried by the fire in 65-80 ℃ of dryer more than 2 hours, then the blowing packing.
Embodiment 20: the resin dedicated machine-shaping on general blow moulding machine of hollow
Compound and the resin dedicated machine-shaping on general blow moulding machine of modification hollow of Biodegradable resin that embodiment 19 is obtained.Extrusion temperature 130-165 ℃, die temperature 20-50 ℃, blow-up ratio are controlled at 1.5-2.5, blowing pressure is controlled at 0.3-0.5MPa, screw speed 40-50r/min, makes the goods such as solution bottle of various moulding.
According to the prescription of embodiment 16～18, and the technology of embodiment 19 and embodiment 20, the compound and modification slush molding goods of Biodegradable resin obtained.Its physicals, degradation rate, sanitary index are: fusing point 115-125 ℃, melting index 1-1.5g/10min, tensile strength 25-35Mpa, tensile break strength 30-40Mpa, elongation at break 50-150%, degradation rate〉90% (90 days), sanitary index belong to actual nontoxic level.
Below table one listed the various biological degradations resin dedicated performance of present embodiment preparation, and with the comparison of petroleum resin.
Table one: the resin dedicated and petroleum resin performance comparison sheet of biological degradation
Be not difficult to find out that by comparison sheet the resin dedicated made product of biological degradation can replace the oil plastic prod fully, and is nontoxic, harmless, pollution-free, degraded is complete, and technology adapts to strong, the low market competitiveness that has more of cost.
Claims (13)
1, a kind of biodegradable compound and modified resin, it is characterized in that it is become to be grouped into by following weight percent: poly butylene succinate 10-73.5%, poly(lactic acid) 5-60%, modified starch 5-35%, activated inorganic filler 9-29.85% and interpolation auxiliary agent 0.15-1.5%, wherein said modified starch is the modified starch of 100-1000 order starch and Biodegradable resin graft modification.
2, biodegradable compound and modified resin according to claim 1 is characterized in that it is become to be grouped into by following weight percent: poly butylene succinate 40%, poly(lactic acid) 10%, modified starch 30%, activated inorganic filler 19.85% and interpolation auxiliary agent 0.15%.
3, biodegradable compound and modified resin according to claim 1 is characterized in that described activated inorganic filler is that the 1200-2000 order is through rare-earth coupling agent activatory lime carbonate and talcum powder.
4, biodegradable compound and modified resin according to claim 1 is characterized in that described interpolation auxiliary agent comprises lubricant paraffin and low-molecular-weight wax, promoting agent stearic acid and thermo-stabilizer calcium stearate.
5, according to claim 1,3 or 4 described biodegradable compound and modified resin, it is characterized in that it is as the injection grade resin, become to be grouped into by following weight percent: poly butylene succinate 10-40%, poly(lactic acid) 10-60%, modified starch 5-35%, activated inorganic filler 14.75-29.5% and interpolation auxiliary agent 0.15-0.5%, and the weight percent sum of mentioned component is 100%.
6, according to claim 1,3 or 4 described biodegradable compound and modified resin, it is characterized in that it as the blowing grade resins, become to be grouped into: poly butylene succinate 50-60%, poly(lactic acid) 5-10%, modified starch 15-20%, activated inorganic filler 14-29% and interpolation auxiliary agent 1-1.5% by following weight percent.
7, according to claim 1,3 or 4 described biodegradable compound and modified resin, it is characterized in that it as the plastic uptake grade resins, become to be grouped into: poly butylene succinate 55-73.5%, poly(lactic acid) 5-8.5%, modified starch 10-20%, activated inorganic filler 10-20% and interpolation auxiliary agent 1-1.5% by following weight percent.
8, according to claim 1,3 or 4 described biodegradable compound and modified resin, it is characterized in that it is as the hollow grade resins, become to be grouped into by following weight percent: poly butylene succinate 40-60%, poly(lactic acid) 15-50%, modified starch 5-15%, activated inorganic filler 9-23.5% and interpolation auxiliary agent 1-1.5%, and the weight percent sum of mentioned component is 100%.
9, a kind of each described biodegradable compound and modified resin in the claim 1～4 is made the preparation method of pellet, it is characterized in that it carries out according to following step:
The first, the preparatory stage
1. poly butylene succinate, poly(lactic acid) are in air flow dryer dry 3-4 hour, temperature 65-75 ℃;
2. each described resin in the claim 1～4 for preparing was stirred 1-3 minute in height stirring mixer high speed, stirring at low speed 3-5 minute to stirring fully; The temperature of high-speed stirring is controlled at 60-80 ℃, and the temperature of stirring at low speed is controlled at 15-25 ℃;
The second, the twin screw granulation stage
1. temperature: 120-150 ℃ of die head 160-200 ℃, metering zone 150-190 ℃, fluxing zone 140-180 ℃, feeding section;
2. screw speed: 60-80r/min;
3. main frame electric current: 50-60A;
4. pelletizing mode: water tie rod material;
5. the granulation material dried by the fire in 65-80 ℃ of dryer more than 2 hours, then the blowing packing.
10, the method for the described biodegradable compound and modified resin forming process goods on general injection moulding machine of claim 5, it is characterized in that: injection temperature be 140-185 ℃, injection pressure be during 30-90Mpa, injection moulding speed are-in fast, the cycle is 5-20 second, is injection molded into disposable tableware.
11, the method for the described biodegradable compound and modified resin forming process film on general plastic film blowing machine of claim 6 is characterized in that:
Blown film temperature: die head 130-140 ℃, threeway 125-130 ℃, 95-100 ℃ of barrel back segment, 100-110 ℃ in barrel stage casing, 110-120 ℃ of barrel leading portion;
Blow-up ratio: 1.5-2.5;
Ratio of drawing: 4-6;
Blown film thickness: 0.04-0.2mm makes membrane product.
12, a kind of described biodegradable compound the and modified resin of claim 7 is made the method for forming process goods, it is characterized in that:
The first step: the described resin of claim 7 goes out sheet material earlier on the general-purpose plastics film-discharging machine
Slice temperature: 150-165 ℃ of die head 190-200 ℃, metering zone 185-195 ℃, fluxing zone 180-190 ℃, feeding section;
Three roll temperatures: top roll 50-60 ℃, central roll 70-80 ℃, lower roll 40-50 ℃;
Make sheet stock: thickness 0.2-1.2mm, width 450-600mm;
Second step: will go out sheet material and send general plastics sucking moulding to be machined to disposable tableware.
13, the method for the described biodegradable compound and modified resin forming process goods on general blow moulding machine of claim 8, it is characterized in that: extrusion temperature 130-165 ℃, die temperature 20-50 ℃, blow-up ratio are controlled at 1.5-2.5, blowing pressure is controlled at 0.3-0.5MPa, screw speed 40-50r/min, makes the bottle product of various moulding.
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| CN103709688A (en) * | 2013-12-26 | 2014-04-09 | 安徽聚美生物科技有限公司 | PBS (polybuthylenesuccinate) fully biodegradable material as well as preparation method and application thereof |
| CN105440606A (en) * | 2014-09-02 | 2016-03-30 | 允友成(宿迁)复合新材料有限公司 | Preparation method of fully biodegradable starch/polylactic acid base resin |
| CN104877316A (en) * | 2015-05-13 | 2015-09-02 | 常州龙骏天纯环保科技有限公司 | Polylactic acid composite material sheet for plastic uptake and preparation method of sheet |
| CN104877250A (en) * | 2015-05-22 | 2015-09-02 | 广州石头造环保科技股份有限公司 | Hollow injection-molded environment-friendly high-inorganic filled chopsticks and preparation process thereof |
| CN105199333A (en) * | 2015-09-17 | 2015-12-30 | 苏州新区佳合塑胶有限公司 | Plant-colored highly-filled degradable plastic |
| DE102016107654A1 (en) * | 2016-04-25 | 2017-10-26 | Spc Sunflower Plastic Compound Gmbh | Process for producing a bio-plastic product |
| CN109897230A (en) * | 2019-03-01 | 2019-06-18 | 山东天一生物降解塑业有限公司 | A kind of environment biological degradation plastics masterbatch and preparation method thereof |
| CN110467801A (en) * | 2019-07-25 | 2019-11-19 | 安徽新翔包装材料有限公司 | A kind of environmental-protection fully-degradable material and preparation method thereof |
| CN111363324A (en) * | 2020-03-17 | 2020-07-03 | 田勇 | Biodegradable composite material and product and preparation method thereof |
| CN115304893B (en) * | 2022-08-05 | 2023-02-24 | 上海盛凯塑胶制品有限公司 | Degradable starch-based plastic and preparation method thereof |
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