CN101798409B - Environmental-friendly plastic additive and preparation method thereof - Google Patents

Environmental-friendly plastic additive and preparation method thereof Download PDF

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CN101798409B
CN101798409B CN2009100069078A CN200910006907A CN101798409B CN 101798409 B CN101798409 B CN 101798409B CN 2009100069078 A CN2009100069078 A CN 2009100069078A CN 200910006907 A CN200910006907 A CN 200910006907A CN 101798409 B CN101798409 B CN 101798409B
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周金树
胡文祥
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Abstract

The invention provides an environmental-friendly plastic additive which contains 1) low-density polyethylene, 2) nano-calcium carbonate, 3) sarin, 4) high-density polyethylene, 5) lubricant, 6) modified starch, 7) low-temperature thermal oxidant, 8) antistatic agent, 9) microorganism preparation, 10) polypropylene and 11) glycerol or propanediol. The invention also provides a preparation method of the environmental-friendly plastic additive and environmental-friendly plastics containing the additive. The plastic products containing the environmental-friendly plastic additive emit toxic gas with low concentration when being burnt so as not to cause air pollution, and can be decomposed by biological degradation after being buried for one year. Furthermore, the environmental-friendly plastic additive can be formed by jetting or extruding technology according to the actual need, and has simple manufacturing technique and strong practicability.

Description

A kind of environmental-friendly plastic additive and preparation method thereof
Technical field
The present invention relates to a kind of environmental-friendly plastic additive and preparation method thereof, belong to chemical field.
Background technology
As everyone knows; Fast development along with twentieth century petrochemical industry after the middle period; Plastic material has become most important material in people's daily life; Like the shell of plastics bag, plastic cup, most of electrical home appliances, footwear material, tableware, raincoat, plastic sheeting for farm use, packing film, container, stationery, leisure goods, household supplies etc. all is plastics, so plastic material is real inseparable with daily life, but the shortcoming of plastic material maximum is the processing of its waste; If use the mode of burying, its characteristic of not changing in thousand will make decline to a great extent the working life of landfill; If the use incineration process then can produce dioxin, HCN, HF, CO, SO because of plastics after burning 2Deng toxic gas, not only can make the air quality variation of incinerator periphery or cause Greenhouse effect, point out that more on evidence it possibly cause serious HUMAN HEALTH problems such as the pregnant woman miscarries, lung cancer; In recent years, because the air pollution problems inherent that incinerator causes causes many serious fight incidents, the difficulty and the crisis of the offal treatment of outstanding more plastics are badly in need of solving.At present, the emission standard of incineration process toxic gas often adopts the ABD-0031 test specification to carry out, and it was a standard with 4 minutes combustion times; Its code requirement is that the emission concentration of HF must be less than 100ppm; The emission concentration of HCl must be less than 150ppm, and the emission concentration of HCN must be less than 150ppm, SO 2Emission concentration must be less than 100ppm, NO XEmission concentration must be less than 100ppm, the emission concentration of CO must be less than 3500ppm.Become people's problem of needs solution day by day so satisfy the plastics of above incineration standard.
Summary of the invention
The present invention's one purpose provides a kind of environmental-friendly plastic additive, and when this additive was added to plastics, these plastics had eco-friendly advantage.
Another purpose of the present invention provides the preparation method of this environmental-friendly plastic additive.
One aspect of the present invention provides a kind of environmental-friendly plastic additive, and this additive contains 1) new LDPE (film grade), 2) nano-calcium carbonate, 3) sarin resin, 4) high density polyethylene(HDPE), 5) lubricant, 6) modified starch, 7) low thermal oxidation agent, 8) static inhibitor, 9) microbial preparation, 10) Vestolen PP 7052 and 11) glycerine or Ucar 35.Described additive can be used for any plastics; Like the shell of plastics bag, plastic cup, electrical home appliances, footwear material, tableware, raincoat, plastic sheeting for farm use, packing film, container, stationery etc.; And make these plastics have eco-friendly advantage; That is: the emission standard after the burning adopts the ABD-0031 test specification to carry out, and various exhaust gas discharging concentration are all within standard; After burying in soil, the plastics that contain above additive can in 1 year, degrade.
Preferably, described additive contains the microbial preparation of its gross weight 1-5%.
Preferably, described microbial preparation is citrobacter freundii (latin name Citrobacterfreundii), stenotrophomonas maltophilia (latin name Stenotrophomonas maltophilia), dead rice sprout spore bacillus (latin name Bacillus vallismortis), acinetobacter calcoaceticus (latin name Acinetobacter calcoaceticus), pseudomonas (latin name Pseudomonassp.), Pseudomonas oleovorans (latin name Pseudomonas oleovorans), Erwinia (latin name Erwinia rhapontici), bacillus pumilis (latin name Curtobacteriumcitreum), Bacillus subtilus (latin name Bacillus subtilis) and Bacillus licheniformis (latin name Bacillus licheniformis).The microbial preparation of being made up of above 10 kinds of bacterial classifications is available from the limited commercial firm of Japanese CORONA, and the said firm is positioned at Tokyo, Japan three hawk cities.After the environmental-friendly plastic additive that contains microbial preparation adds plastics, can be so that the depleted plastics when in soil, burying, ferment when suitable sunlight, humidity, temperature.This microbial preparation can play the effect of eliminating the waste plastic goods with after natural wild bacterium combines, and when burning, plastics are easy to incinerate.
Preferably, described additive contains its gross weight 1) new LDPE (film grade), 2 of 1-10%) nano-calcium carbonate, 3 of 1-12%) the sarin resin, 4 of 1-2%) high density polyethylene(HDPE), 5 of 1-10%) lubricant, 6 of 1-5%) modified starch, 7 of 1-16%) the low thermal oxidation agent, 8 of 1-6%) static inhibitor, 9 of 1-4%) microbial preparation, 10 of 1-5%) Vestolen PP 7052 and 11 of 1-20%) glycerine or the Ucar 35 of surplus.Low thermal oxidation agent in the environmental-friendly plastic additive is novel prodegradant, the environmental protection plastic products that adds this low thermal oxidation agent in storage and transportation and use, stable performance, with after then can degrade rapidly.The equal colorless and odorless of glycerine and Ucar 35 all can be as the raw material of plastics.
Preferably, described modified starch is that modified corn starch, described lubricant are that internal lubricant, described nano-calcium carbonate are 6000-12000 purpose nano-calcium carbonate.Modified corn starch has the characteristic of easy suction, and this makes the plastics that add environmental-friendly plastic additive bury the easy suction in back and decompose.Internal lubricant can have good consistency with plastic polymer, and it plays the effect that reduces polymkeric substance force of cohesion in polymkeric substance inside, thereby the internal friction that reduces melt is given birth to heat and the flowability that improves melt.Normally used internal lubricant is fatty compounds, organosilicon material, silicone master batch etc.Nano-calcium carbonate can be so that the performance of environmentally-friendly plastic strengthens.
The present invention also provides a kind of method for preparing environmental-friendly plastic additive of the present invention on the other hand, and this method may further comprise the steps:
A. carry out merging the first time at first with new LDPE (film grade), nano-calcium carbonate and sarin mixed with resin, and with the mixture that obtains;
B. in the product that step a fusion obtains, add high density polyethylene(HDPE), lubricant, low thermal oxidation agent, static inhibitor and Vestolen PP 7052, and carry out merging the second time;
C. merge in the product that obtains to step b and add 1) modified starch, 2) microbial preparation and 3) glycerine or Ucar 35, and merge for the third time;
D. with step c obtain merge for the third time after product penetrate or extrude and be shaped, obtain described environmental-friendly plastic additive.
Preferably, the temperature that merges for the first time among the described step a is 140-180 ℃, and time of fusion is 5-10min.
More preferably, the temperature that merges for the first time is 150 ℃.
Preferably, the temperature that merges for the second time among the described step b is 170-230 ℃, and time of fusion is 5-10min.
More preferably, the temperature that merges for the second time is 190 ℃.
Preferably, the temperature that merges for the third time among the wherein said step c is 90-120 ℃, and time of fusion is 5-10min.
More preferably, the temperature that merges for the third time is 110 ℃.
Further aspect of the present invention provides a kind of environmentally-friendly plastic, and described environmentally-friendly plastic contains environmental-friendly plastic additive of the present invention.This environmentally-friendly plastic can be any plastics: like the shell of plastics bag, plastic cup, electrical home appliances, footwear material, tableware, raincoat, plastic sheeting for farm use, packing film, container, stationery etc.
Beneficial effect of the present invention is: the concentration of the poisonous gas that the plastics that environmental-friendly plastic additive of the present invention added give off when burning is low, can not cause atmospheric pollution.Plastics among the present invention burned after four minutes, and the concentration of the HF that is given off is not higher than 0.5ppm, and the HCl concentration that gives off is not higher than 0.5ppm, and the concentration of the HCN that gives off is not higher than 1ppm, the SO that gives off 2Concentration be not higher than 0.5ppm, the NO that gives off XConcentration be not higher than 3ppm, the CO concentration that gives off is not higher than 100ppm, is far smaller than the emission standard of the toxic gas in the ABD-0031 test specification.The plastics that simultaneously environmental-friendly plastic additive of the present invention added are in that bury can biological degradation in back 1 year.And environmental-friendly plastic additive of the present invention can form environmental-friendly plastic additive through penetrating or extrude technology according to the demand of reality, and the manufacture craft of additive is simple, and is practical.Through controlled aerobic composting test; Detected the biolysis ability of the plastics that contain environmental-friendly plastic additive of the present invention according to GB/T 19277-2003 (IDT ISO14855:1999), wherein reference material is a Mierocrystalline cellulose, compost fertile 3 months ages; Test chamber volume 3L; Measuring the carbonic acid gas method is after absorbing with sodium hydroxide solution, to measure the amount of carbon dioxide that dissolved inorganic carbon (DIC) is emitted as accumulative total, and detected result is following:
Figure GSB00000672216100041
Can find out that through above result above TP is effective, and it is good to contain the biolysis ability of plastics of environmental-friendly plastic additive of the present invention.
Description of drawings
Fig. 1 representes to prepare the schema of the method for environmental-friendly plastic additive of the present invention.
Embodiment
Embodiment 1
Be 6000-9000 purpose nano-calcium carbonate and sarin mixed with resin at first, then carry out merging the first time, merged 8 minutes at 150 ℃ with low-density Vilaterm, particle diameter.In primary fusion product, add highdensity Vilaterm, lubricant, low thermal oxidation agent, static inhibitor and Vestolen PP 7052 again, and carry out merging the second time, merged 10 minutes at 190 ℃.In secondary fusion product, add modified corn starch, microbial preparation and Ucar 35 again, and merge for the third time at 110 ℃, the product that again fusion is obtained passes through ejection formation.
In the raw material of preparation environmental-friendly plastic additive, the weight percent that each composition accounts for the additive gross weight is:
Low-density Vilaterm (English be called for short LDPE) 10%, particle diameter are the lime carbonate 12%, sarin resin (English Surlyn) 2%, highdensity Vilaterm (the English HDPE of abbreviation) 10%, lubricant 5%, modified corn starch 16%, low thermal oxidation agent 6%, static inhibitor 4%, Vestolen PP 7052 20%, Ucar 35 10% of 6000-9000 purpose nanometer and 5% microbial preparation.Described microbial preparation is citrobacter freundii (latin name Citrobacter freundii); Stenotrophomonas maltophilia (latin name Stenotrophomonas maltophilia); Dead rice sprout spore Bacillaceae (latin name Bacillus vallismortis); Acinetobacter calcoaceticus (latin name Acinetobacter calcoaceticus); Pseudomonas (latin name Pseudomonas sp.); Pseudomonas oleovorans (latin name Pseudomonas oleovorans); Erwinia (latin name Erwinia rhapontici); Bacillus pumilis (latin name Curtobacterium citreum); Bacillus subtilus (latin name Bacillus subtilis) and Bacillus licheniformis (latin name Bacilluslicheniformis).The microbial preparation of being made up of above 10 kinds of bacterial classifications is available from the limited commercial firm of Japanese CORONA, and the said firm is positioned at Tokyo, Japan three hawk cities.
Above environmental-friendly plastic additive is added in the plastic material, process environmentally-friendly plastic.The adding method is following: the weight ratio of above environmental-friendly plastic additive with 3: 7 added in the material of various plastics, and the conventional preparation method according to various plastics processes various plastics again.
Get three samples of above plastics, according to standard detection first sample, second sample and the 3rd sample of ABD-0031.Detected result shows: burn after four minutes, the HF concentration of three samples is 0ppm; The concentration of HCl is 0ppm; The concentration of HCN is 1ppm; SO 2Concentration be 0ppm; The concentration of CO is 100ppm, for NO XConcentration: first sample is 2ppm, and second sample is 2ppm, and the 3rd sample is 3ppm, sees table 1 for details.
The normative testing standard of ABD-0031: burnt 4 minutes, HF concentration is less than 100ppm, and HCl concentration is 150ppm, and HCN concentration is less than 150ppm, SO 2Concentration less than 100ppm, NO XConcentration less than 100ppm, the concentration of CO is less than 3500ppm.
This shows that the plastics of present embodiment burn the back discharging waste gas within the normative testing standard of ABD-0031, belong to environment-friendly type plastic.
Table 1 is according to ABD-0031 test specification discharge of harmful gases
Figure GSB00000672216100051

Claims (8)

1. environmental-friendly plastic additive, said additive contains its gross weight 1) new LDPE (film grade), 2 of 1-10%) nano-calcium carbonate, 3 of 1-12%) the sarin resin, 4 of 1-2%) high density polyethylene(HDPE), 5 of 1-10%) lubricant, 6 of 1-5%) modified starch, 7 of 1-16%) the low thermal oxidation agent, 8 of 1-6%) static inhibitor, 9 of 1-4%) microbial preparation, 10 of 1-5%) Vestolen PP 7052 and 11 of 1-20%) glycerine or the Ucar 35 of surplus; Described microbial preparation is citrobacter freundii (Citrobacter freundii); Stenotrophomonas maltophilia (Stenotrophomonas maltophilia); Dead rice sprout spore bacillus (Bacillus vallismortis); Acinetobacter calcoaceticus (Acinetobacter calcoaceticus); Pseudomonas (Pseudomonas sp.); Pseudomonas oleovorans (Pseudomonas oleovorans); Erwinia (Erwinia rhapontici); Bacillus pumilis (Curtobacterium citreum); Bacillus subtilus (Bacillus subtilis) and Bacillus licheniformis (Bacillus licheniformis); Described nano-calcium carbonate is a 6000-12000 purpose nano-calcium carbonate, and described modified starch is a modified corn starch, and described lubricant is an internal lubricant.
2. method for preparing the described environmental-friendly plastic additive of claim 1, this method may further comprise the steps:
A. carry out merging the first time at first with new LDPE (film grade), nano-calcium carbonate and sarin mixed with resin, and with the mixture that obtains;
B. in the product that step a fusion obtains, add high density polyethylene(HDPE), lubricant, low thermal oxidation agent, static inhibitor and Vestolen PP 7052, and carry out merging the second time;
C. merge in the product that obtains to step b and add 1) modified starch, 2) microbial preparation and 3) glycerine or Ucar 35, and merge for the third time;
D. with step c obtain merge for the third time after product penetrate or extrude and be shaped, obtain described environmental-friendly plastic additive.
3. method according to claim 2, the temperature that merges for the first time among the wherein said step a is 140-180 ℃, time of fusion is 5-10min.
4. method according to claim 3, the temperature that merge with the wherein said first time is 150 ℃.
5. method according to claim 2, the temperature that merges for the second time among the wherein said step b is 170-230 ℃, time of fusion is 5-10min.
6. method according to claim 5, the temperature that merge with the wherein said second time is 190 ℃.
7. method according to claim 2, the temperature that merges for the third time among the wherein said step c is 90-120 ℃, time of fusion is 5-10min.
8. method according to claim 7, the wherein said temperature that merges for the third time is 110 ℃.
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CN103589182A (en) * 2013-10-19 2014-02-19 安徽美翔塑业有限公司 Environment-friendly plastic bag
CN104327361A (en) * 2014-11-25 2015-02-04 侨健新能源科技(苏州)有限公司 High-performance degradable modified plastic material
CN107434868A (en) * 2016-05-25 2017-12-05 鸿明环保科技股份有限公司 Biodegradable foamed material and its product
CN107298795A (en) * 2017-06-29 2017-10-27 合肥达户电线电缆科技有限公司 A kind of preparation method of novel environment friendly plastic additive
CN108559160A (en) * 2018-05-14 2018-09-21 南安市创培电子科技有限公司 A kind of environmental-friendly plastic additive
CN110818983A (en) * 2019-11-14 2020-02-21 张小飞 Preparation method of plastic additive
CN114951237B (en) * 2022-05-09 2023-04-07 中南大学 Method for degrading micro-nano plastic
CN116606755B (en) * 2023-03-15 2024-05-14 中国国际海运集装箱(集团)股份有限公司 Bacillus licheniformis and application thereof in degradation of polyolefin

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