CN110819085A - High-toughness full-biodegradable plastic bag and preparation method thereof - Google Patents
High-toughness full-biodegradable plastic bag and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-toughness fully biodegradable plastic bag and a preparation method thereof. The high-toughness full-biodegradable plastic bag comprises the following raw materials in parts by weight: 5-30 parts of polybutylene succinate, 69.4-86.8 parts of polybutylene adipate terephthalate, 0.5-8 parts of plasticizer and 0.05-0.2 part of antioxidant. The high-toughness full-biodegradable plastic bag disclosed by the invention has the advantages of high toughness and tear resistance, high bearing capacity, high degradation speed and strong antistatic and antibacterial effects.
Description
Technical Field
The invention relates to the technical field of plastic bag preparation, in particular to a high-toughness fully-biodegradable plastic bag and a preparation method thereof.
Background
The plastic bags do bring convenience to our lives, but the convenience brings long-term harm, the recycling value of the plastic bags is low, the plastic bags are scattered in urban streets, tourist areas, water bodies and two sides of roads and railways to cause visual pollution in the using process, potential harm also exists, the plastic bags are stable in structure and not easy to degrade by natural microorganisms, the plastic bags are not separated in the natural environment for a long time, a large amount of land can be occupied for a long time, the pressure of land resources is increased, waste plastic garbage is changed into pollutants to exist permanently and accumulate continuously in the environment if not recycled, and great harm can be caused to the environment.
The environmental protection plastic bag is the abbreviation of various biodegradable plastic bags, and along with the development of science and technology, the material of various alternative traditional PE plastics appears, including polymer materials such as PLA, PHAs, PBA, PBS, environmental protection plastic bag uses comparatively extensively at present: supermarket shopping bags, rolling freshness protection bags, mulching films and the like have large-scale application examples in China.
In the prior art, a chinese patent application with application number CN201510819999.7 discloses an environment-friendly plastic bag and a processing method thereof, which comprises the following raw materials in parts by weight: 30-50 parts of OPS (p-octyl phenyl salicylate), 30-50 parts of PET (polyethylene terephthalate), 30-50 parts of PLA (lactide polyester, commonly known as polylactic acid), 20-30 parts of corn starch pasting modified master batch and 8-10 parts of calcium carbonate.
The existing environment-friendly plastic bag uses PLA, OPS, PET and corn starch pasting modified master batch to replace polyethylene materials, and has the advantages of natural decomposition of raw materials, no toxicity, no secondary pollution, environmental protection and safety; however, the polylactic acid plastic has low toughness and strength and poor bearing performance, when too much things are loaded in the plastic bag, the plastic bag can not bear the weight in the bag and is broken, the outer side of some food packaging bags is provided with a tip which can puncture the plastic bag, and the polylactic acid plastic products can be completely decomposed into CO within 4-6 months under the action of microorganisms such as bacteria and the like2And water, the degradation time is longer, and the environmental protection is poorer.
Therefore, the plastic bag with good toughness and tear resistance, high bearing capacity and high degradation speed needs to be developed.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a high-toughness fully biodegradable plastic bag which has the advantages of high toughness and tear resistance, high bearing capacity and high degradation speed.
The second purpose of the invention is to provide a preparation method of a high-toughness fully biodegradable plastic bag, which has the advantages of simple preparation method and easy operation.
In order to achieve the first object, the invention provides the following technical scheme: a high-toughness full-biodegradable plastic bag comprises the following raw materials in parts by weight: 5-30 parts of polybutylene succinate, 69.4-86.8 parts of polybutylene adipate terephthalate, 0.5-8 parts of plasticizer and 0.05-0.2 part of antioxidant.
By adopting the technical scheme, the polybutylene succinate is easily decomposed and metabolized by enzymes in various microorganisms or animals and plants to be decomposed into carbon dioxide and water, is a completely degradable material and has good biocompatibility, and the polybutylene adipate-terephthalate serving as a completely biodegradable material has good toughness, ductility and elongation at break, good heat resistance and impact resistance, good transparency and flexibility and less antioxidant addition, can prevent thermal oxidation degradation in the heating process, enables a plastic bag to be processed and molded smoothly, can increase the toughness of the plastic bag and strengthen the bearing capacity of the plastic bag, and the plastic bag prepared by mixing various raw materials has good toughness, high tear resistance, strong bearing capacity, good transparency and rapid degradation.
Further, the raw materials in parts by weight are as follows: 15-20 parts of polybutylene succinate, 72.4-80.8 parts of polybutylene adipate terephthalate, 3-5.5 parts of plasticizer and 0.1-0.15 part of antioxidant.
By adopting the technical scheme, the using amount of each raw material of the plastic bag is more accurate, so that the manufactured plastic bag has more excellent mechanical property, good transparency and high bearing capacity.
Further, the antioxidant is prepared by the following method: extracting Bulbus Allii essential oil by supercritical carbon dioxide extraction, mixing Bulbus Allii essential oil with isotridecanol polyoxyethylene ether, heating to 50-100 deg.C, adding green tea extract, rhizoma Zingiberis recens extract, citric acid and vitamin C, homogenizing, and cooling to obtain antioxidant; the antioxidant comprises the following components in parts by weight: 3-5 parts of garlic essential oil, 0.1-0.3 part of isotridecanol polyoxyethylene ether, 1.2-1.8 parts of green tea extract, 0.8-1.4 parts of ginger extract, 1.4-2 parts of citric acid and 2-2.8 parts of vitamin C.
By adopting the technical scheme, the garlic essential oil contains more sulfur-containing organic compounds in a reduction state, peroxide formed during automatic oxidation of polyunsaturated fatty acid can be reduced, the peroxide value is reduced, meanwhile, the green tea extract and the ginger extract have better antioxidation, the citric acid and the vitamin C also have stronger reducibility, and the antioxidant prepared by mixing various substances with the garlic essential oil has the effects of antioxidation and easy degradation, and the degradation speed of the plastic bag cannot be influenced.
Further, the weight average molecular weight of the polybutylene adipate terephthalate is 6-10 ten thousand, and the melt index is (3.2-3.5) g/10 min.
Further, the plasticizer is one or a combination of more of glycerol, dimethyl phthalate and dioctyl phthalate.
Furthermore, the raw materials also comprise polyhydroxybutyrate and PETG, and the mass ratio of the polyhydroxybutyrate to the PETG is 1:0.2-0.4: 0.3-0.5.
By adopting the technical scheme, polyhydroxybutyrate is high in cleanliness, can be quickly degraded, cannot cause environmental pollution, but is poor in mechanical property, PETG has outstanding toughness and high impact strength, excellent mechanical strength and flexibility, high in transparency, good in glossiness and environment-friendly advantage, polyhydroxybutyrate and PETG are mixed to serve as raw materials, the impact strength, the tearing strength and the tensile strength of a plastic bag can be improved, and the transparency of the plastic bag can be improved.
Furthermore, the raw materials also comprise antistatic agent and antibacterial agent, wherein the dosage of the antistatic agent is 2.6-3.2 parts and the dosage of the antibacterial agent is 3.5-4.8 parts by weight.
Through adopting above-mentioned technical scheme, because of the plastic bag is in the use, ubiquitous static problem, very easily adsorb the dust, and can be used for splendid attire domestic waste mostly after a large amount of shopping bags that obtain from the supermarket are used up, because most all contain the organic matter among the domestic waste, the organic matter is very easily fermented in the plastic bag, rot, give off various peculiar smells, thereby influence living environment quality, consequently mix antistatic agent and antibacterial agent in the raw materials of plastic bag, thereby promote the antistatic properties and the bacterinertness of plastic bag, make the plastic bag be difficult for adsorbing the dust in the use, and during the splendid attire rubbish, be difficult for breeding the bacterium, have anticorrosive, antibacterial function.
Further, the preparation method of the antistatic agent is as follows: (1) drying the aromatic carboxylate nucleating agent in a vacuum drying oven at 60-120 ℃ for 12-40 h;
(2) mixing graphene and hydrazine hydrate, adding the mixture into glycerol with the concentration of 10-20%, and ultrasonically dispersing for 5-20min at the ultrasonic frequency of 50-60kHz and the power of 100-200W at the temperature of 30-70 ℃, filtering and drying to obtain mixed powder, wherein the mass ratio of the graphene to the hydrazine hydrate to the glycerol is 1:0.06-0.2: 3-5;
(3) and (2) placing the mixed powder into N-methyl pyrrolidone, carrying out ultrasonic dispersion for 5-20min at the ultrasonic frequency of 50-60kHz and the power of 100-200W at the temperature of 30-70 ℃, adding the aromatic carboxylate nucleating agent dried in the step (1), stirring for 0.5-2h at the temperature of 30-100 ℃ and the stirring speed of 500-2000r/min, filtering, washing, and carrying out vacuum drying for 12-36h at the temperature of 40-80 ℃ to obtain the antistatic agent, wherein the mass ratio of the mixed powder, the N-methyl pyrrolidone and the aromatic carboxylate nucleating agent is 1:3-5: 0.3-0.6.
By adopting the technical scheme, the nucleating agent is dried and then mixed with the mixed solution of the graphene, the hydrazine hydrate and the N-methyl pyrrolidone, the crystallization behavior of the graphene is changed, the crystallization density is increased, and the grain size is refined under the action of the aromatic carboxylate nucleating agent, so that the amorphous region interval is reduced, the thermal property and the mechanical property of the graphene are improved, the antistatic agent prepared from the graphene has a strong antistatic effect, and the mechanical property and the processing property of the antistatic agent in a plastic bag are enhanced.
The antibacterial agent is prepared by the following method: mixing the pineapple leaf fiber, the chitosan and a silver nitrate solution in a mass ratio of 1:0.3-0.5:0.6-1.2, ultrasonically dispersing at an ultrasonic frequency of 40-50kHz for 120min, dispersing for 120min, placing in a reaction kettle at a temperature of 140-150 ℃ and a pressure of 0.7-0.8MPa, preserving heat for 160min, then heating to 310 ℃ at a temperature of 300 ℃ and a pressure of 7.5-7.8MPa for 300min, cooling, centrifuging, washing for 10-15min with absolute ethanol, performing suction filtration, drying and grinding to obtain the antibacterial agent with the particle size of 1-5 mu m.
By adopting the technical scheme, the pineapple leaf fibers, the chitosan and the silver nitrate solution are subjected to ultrasonic dispersion, so that the chitosan and the silver nitrate are loaded on the pineapple leaf fibers, the pineapple leaf fibers loaded with the chitosan and the silver nitrate are heated and pressurized, and are hydrolyzed and carbonized to form silver-loaded carbon microspheres, and the prepared antibacterial agent is good in antibacterial effect and high in purity by compounding the pineapple leaf fibers with the antibacterial effect, the chitosan and the silver nitrate.
In order to achieve the second object, the invention provides the following technical scheme: a preparation method of a high-toughness fully biodegradable plastic bag comprises the following steps:
s1, mixing polybutylene succinate, polybutylene adipate terephthalate, an antioxidant and a plasticizer, adding the mixture into a stirrer, and stirring at the stirring speed of 200-400r/min for 5-10min to obtain a mixture A;
s2, adding polyhydroxybutyrate and PETG into the mixture A, uniformly mixing, adding an antibacterial agent and an antistatic agent, and uniformly mixing to obtain a mixture B;
s3, adding the mixture B into a double-screw extruder, melting and extruding to obtain material particles, and performing blow molding, traction, rolling and bag making on the material particles by a high-low pressure film blowing machine to obtain the high-toughness fully biodegradable plastic bag, wherein the melting temperature is 165-185 ℃.
By adopting the technical scheme, the polybutylene succinate, the polybutylene adipate terephthalate, the antioxidant and the plasticizer are mixed firstly and then are mixed and melted with the polyhydroxybutyrate, the PETG, the antibacterial agent and the antistatic agent, so that the raw materials are uniformly and fully mixed, the operation is simple, and the industrial production is convenient.
In conclusion, the invention has the following beneficial effects:
firstly, because the invention adopts the poly butylene succinate and the poly butylene adipate terephthalate as the main raw materials of the plastic bag and adds a small amount of plasticizer and antioxidant, because the poly butylene succinate and the poly butylene adipate terephthalate are all biodegradable materials, the degradation speed is fast, the environment is not polluted, the impact resistance of the poly butylene succinate and the poly butylene adipate terephthalate is good, the transparency is high, the poly butylene succinate and the poly butylene adipate terephthalate have better ductility and elongation at break, the plasticizer can enhance the toughness thereof, and the antioxidant can prevent thermal oxidative degradation in the heating process, so that the plastic bag is easy to form.
Secondly, the antioxidant is preferably prepared from garlic essential oil, green tea extract, vitamin C and the like, the garlic essential oil, the citric acid and the ginger extract have good anti-reduction effect, and the garlic essential oil and the like are easy to degrade and free of pollution and do not influence the degradation speed of the plastic bag.
And thirdly, polyhydroxybutyrate and PETG are preferably added into the plastic bag raw material, and both polyhydroxybutyrate and PETG have the advantages of high cleanliness, good transparency, rapid degradation and environmental protection, and have high mechanical strength and good flexibility, so that the impact strength and the tear resistance of the plastic bag can be improved, and the transparency of the plastic bag is increased.
Fourthly, the antistatic agent prepared from the aromatic carboxylate nucleating agent, the graphene and other raw materials is preferably doped into the plastic bag raw material, so that the thermal property and the mechanical property of the graphene can be improved, the mechanical property and the processing property of the antistatic agent in the plastic bag can be enhanced, the plastic bag has an excellent antistatic effect, and the plastic bag is prevented from adsorbing dust in use.
Fifthly, the invention preferably mixes the antibacterial agent made of pineapple leaf fiber, chitosan and silver nitrate into the plastic bag raw material, the silver nitrate and chitosan are loaded on the pineapple leaf fiber, the pineapple leaf fiber is heated and pressurized, and after hydrolysis and carbonization, the pineapple leaf fiber becomes silver-loaded carbon microspheres, so that the silver-loaded carbon microspheres are uniformly mixed when being mixed, melted and extruded with the plastic bag raw material, and the antibacterial and anticorrosion effects of the plastic bag are enhanced.
Detailed Description
The present invention will be described in further detail with reference to examples.
Preparation examples 1 to 3 of antioxidant
Preparation examples 1-3 the green tea extract was selected from the group consisting of 84650 marketed by Zhang Xin Biotech, Suzhou and 0154 marketed by Xianlong Biotech.
Preparation example 1: extracting garlic essential oil by supercritical carbon dioxide extraction method, mixing 3kg garlic essential oil and 0.1kg isotridecanol polyoxyethylene ether, heating to 50 deg.C, adding 1.2kg green tea extract, 0.8kg rhizoma Zingiberis recens extract, 1.4kg citric acid and 2kg vitamin C, homogenizing, and cooling to obtain antioxidant.
Preparation example 2: extracting garlic essential oil by using a supercritical carbon dioxide extraction method, mixing 4kg of garlic essential oil with 0.2kg of isotridecanol polyoxyethylene ether, heating to 80 ℃, adding 1.5kg of green tea extract, 1.1kg of ginger extract, 1.7kg of citric acid and 2.4kg of vitamin C, homogenizing, and cooling to obtain the antioxidant.
Preparation example 3: extracting garlic essential oil by supercritical carbon dioxide extraction method, mixing 5kg garlic essential oil and 0.3kg isotridecanol polyoxyethylene ether, heating to 100 deg.C, adding 1.8kg green tea extract, 1.4kg rhizoma Zingiberis recens extract, 2kg citric acid and 2.8kg vitamin C, homogenizing, and cooling to obtain antioxidant.
Preparation examples 4 to 6 of antistatic agent
Preparation example 4: (1) drying the aromatic carboxylate nucleating agent in a vacuum drying oven at 60 ℃ for 40h, wherein the aromatic carboxylate nucleating agent is sodium benzoate;
(2) mixing graphene and hydrazine hydrate, adding the mixture into 10% glycerol, performing ultrasonic treatment in an ultrasonic dispersion machine for 5min at the ultrasonic frequency of 60kHz and the power of 200W at the temperature of 30 ℃, filtering, and drying to obtain mixed powder, wherein the mass ratio of the graphene to the hydrazine hydrate to the glycerol is 1:0.06: 3;
(3) and (2) placing the mixed powder into N-methyl pyrrolidone, carrying out ultrasonic dispersion for 5min, wherein the ultrasonic frequency is 60kHz, the power is 200W, the temperature is 30 ℃, adding the sodium benzoate dried in the step (1), stirring for 2h at 30 ℃, the stirring speed is 500r/min, filtering, washing, and carrying out vacuum drying for 36h at 40 ℃ to obtain the antistatic agent, wherein the mass ratio of the mixed powder to the N-methyl pyrrolidone to the sodium benzoate is 1:3: 0.3.
Preparation example 5: (1) drying the aromatic carboxylate nucleating agent in a vacuum drying oven at 90 ℃ for 26 hours, wherein the aromatic carboxylate nucleating agent is sodium benzoate;
(2) mixing graphene and hydrazine hydrate, adding the mixture into 15% glycerol, carrying out ultrasonic treatment in an ultrasonic dispersion machine for 10min at the ultrasonic frequency of 55kHz and the power of 150W and at the temperature of 50 ℃, filtering and drying to obtain mixed powder, wherein the mass ratio of the graphene to the hydrazine hydrate to the glycerol is 1:0.13: 4;
(3) and (2) placing the mixed powder into N-methyl pyrrolidone, carrying out ultrasonic dispersion for 10min at an ultrasonic frequency of 55kHz and a power of 150W at a temperature of 50 ℃, adding the sodium benzoate dried in the step (1), stirring for 1.5h at a temperature of 70 ℃, at a stirring speed of 1500r/min, filtering, washing, and carrying out vacuum drying for 28h at a temperature of 60 ℃ to obtain the antistatic agent, wherein the mass ratio of the mixed powder to the N-methyl pyrrolidone to the sodium benzoate is 1:4: 0.5.
Preparation example 6: (1) drying the aromatic carboxylate nucleating agent in a vacuum drying oven at 120 ℃ for 12 hours, wherein the aromatic carboxylate nucleating agent is sodium benzoate;
(2) mixing graphene and hydrazine hydrate, adding the mixture into glycerol with the concentration of 20%, carrying out ultrasonic treatment in an ultrasonic dispersion machine for 20min at the ultrasonic frequency of 50kHz and the power of 100W and at the temperature of 70 ℃, filtering and drying to obtain mixed powder, wherein the mass ratio of the graphene to the hydrazine hydrate to the glycerol is 1:0.2: 5;
(3) and (2) placing the mixed powder into N-methyl pyrrolidone, carrying out ultrasonic dispersion for 20min at the ultrasonic frequency of 50kHz and the power of 100W at the temperature of 70 ℃, adding the sodium benzoate dried in the step (1), stirring for 0.5h at the temperature of 100 ℃, at the stirring speed of 2000r/min, filtering, washing, and carrying out vacuum drying for 12h at the temperature of 80 ℃ to obtain the antistatic agent, wherein the mass ratio of the mixed powder to the N-methyl pyrrolidone to the sodium benzoate is 1:5: 0.6.
Preparation examples 7 to 9 of antibacterial agent
Preparation example 7: mixing the pineapple leaf fibers, the chitosan and a silver nitrate solution according to the mass ratio of 1:0.3:0.6, performing ultrasonic dispersion, performing ultrasonic frequency of 40kHz and dispersion time of 120min, placing the mixture in a reaction kettle at the temperature of 140 ℃ and the pressure of 0.7MPa after dispersion, performing heat preservation for 100min, then heating to 300 ℃ and the pressure of 7.5MPa, performing heat preservation for 200min, cooling, centrifuging, washing for 10min by using absolute ethyl alcohol, performing suction filtration, drying and grinding to obtain the antibacterial agent with the particle size of 1 mu m.
Preparation example 8: mixing the pineapple leaf fibers, the chitosan and a silver nitrate solution according to the mass ratio of 1:0.4:0.9, performing ultrasonic dispersion, performing ultrasonic frequency of 45kHz and dispersion time of 110min, placing the mixture in a reaction kettle at the temperature of 145 ℃ and the pressure of 0.75MPa after dispersion, performing heat preservation for 130min, then heating to 305 ℃ and the pressure of 7.6MPa, performing heat preservation for 250min, cooling, centrifuging, washing for 13min by using absolute ethyl alcohol, performing suction filtration, drying and grinding to obtain the antibacterial agent with the particle size of 3 mu m.
Preparation example 9: mixing the pineapple leaf fibers, the chitosan and a silver nitrate solution according to the mass ratio of 1:0.5:1.2, performing ultrasonic dispersion at an ultrasonic frequency of 50kHz and a dispersion time of 100min, placing the mixture in a reaction kettle at a temperature of 150 ℃ and a pressure of 0.8MPa after dispersion, preserving heat for 160min, then heating to 310 ℃ and a pressure of 7.8MPa, preserving heat for 300min, cooling, centrifuging, washing with absolute ethyl alcohol for 15min, performing suction filtration, drying and grinding to obtain the antibacterial agent with the particle size of 5 microns.
Examples
In the following examples the polybutylene succinate is selected from polybutylene succinate sold by Thailand PTT under the model FD92PK and the polybutylene adipate terephthalate is selected from polybutylene adipate terephthalate sold by Goldson technology under the model Flex-64D.
Example 1: the preparation method of the high-toughness fully biodegradable plastic bag comprises the following steps of:
s1, mixing 5kg of polybutylene succinate, 69.4kg of polybutylene adipate terephthalate, 0.05kg of antioxidant and 0.5kg of plasticizer, adding the mixture into a stirrer, stirring at the speed of 200r/min for 10min to obtain a mixture A, wherein the antioxidant is prepared by the preparation example 1;
s2, adding the mixture A into a double-screw extruder, melting and extruding to obtain material particles, blowing, drawing, rolling and making bags by a high-low pressure film blowing machine to obtain the high-toughness fully biodegradable plastic bag, wherein the melting temperature is 165 ℃.
Table 1 examples 1-4 raw material ratios of high toughness fully biodegradable plastic bags
Example 2: the preparation method of the high-toughness fully biodegradable plastic bag comprises the following steps of:
s1, mixing 15kg of polybutylene succinate, 72.4kg of polybutylene adipate terephthalate, 0.1kg of antioxidant and 3kg of plasticizer, and adding the mixture into a stirrer, wherein the stirring speed is 300r/min, and stirring for 8min to obtain a mixture A, wherein the antioxidant is prepared from preparation example 2;
s2, adding the mixture A into a double-screw extruder, melting and extruding to obtain material particles, blowing, drawing, rolling and making bags by a high-low pressure film blowing machine to obtain the high-toughness fully biodegradable plastic bag, wherein the melting temperature is 175 ℃.
Example 3: the preparation method of the high-toughness fully biodegradable plastic bag comprises the following steps of:
s1, mixing 20kg of polybutylene succinate, 80.8kg of polybutylene adipate terephthalate, 0.15kg of antioxidant and 5.5kg of plasticizer, adding the mixture into a stirrer, stirring at the speed of 400r/min for 5min to obtain a mixture A, wherein the antioxidant is prepared by the preparation example 3;
s2, adding the mixture A into a double-screw extruder, melting and extruding to obtain material particles, blowing, drawing, rolling and making bags by a high-low pressure film blowing machine to obtain the high-toughness fully biodegradable plastic bag, wherein the melting temperature is 185 ℃.
Example 4: the preparation method of the high-toughness fully biodegradable plastic bag comprises the following steps of:
s1, mixing 30kg of polybutylene succinate, 86.8kg of polybutylene adipate terephthalate, 0.2kg of antioxidant and 8kg of plasticizer, and adding the mixture into a stirrer, wherein the stirring speed is 200r/min, and stirring for 10min to obtain a mixture A, wherein the antioxidant is prepared by the preparation example 1;
s2, adding the mixture A into a double-screw extruder, melting and extruding to obtain material particles, blowing, drawing, rolling and making bags by a high-low pressure film blowing machine to obtain the high-toughness fully biodegradable plastic bag, wherein the melting temperature is 165 ℃.
Example 5: the high-toughness fully biodegradable plastic bag is different from the plastic bag in example 1 in that the raw materials further comprise polyhydroxybutyrate and PETG, and the preparation method of the high-toughness fully biodegradable plastic bag comprises the following steps:
s1, mixing 30kg of polybutylene succinate, 86.8kg of polybutylene adipate terephthalate, 0.2kg of antioxidant and 8kg of plasticizer, and adding the mixture into a stirrer, wherein the stirring speed is 200r/min, and stirring for 10min to obtain a mixture A, wherein the antioxidant is prepared by the preparation example 1;
s2, adding polyhydroxybutyrate and PETG into the mixture A, and uniformly mixing to obtain a mixture B, wherein the mass ratio of the polybutylene succinate to the polyhydroxybutyrate to the PETG is 1:0.2: 0.3;
s3, adding the mixture B into a double-screw extruder, melting and extruding to obtain material particles, blowing, drawing, rolling and making bags by using a high-low pressure film blowing machine to obtain the high-toughness fully biodegradable plastic bag, wherein the melting temperature is 165 ℃.
Example 6: a high-toughness fully biodegradable plastic bag is different from the plastic bag in example 5 in that the mass ratio of polybutylene succinate to polyhydroxybutyrate to PETG in raw materials is 1:0.3: 0.4.
Example 7: a high-toughness fully biodegradable plastic bag is different from the plastic bag in example 5 in that the mass ratio of polybutylene succinate to polyhydroxybutyrate to PETG in raw materials is 1:0.4: 0.5.
Example 8: a high-toughness fully biodegradable plastic bag is different from the plastic bag in example 5 in that 2.6kg of antistatic agent and 3.5kg of antibacterial agent are also included in the raw materials, and the preparation method of the high-toughness fully biodegradable plastic bag comprises the following steps: s1, mixing 30kg of polybutylene succinate, 86.8kg of polybutylene adipate terephthalate, 0.2kg of antioxidant and 8kg of plasticizer, and adding the mixture into a stirrer, wherein the stirring speed is 200r/min, and stirring for 10min to obtain a mixture A, wherein the antioxidant is prepared by the preparation example 1;
s2, adding polyhydroxybutyrate and PETG into the mixture A, uniformly mixing, adding 3.5kg of an antibacterial agent and 2.6 of an antistatic agent, uniformly mixing to obtain a mixture B, wherein the mass ratio of polybutylene succinate to polyhydroxybutyrate to PETG is 1:0.2:0.3, the antistatic agent is prepared from preparation example 4, and the antibacterial agent is prepared from preparation example 7;
s3, adding the mixture B into a double-screw extruder, melting and extruding to obtain material particles, blowing, drawing, rolling and making bags by using a high-low pressure film blowing machine to obtain the high-toughness fully biodegradable plastic bag, wherein the melting temperature is 165 ℃.
Example 9: a high-toughness fully biodegradable plastic bag is different from that in example 8 in that the antistatic agent is used in an amount of 2.9kg, the antibacterial agent is used in an amount of 4.2kg, the antistatic agent is prepared in preparation example 5, and the antibacterial agent is prepared in preparation example 8.
Example 10: a high-toughness fully biodegradable plastic bag is different from that in example 8 in that the antistatic agent is used in an amount of 3.2kg, the antibacterial agent is used in an amount of 4.8kg, the antistatic agent is prepared in preparation example 6, and the antibacterial agent is prepared in preparation example 9.
Comparative example
Comparative example 1: a high-toughness fully biodegradable plastic bag is different from that in example 1 in that polylactic acid is used instead of polybutylene succinate.
Comparative example 2: a high-toughness fully biodegradable plastic bag, which differs from example 1 in that the antioxidant in the raw material is replaced by an antioxidant sold by zephyr chemical sales ltd under model 1010.
Comparative example 3: a high-toughness fully biodegradable plastic bag is different from the plastic bag in example 8 in that the mass ratio of polybutylene succinate to polyhydroxybutyrate to PETG in raw materials is 1:0.1: 0.2.
Comparative example 4: a high-toughness fully biodegradable plastic bag is different from the plastic bag in example 8 in that the mass ratio of polybutylene succinate to polyhydroxybutyrate to PETG in raw materials is 1:0.5: 0.6.
Comparative example 5: a high-toughness fully biodegradable plastic bag, which is different from the plastic bag in example 8 in that an antistatic agent of 154 kelvin chemical type is used as a substitute for the antistatic agent in the raw material.
Comparative example 6: a high-toughness fully biodegradable plastic bag, which is different from example 8 in that the antibacterial agent in the raw material is replaced by an antibacterial agent sold by Wu Yi great Fine chemical Co., Ltd, model No. WD-15 SG.
Comparative example 7: using the bio-based biodegradable plastic bag material prepared in example 1 of the chinese invention patent document with the application number of cn201410421993.x as a control, 5% of PLA (melt index: 10), 48% of PBST (bio-based succinic acid, melt index: 4.8), 15% of poly-3-hydroxybutyrate 4-hydroxybutyrate (melt index: 15), 30% of tapioca starch, 1% of epoxy fatty acid methyl ester, 0.5% of 4, 4-diphenylmethane diisocyanate trimer, and 0.5% of carnauba wax are sequentially added into a high-speed mixer, and after uniform mixing, the mixture is added into a co-rotating twin-screw parallel extruder to be plasticized, extruded and granulated to obtain plastic particles, and then a film blowing machine and a bag making machine are sequentially used to make bags to obtain bags (vest bags).
Performance test
Firstly, mechanical property detection: plastic bags were prepared according to the methods in examples 1-10 and comparative examples 1-7, and part 3 of the determination of tensile Properties of plastics according to the following method GB/T1040.3-2006: test conditions for films and sheets "were measured under 200mm/min, and the results are shown in Table 2.
Table 2 mechanical property test of plastic bags prepared in each example and each comparative example
As can be seen from the data in table 2, the high toughness fully biodegradable plastic bags prepared according to the methods in examples 1 to 4 have a transverse tensile modulus of 284.67MPa or more, a longitudinal tensile modulus of 271.67MPa or more, a transverse tensile strength of 19.93MPa or more, a longitudinal tensile strength of 18.06MPa or more, a transverse elongation at break of 580% or more, and a longitudinal elongation at break of greater than 646.67%, and thus it can be seen that the plastic bags prepared according to the methods in examples 1 to 4 have high tensile strength, good tear resistance, high load bearing capacity, repeated use, and wide application.
In examples 5 to 7, polyhydroxybutyrate and PETG are added on the basis of the raw materials in examples 1 to 4, and the detection results show that plastic bags made of polyhydroxybutyrate and PETG have higher toughness, better tear resistance and higher bearing capacity.
Examples 8-10 polyhydroxybutyrate, PETG, an antibacterial agent and an antistatic agent were added to the extrusion of the raw materials of examples 1-4, and it can be seen from the results of the tests that the mechanical properties of the plastic bags prepared in examples 8-10 are not much different from those of examples 5-7, and the plastic bags have strong tensile strength and tear resistance.
Comparative example 1 since polylactic acid was used instead of polybutylene succinate, the plastic bag manufactured in comparative example 1 had a reduced tensile strength, a reduced elongation at break, a deteriorated toughness, and a reduced load-bearing capacity, as compared to examples 1 to 10.
Comparative example 2 since the commercially available antioxidant was used instead of the antioxidant prepared according to the present invention, it was found from the test results that the mechanical properties of the plastic bag prepared according to comparative example 2 were not much different from those of the plastic bag prepared according to example 1.
Comparative example 3 because the mass ratio of polybutylene succinate to polyhydroxybutyrate to PETG in the raw materials is 1:0.1:0.2 based on example 8, and comparative example 4 because the mass ratio of polybutylene succinate to polyhydroxybutyrate to PETG in the raw materials is 1:0.5:0.6 based on example 8, it can be seen from the detection results that the mechanical properties of the plastic bags prepared in comparative examples 3 and 4 are greatly different from those of the plastic bags prepared in examples 1-10, the toughness is reduced, and the bearing capacity is deteriorated.
Comparative example 5 the mechanical properties of plastic bags prepared in comparative example 5 and comparative example 6 were not much different from those of examples 8 to 10, and had better mechanical properties, because a commercially available antistatic agent was used on the basis of example 8, and a commercially available antibacterial agent was used on the basis of example 8 in comparative example 6.
Comparative example 7 is a plastic bag prepared in the prior art using PLA and PBST as main raw materials, and its mechanical properties are greatly different from those of the plastic bags prepared in examples 1 to 10.
Secondly, detecting the biodegradation rate: plastic bags were prepared according to the methods of examples 1 to 10 and comparative examples 1 to 7, and the biodegradation rates of the plastic bags were measured according to QB/T2670-2004 "definition, classification, labeling and requirement for degradation properties of degraded plastic sheets" and GB/T20197-2006 "definition, classification, labeling and requirement for degradation properties of degraded plastics", and the measurement results are recorded in table 3.
Table 3 biodegradation rate test of plastic bags prepared in each example and each comparative example
As can be seen from the data in Table 3, the biodegradation rate of the plastic bags prepared according to the methods in examples 1-10 reaches 65.5-70.3% in 80 days, approaches 100% in 110 days, and reaches 100% full degradation in 120 days, and the degradation time is relatively fast.
Comparative example 1 the plastic bag prepared in comparative example 1 also completed 100% total degradation at 120 days, since PLA was used instead of polybutylene succinate, and since PLA was also a degradable material.
Comparative example 2 since the commercially available antioxidant was used instead of the antioxidant prepared according to the present invention, it can be seen from the data in the table that the biodegradation rate of the plastic bag prepared according to comparative example 2 was slow, reaching 93.4% only in 120 days, and not reaching 100% full degradation.
Comparative example 3 because the mass ratio of polybutylene succinate to polyhydroxybutyrate to PETG in the raw materials is 1:0.1:0.2 based on example 8, and comparative example 4 because the mass ratio of polybutylene succinate to polyhydroxybutyrate to PETG in the raw materials is 1:0.5:0.6 based on example 8, when the doping amount is changed because polyhydroxybutyrate and PETG are degradation materials, the degradation rate is reduced compared with examples 1-10, but 100% full degradation can be completed in 120 days.
Comparative example 5 since a commercially available antistatic agent was used on the basis of example 8, and comparative example 6 since a commercially available antibacterial agent was used on the basis of example 8, it can be seen from the results of the test that the biodegradation rates of the plastic bags prepared in comparative example 5 and comparative example 6 were slow, the degradation rates were 92.8% and 94.3% at 120 days, respectively, and 100% full degradation was not achieved at 120 days.
Comparative example 7 is a plastic bag prepared using PLA and PBST in the prior art, the biodegradation rate was reduced compared to examples 1-10, with a degradation rate of 98.5% at 120 days, not reaching 100% full degradation.
Thirdly, detecting other performances: plastic bags were prepared according to the methods of examples 1 to 10 and comparative examples 1 to 7, and the transparency, antibacterial property and antistatic property of the plastic bags were measured according to the following methods, and the measurement results are recorded in table 4:
1. haze: detecting according to GB/T2410-2008 'determination standard of transparent plastic light transmittance and haze';
2. and (3) antibacterial property: according to the detection indexes of ASTME-2149-01, namely the antibacterial behavior of the steady-state antibacterial agent under the dynamic contact condition, the detection indexes are Escherichia coli ATCC25922 and staphylococcus aureus ATC 6538;
3. antistatic property: detection is carried out according to GB/T14447-1993 half-life method of electrostatic testing methods for plastic films.
Table 4 testing of properties such as transparency of plastic bags prepared in each example and each comparative example
As can be seen from the data in table 4, the plastic bags prepared by the methods in examples 1 to 4 have a small haze value, a low surface resistance, an antibacterial rate of more than 92%, and high transparency, antibacterial rate, and antistatic property.
Examples 5-7 the haze values of the plastic bags prepared in examples 5-7 were reduced and the transparency was significantly enhanced by adding polyhydroxybutyrate and PETG to example 1.
Examples 8-10 the antistatic agent and the antibacterial agent were added to example 5, and the haze values of the plastics prepared in examples 8-10 were improved due to polyhydroxybutyrate and PETG, and the antibacterial and antistatic properties of the plastic bags were enhanced due to the addition of the antibacterial agent and the antistatic agent.
In comparative example 1, the haze value is increased by using PLA instead of polybutylene succinate, and the differences between the antibacterial property and the surface resistance are not large compared with those of example 1, which shows that the haze value of the plastic bag is increased and the transparency is reduced by using PLA instead of polybutylene succinate.
Comparative example 2 since the existing antioxidant was used instead of the antioxidant prepared according to the present invention, the difference in transparency, antibacterial property and surface resistance was not significant as compared to the plastic bag prepared in example 1.
Comparative example 3 the haze value of the plastic bag was increased and the transparency was decreased compared with example 8, because the mass ratio of polybutylene succinate, polyhydroxybutyrate and PETG in the raw materials was 1:0.1:0.2 based on example 8, and comparative example 4 the mass ratio of polybutylene succinate, polyhydroxybutyrate and PETG in the raw materials was 1:0.5:0.6 based on example 8.
Comparative example 5 since a commercially available antistatic agent was used on the basis of example 8, and comparative example 6 since a commercially available antibacterial agent was used on the basis of example 8, the surface resistance of the plastic bag prepared in comparative example 5 was increased and the antibacterial property of the plastic bag prepared in comparative example 6 was decreased, compared to example 8, indicating that the antibacterial agent and antistatic agent prepared in the present invention can effectively improve the antibacterial property and antistatic property of the plastic bag.
Comparative example 7 is a plastic bag prepared using PLA and PBST in the prior art, which has inferior haze value, antibacterial efficiency and antistatic effect to those of the plastic bags prepared in examples 1-10 of the present invention.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. A high-toughness full-biodegradable plastic bag is characterized by comprising the following raw materials in parts by weight: 5-30 parts of polybutylene succinate, 69.4-86.8 parts of polybutylene adipate terephthalate, 0.5-8 parts of plasticizer and 0.05-0.2 part of antioxidant.
2. The high-toughness fully biodegradable plastic bag according to claim 1, wherein the weight parts of the raw materials are: 15-20 parts of polybutylene succinate, 72.4-80.8 parts of polybutylene adipate terephthalate, 3-5.5 parts of plasticizer and 0.1-0.15 part of antioxidant.
3. A high toughness fully biodegradable plastic bag according to any of claims 1-2, characterized in that said antioxidant is made by the following method: extracting Bulbus Allii essential oil by supercritical carbon dioxide extraction, mixing Bulbus Allii essential oil with isotridecanol polyoxyethylene ether, heating to 50-100 deg.C, adding green tea extract, rhizoma Zingiberis recens extract, citric acid and vitamin C, homogenizing, and cooling to obtain antioxidant; the antioxidant comprises the following components in parts by weight: 3-5 parts of garlic essential oil, 0.1-0.3 part of isotridecanol polyoxyethylene ether, 1.2-1.8 parts of green tea extract, 0.8-1.4 parts of ginger extract, 1.4-2 parts of citric acid and 2-2.8 parts of vitamin C.
4. A high tenacity fully biodegradable plastic bag according to any one of claims 1-2, wherein said polybutylene adipate terephthalate has a weight average molecular weight of 6-10 ten thousand and a melt index of (3.2-3.5) g/10 min.
5. A high toughness fully biodegradable plastic bag according to any one of claims 1-2, characterized in that said plasticizer is one or a combination of glycerol, dimethyl phthalate and dioctyl phthalate.
6. The high-toughness full-biodegradable plastic bag according to any one of claims 1-2, wherein the raw materials further comprise polyhydroxybutyrate and PETG, and the mass ratio of the polyhydroxybutyrate to the PETG is 1:0.2-0.4: 0.3-0.5.
7. A high-toughness fully biodegradable plastic bag according to any one of claims 1-2, characterized in that the raw materials further comprise an antistatic agent and an antibacterial agent, wherein the antistatic agent is used in an amount of 2.6-3.2 parts and the antibacterial agent is used in an amount of 3.5-4.8 parts by weight.
8. The high-toughness full-biodegradable plastic bag according to claim 7, wherein the antistatic agent is prepared by the following steps: (1) drying the aromatic carboxylate nucleating agent in a vacuum drying oven at 60-120 ℃ for 12-40 h;
(2) mixing graphene and hydrazine hydrate, adding the mixture into glycerol with the concentration of 10-20%, and ultrasonically dispersing for 5-20min at the ultrasonic frequency of 50-60kHz and the power of 100-200W at the temperature of 30-70 ℃, filtering and drying to obtain mixed powder, wherein the mass ratio of the graphene to the hydrazine hydrate to the glycerol is 1:0.06-0.2: 3-5;
(3) and (2) placing the mixed powder into N-methyl pyrrolidone, carrying out ultrasonic dispersion for 5-20min at the ultrasonic frequency of 50-60kHz and the power of 100-200W at the temperature of 30-70 ℃, adding the aromatic carboxylate nucleating agent dried in the step (1), stirring for 0.5-2h at the temperature of 30-100 ℃ and the stirring speed of 500-2000r/min, filtering, washing, and carrying out vacuum drying for 12-36h at the temperature of 40-80 ℃ to obtain the antistatic agent, wherein the mass ratio of the mixed powder, the N-methyl pyrrolidone and the aromatic carboxylate nucleating agent is 1:3-5: 0.3-0.6.
9. The high toughness fully biodegradable plastic bag according to claim 7, wherein said antibacterial agent is made by the following method: mixing the pineapple leaf fiber, the chitosan and a silver nitrate solution in a mass ratio of 1:0.3-0.5:0.6-1.2, ultrasonically dispersing at an ultrasonic frequency of 40-50kHz for 120min, dispersing for 120min, placing in a reaction kettle at a temperature of 140-150 ℃ and a pressure of 0.7-0.8MPa, preserving heat for 160min, then heating to 310 ℃ at a temperature of 300 ℃ and a pressure of 7.5-7.8MPa for 300min, cooling, centrifuging, washing for 10-15min with absolute ethanol, performing suction filtration, drying and grinding to obtain the antibacterial agent with the particle size of 1-5 mu m.
10. The method for preparing the high-toughness fully biodegradable plastic bag according to any one of claims 1 to 9, comprising the following steps:
s1, mixing polybutylene succinate, polybutylene adipate terephthalate, an antioxidant and a plasticizer, adding the mixture into a stirrer, and stirring at the stirring speed of 200-400r/min for 5-10min to obtain a mixture A;
s2, adding polyhydroxybutyrate and PETG into the mixture A, uniformly mixing, adding an antibacterial agent and an antistatic agent, and uniformly mixing to obtain a mixture B;
s3, adding the mixture B into a double-screw extruder, melting and extruding to obtain material particles, and performing blow molding, traction, rolling and bag making on the material particles by a high-low pressure film blowing machine to obtain the high-toughness fully biodegradable plastic bag, wherein the melting temperature is 165-185 ℃.
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