CN103435981A - Preparation method of full biodegradation film - Google Patents

Preparation method of full biodegradation film Download PDF

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Publication number
CN103435981A
CN103435981A CN2013103381871A CN201310338187A CN103435981A CN 103435981 A CN103435981 A CN 103435981A CN 2013103381871 A CN2013103381871 A CN 2013103381871A CN 201310338187 A CN201310338187 A CN 201310338187A CN 103435981 A CN103435981 A CN 103435981A
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film
parts
preparation
full
pbat
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杨海全
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DONGGUAN XINHAI ENVIRONMENT PROTECTION MATERIAL Co Ltd
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DONGGUAN XINHAI ENVIRONMENT PROTECTION MATERIAL Co Ltd
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Abstract

The invention discloses a preparation method of a full biodegradation film, which takes poly adipic acid/polybutylene terephthalate (PBAT) and starch as base materials, poly-epsilon carpolaction (PCL), epoxidized soybean oil (ESO), and phosphorous acid dialkyl ester as plasticizers, and montmorillonoid or calcium carbonate, talcum powder and the like as inorganic fillers. The method comprises the steps that modification and pelleting are performed in a twin screw; modified resin is added to a film blowing machine for film blowing; and the full biodegradation film can be obtained finally. The full biodegradation film produced by the method is better in physical characteristic, can be directly prepared into a film bag, and can serve as a daily-used packaging film, a waistcoat bag, a food packaging bag and the like; the preparation method of the full biodegradation film is simple in technology, and easy to control, and is suitable for industrial mass production; the film bag produced by the method is high in strength, can be biodegraded fully after use, and is easy to dispose; and environmental pollution is reduced.

Description

A kind of preparation method of full-biodegradable film
Technical field
The present invention relates to technical field of polymer materials, the film grade resins modification that to be specifically related to a kind of PBAT of take and starch be base material and the preparation method of film.
Background technology
Over nearest 100 years, along with the development of high polymer material technology, grow out of nothing and expand from small to large for plastics industry, and global plastics consumption is also more and more.According to statistics, 2011, the usage quantity of global plastics reached the scale of nearly 200,000,000 tons.But in the time of the plastics develop rapidly, also brought two serious problems: the first, a large amount of plastic refuses has brought and has been difficult to bear pollution to environment, the white pollution problems puzzlement whole world; The second, plastic prod, in the process of production and discarded aftertreatment, has produced a large amount of Carbon emissions.
In the wrapping material field, PBAT(gathers adipic acid/butylene terephthalate) be the biodegradable plastic that tool business development is worth, at present, in the packaging group biodegradable plastic of using, have that to approach 60% be that PBAT is all kinds of material modified of base material.The great market demand, cause countries in the world to fall over each other research and development, investment, accelerated its commercialization process.Certainly, the biodegradable industry is a tool high development and the strategic industry that concerns environmental protection, reduction of discharging.
PBAT has superior physical property and degradation property, but that common PBAT also exists elongation at break is low, high cost, and degradation speed waits defect too slowly, has affected its acceptance on market.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind ofly has that the intensity of drawing high is high, Young's modulus good, have the preparation method of elongation at break, biodegradable film preferably.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: a kind of preparation method of full-biodegradable film, it is characterized in that: take gather adipic acid/butylene terephthalate (PBAT), starch is base material, take that to gather ε caprolactone (PCL), epoxy soybean oil (ESO), phosphorous acid dialkyl ester be softening agent, take polynite or calcium carbonate, talcum powder is mineral filler, form multipolymer under the effect of twin screw, the parts by weight of each feed composition are respectively:
40-90 parts of poly-adipic acid/butylene terephthalate
1-30 parts of starch
1-5 parts of poly-ε caprolactones
1-10 parts of epoxy soybean oils
1-10 parts of phosphorous acid dialkyl esters
0-10 parts of mineral fillers
Preferably, the weight-average molecular weight of described poly-adipic acid/butylene terephthalate is between 10-20 ten thousand, and melting index is between 3-20.
Preferably, the weight-average molecular weight of described poly-ε caprolactone is between 10000-100000.
Preferably, the oxirane value of described epoxy soybean oil >=6.0%.
Its production stage of described film is:
(1), proportionally take various raw-material weight;
(2), each starting material are added in high speed mixer in a certain order, high-speed mixing 10-20 minutes is to evenly; The starting material addition sequence is followed successively by powder, liquid material, particulate material;
(3), the raw material mixed is joined in the hopper of twin screw extruder, set each warm area of twin screw extruder, service temperature is 100-180 ℃, after the tie rod pelletizing, can obtain PBAT modified resin;
(4), PBAT modified resin is put into to drying machine and fully be dried to water content≤500ppm;
(5), dried PBAT modified resin is put into to the inflation film manufacturing machine blown film, each warm area service temperature of inflation film manufacturing machine is 100-180 ℃, finally obtains the film of biodegradable.
Preferably, adopt in the twin screw extruder moulding process, screw speed is 50-500RPM, and the length-to-diameter ratio of screw rod is between 25:1-55:1.
The present invention is base material by take PBAT, starch, take gather ε caprolactone (PCL), epoxy soybean oil is (ESO), take polynite or calcium carbonate, talcum powder is mineral filler, through twin screw modification granulation, again the resin after modification is added to the inflation film manufacturing machine blown film, finally obtain the film of biodegradable.This film has the advantages such as the intensity of drawing high is high, Young's modulus good, elongation at break is good.And owing to having added the lower-cost components such as starch, mineral filler, reduced significantly production cost, more easily accepted by market.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described:
Embodiment 1:
(1), take 40 parts of PBAT, 30 parts of starch, 10 parts of PCL, 10 parts of epoxy soybean oils, 10 parts of talcum powder;
(2), each starting material are added in high speed mixer in a certain order, the order added is followed successively by starch, talcum powder, PCL, epoxy soybean oil for, PBAT; Batch mixing speed is left to high speed, and high-speed mixing got final product discharging about 15 minutes;
(3), the raw material mixed is joined in the hopper of twin screw extruder, set each warm area of twin screw extruder, service temperature is 100-180 ℃, after the tie rod pelletizing, can obtain PBAT modified resin;
(4), PBAT modified resin is put into to vacuum rake dryer, temperature setting is set to 80 ℃, and vacuum bag keeps 0.01MPa, dryly within about 4 hours, can be dried to resin water content≤500ppm;
(5), dried PBAT modified resin is put into to the inflation film manufacturing machine blown film, each warm area service temperature of inflation film manufacturing machine is 100-180 ℃, finally can obtain a kind of film of complete biodegradable.
Embodiment 2:
(1), take 50 parts of PBAT, 30 parts of starch, 10 parts of PCL, 10 parts of epoxy soybean oils, 0 part of talcum powder;
(2), each starting material are added in high speed mixer in a certain order, the sequencing added be starch, talcum powder, PCL, epoxy soybean oil is, PBAT; Batch mixing speed is left to high speed, and high-speed mixing got final product discharging about 15 minutes;
(3), the raw material mixed is joined in the hopper of twin screw extruder, set each warm area of twin screw extruder, service temperature is 100-180 ℃, after the tie rod pelletizing, can obtain PBAT modified resin;
(4), PBAT modified resin is put into to vacuum rake dryer, temperature setting is set to 80 ℃, and vacuum bag keeps 0.01MPa, dryly within about 4 hours, can be dried to resin water content≤500ppm;
(5), dried PBAT modified resin is put into to the inflation film manufacturing machine blown film, each warm area service temperature of inflation film manufacturing machine is 100-180 ℃, finally can obtain a kind of film of complete biodegradable.
Embodiment 3:
(1), take 55 parts of PBAT, 30 parts of starch, 5 parts of PCL, 10 parts of epoxy soybean oils, 0 part of talcum powder;
(2), each starting material are added in high speed mixer in a certain order, the sequencing added be starch, talcum powder, PCL, epoxy soybean oil is, PBAT; Batch mixing speed is left to high speed, and high-speed mixing got final product discharging about 15 minutes.
(3), the raw material mixed is joined in the hopper of twin screw extruder, set each warm area of twin screw extruder, service temperature is 100-180 ℃, after the tie rod pelletizing, can obtain PBAT modified resin;
(4), PBAT modified resin is put into to vacuum rake dryer, temperature setting is set to 80 ℃, and vacuum bag keeps 0.01MPa, dryly within about 4 hours, can be dried to resin water content≤500ppm;
(5), dried PBAT modified resin is put into to the inflation film manufacturing machine blown film, each warm area service temperature of inflation film manufacturing machine is 100-180 ℃, finally can obtain a kind of film of complete biodegradable.
Embodiment 4:
(1), take 60 parts of PBAT, 25 parts of starch, 5 parts of PCL, 8 parts of epoxy soybean oils, 2 parts of talcum powder;
(2), each starting material are added in high speed mixer in a certain order, the sequencing added be starch, talcum powder, PCL, epoxy soybean oil is, PBAT; Batch mixing speed is left to high speed, and high-speed mixing got final product discharging about 15 minutes;
(3), the raw material mixed is joined in the hopper of twin screw extruder, set each warm area of twin screw extruder, service temperature is 100-180 ℃, after the tie rod pelletizing, can obtain PBAT modified resin;
(4), PBAT modified resin is put into to vacuum rake dryer, temperature setting is set to 80 ℃, and vacuum bag keeps 0.01MPa, dryly within about 4 hours, can be dried to resin water content≤500ppm;
(5), dried PBAT modified resin is put into to the inflation film manufacturing machine blown film, each warm area service temperature of inflation film manufacturing machine is 100-180 ℃, finally can obtain a kind of film of complete biodegradable.
Embodiment 5:
(1), take 65 parts of PBAT, 20 parts of starch, 5 parts of PCL, 6 parts of epoxy soybean oils, 4 parts of talcum powder;
(2), each starting material are added in high speed mixer in a certain order, the sequencing added be starch, talcum powder, PCL, epoxy soybean oil is, PBAT; Batch mixing speed is left to high speed, and high-speed mixing got final product discharging about 15 minutes;
(3), the raw material mixed is joined in the hopper of twin screw extruder, set each warm area of twin screw extruder, service temperature is 100-180 ℃, after the tie rod pelletizing, can obtain PBAT modified resin;
(4), PBAT modified resin is put into to vacuum rake dryer, temperature setting is set to 80 ℃, and vacuum bag keeps 0.01MPa, dryly within about 4 hours, can be dried to resin water content≤500ppm;
(5), dried PBAT modified resin is put into to the inflation film manufacturing machine blown film, each warm area service temperature of inflation film manufacturing machine is 100-180 ℃, finally can obtain a kind of film of complete biodegradable.
Embodiment 6:
(1), take 70 parts of PBAT, 25 parts of starch, 4 parts of PCL, 6 parts of epoxy soybean oils, 4 parts of talcum powder;
(2), each starting material are added in high speed mixer in a certain order, the sequencing added be starch, talcum powder, PCL, epoxy soybean oil is, PBAT; Batch mixing speed is left to high speed, and high-speed mixing got final product discharging about 15 minutes;
(3), the raw material mixed is joined in the hopper of twin screw extruder, set each warm area of twin screw extruder, service temperature is 100-180 ℃, after the tie rod pelletizing, can obtain PBAT modified resin;
(4), PBAT modified resin is put into to vacuum rake dryer, temperature setting is set to 80 ℃, and vacuum bag keeps 0.01MPa, dryly within about 4 hours, can be dried to resin water content≤500ppm;
(5), dried PBAT modified resin is put into to the inflation film manufacturing machine blown film, each warm area service temperature of inflation film manufacturing machine is 100-180 ℃, finally can obtain a kind of film of complete biodegradable.
Embodiment 7:
(1), take 60 parts of PBAT, 20 parts of starch, 5 parts of PCL, 5 parts of epoxy soybean oils, 10 parts of talcum powder;
(2), each starting material are added in high speed mixer in a certain order, the sequencing added be starch, talcum powder, PCL, epoxy soybean oil is, PBAT; Batch mixing speed is left to high speed, and high-speed mixing got final product discharging about 15 minutes;
(3), the raw material mixed is joined in the hopper of twin screw extruder, set each warm area of twin screw extruder, service temperature is 100-180 ℃, after the tie rod pelletizing, can obtain PBAT modified resin;
(4), PBAT modified resin is put into to vacuum rake dryer, temperature setting is set to 80 ℃, and vacuum bag keeps 0.01MPa, dryly within about 4 hours, can be dried to resin water content≤500ppm;
(5), dried PBAT modified resin is put into to the inflation film manufacturing machine blown film, each warm area service temperature of inflation film manufacturing machine is 100-180 ℃, finally can obtain a kind of film of complete biodegradable.
The performance of the prepared material of table 1: embodiment 1-7 each component:
Composition (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
PBAT 40 50 55 60 65 70 60
Starch 30 30 30 25 20 25 20
PCL 10 10 5 5 5 5 5
ESO 10 10 10 8 6 6 5
Talcum powder 10 0 0 2 4 4 10
Tensile strength 1.2Mpa 1.5Mpa 2.7Mpa 2.1Mpa 2.7Mpa 2.1Mpa 2.9Mpa
Elongation at break 97% 271% 199% 172% 173% 231% 139%
As can be seen from the above table, per-cent along with PBAT in material increases, the gentle tensile strength of material presents ascendant trend, elongation at break changes with the content relational degree of PBAT little, but the variation of elongation at break presents inverse ratio with talcous than row, and the add-on of epoxy soybean oil can be plastified starch, add-on is directly proportional to starch content, and PCL can increase slickness and the film-forming properties of film.

Claims (6)

1. the preparation method of a full-biodegradable film, it is characterized in that: take gather adipic acid/butylene terephthalate, starch is base material, take that to gather ε caprolactone, epoxy soybean oil, phosphorous acid dialkyl ester be softening agent, take polynite or calcium carbonate, talcum powder is mineral filler, form multipolymer under the effect of twin screw, the parts by weight of each feed composition are respectively:
40-90 parts of poly-adipic acid/butylene terephthalate
1-30 parts of starch
1-5 parts of poly-ε caprolactones
1-10 parts of epoxy soybean oils
1-10 parts of phosphorous acid dialkyl esters
0-10 parts of mineral fillers.
2. the preparation method of full-biodegradable film according to claim 1, it is characterized in that: the weight-average molecular weight of described poly-adipic acid/butylene terephthalate is between 10-20 ten thousand, and melting index is between 3-20.
3. the preparation method of full-biodegradable film according to claim 1, it is characterized in that: the weight-average molecular weight of described poly-ε caprolactone is between 10000-100000.
4. the preparation method of full-biodegradable film according to claim 1, is characterized in that: the oxirane value of described epoxy soybean oil >=6.0%.
5. the preparation method of full-biodegradable film according to claim 1, it is characterized in that: its production stage is:
(1), proportionally take various raw-material weight;
(2), each starting material are added in high speed mixer in a certain order, high-speed mixing 10-20 minutes is to evenly; The starting material addition sequence is followed successively by powder, liquid material, particulate material;
(3), the raw material mixed is joined in the hopper of twin screw extruder, set each warm area of twin screw extruder, service temperature is 100-180 ℃, after the tie rod pelletizing, can obtain PBAT modified resin;
(4), PBAT modified resin is put into to drying machine and fully be dried to water content≤500ppm;
(5), dried PBAT modified resin is put into to the inflation film manufacturing machine blown film, each warm area service temperature of inflation film manufacturing machine is 100-180 ℃, finally obtains the film of biodegradable.
6. the preparation method of full-biodegradable film according to claim 5 is characterized in that: adopt in the twin screw extruder moulding process, screw speed is 50-500RPM, and the length-to-diameter ratio of screw rod is between 25:1-55:1.
CN2013103381871A 2013-08-06 2013-08-06 Preparation method of full biodegradation film Pending CN103435981A (en)

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CN103724950A (en) * 2013-12-26 2014-04-16 安徽聚美生物科技有限公司 Composition containing PBAT (polybutyrate adipate terephthalate) and preparation method thereof as well as PBAT preservative film
CN104893004A (en) * 2015-05-27 2015-09-09 铜陵方正塑业科技有限公司 Ramie stick reinforced starch-based fully-degradable plastic film and preparation method thereof
CN104910441A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Agriculture plastic film capable of increasing soil activity directly after degradation and preparation method thereof
CN104910433A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 High temperature-resistant full-degradable plastic film and preparation method thereof
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CN104910440A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Antibacterial starch-blended full-degradable plastic film and preparation method thereof
CN104910434A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 High-efficiency oxygen-insulation water-insulation blended full-degradable plastic film and preparation method thereof
CN104910432A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Glass-fiber tension-resistant reinforced starch-polyvinyl alcohol blended full-degradable plastic film and preparation method thereof
CN104910442A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Full-degradable plastic film capable of adsorbing peculiar smell, and preparation method thereof
CN104910436A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Flame-retardant plastic film capable of being completely degraded, and preparation method thereof
CN104910426A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Full-degradable plastic film taking surface hydrophobically modified starch as base material and preparation method thereof
CN104910427A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Double-degradable plastic film with high tensile strength, and preparation method thereof
CN104910430A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Full-degradable plastic film used for far-infrared food fresh-keeping and preparation method thereof
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CN104910429A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Thermoplastic full-degradable plastic film with excellent processability and preparation method thereof
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CN104927092A (en) * 2015-05-27 2015-09-23 铜陵方正塑业科技有限公司 Starch blended degradable plastic film with antistatic effect and preparation method for starch blended degradable plastic film
CN104927095A (en) * 2015-05-27 2015-09-23 铜陵方正塑业科技有限公司 Blended degradable thin film with high gas barrier property and preparation method for blended degradable thin film
CN104893004A (en) * 2015-05-27 2015-09-09 铜陵方正塑业科技有限公司 Ramie stick reinforced starch-based fully-degradable plastic film and preparation method thereof
CN104910441A (en) * 2015-05-27 2015-09-16 铜陵方正塑业科技有限公司 Agriculture plastic film capable of increasing soil activity directly after degradation and preparation method thereof
CN105199335A (en) * 2015-09-17 2015-12-30 苏州新区佳合塑胶有限公司 Preparation method of degradable plastic thin film

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Application publication date: 20131211