CN115197557B - Low-carbon bio-based full-degradable film material and preparation method thereof - Google Patents
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Abstract
A low-carbon bio-based full-degradable film material relates to a biodegradable film, which comprises the following materials in parts by mass: 5-15 parts of polylactic acid (PLA); 20-35 parts of corn starch; 50-70 Parts of Polypropylene Carbonate (PPC); 5 parts of talcum powder; 3-7 parts of plasticizer; 0.2-0.35 part of adipic acid; 0.04-0.07 part of macromolecule super-dispersion modifier JL-G02 FX-P; 0.05 part of aluminum-titanium composite coupling agent JL-G08A/T/F; 0.5 part of hydroquinone dihydroxyethyl ether and 3280.2-0.5 part of UV; UV9440.2-0.5 part; 0.3 parts of antioxidant BHT; 1680.2 parts of an antioxidant; white oil 0.3 parts. The invention has the characteristics of degradability, difficult moisture absorption, excellent mechanical property and low carbon emission.
Description
Technical Field
The invention belongs to the technical field of full-biodegradable materials, relates to a biodegradable film, and in particular relates to a low-carbon bio-based full-degradable film material and a preparation method thereof.
Background
The disposable plastic packaging film bags are used to penetrate all corners of our lives, such as supermarket shopping bags, takeaway packing bags, garbage bags, express bags and the like, so that great convenience is brought to our lives. However, the conventional disposable plastic packaging bags are mostly made of non-degradable petroleum-based materials, so that a large amount of waste disposable plastic packaging bags not only cause waste of resources, but also cause burden of white pollution to the environment. From a long-term development, popularization of application of biodegradable materials in the field of disposable plastic packaging bags is considered as the most fundamental and effective way to solve the problem.
Among the numerous biodegradable films, starch-based biodegradable films have attracted a great deal of attention due to their low cost, high bio-based content, and the like.
The invention patent with publication number of CN113754992A (a biodegradable plastic film and a preparation method thereof) takes polylactic acid, polybutylene adipate terephthalate and starch as base materials, and the reactive solubilizer dicumyl peroxide is added into a formula system, so that the mechanical property of the film material is improved, the operation is simple, and the cost is saved.
The invention patent with publication number CN113845621A (a compatibilizer and a full-biodegradable film with high starch content adopting the compatibilizer) also uses PLA, PBAT and corn starch as base materials, and ethylene thermoplastic elastomer-maleic anhydride-glycidyl methacrylate copolymer is added into a formula system, and finally the prepared film has the advantages of high tensile strength and tearing strength, good elastic modulus, good elongation at break, good barrier property, good degradation performance, strong water resistance and moisture resistance and the like; and the filling of the modified starch with high content greatly reduces the cost.
In the patent application publication No. CN113956627A (a starch-based fully biodegradable PBAT alloy with precipitation resistance and low haze and a preparation method thereof), the crosslinking degree of the material can be improved by adding epoxy urushiol glycidyl ether with multiple epoxy groups into a PLA/PBAT/starch formula system, so that the tear resistance and dart impact resistance of the film are improved.
The three documents all use petroleum-based biodegradable resin PBAT as a main base material in a formula system, so that the defect of higher carbon emission exists; in addition, the existing starch-based biodegradable film has a series of defects of easy moisture absorption, easy migration and precipitation of plasticizer, performance degradation, narrow film blowing processing temperature and the like, so that the popularization of the starch-based biodegradable film suffers from a certain obstacle.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a low-carbon bio-based fully-degradable film material which has the characteristics of degradability, difficult moisture absorption, excellent mechanical property and low carbon emission.
The aim of the invention can be achieved by the following technical scheme: the low-carbon bio-based full-degradable film material comprises the following materials in parts by weight:
5-15 parts of polylactic acid (PLA);
20-35 parts of corn starch;
50-70 Parts of Polypropylene Carbonate (PPC);
5 parts of talcum powder;
3-7 parts of plasticizer;
0.2-0.35 part of adipic acid;
0.04-0.07 part of macromolecule super-dispersion modifier JL-G02 FX-P;
0.05 part of aluminum-titanium composite coupling agent JL-G08A/T/F;
0.5 part of hydroquinone dihydroxyethyl ether;
UV3280.2-0.5 part;
UV9440.2-0.5 parts;
0.3 parts of antioxidant BHT;
168.2 parts of an antioxidant;
white oil 0.3 parts.
Preferably, the M of polylactic acid (PLA) W 200000, optical purity 96% L.
Preferably, the polypropylene carbonate (PPC) has a melt flow rate MFR of less than or equal to 5g/10min.
Preferably, the talcum powder has a silicon content of > 55%, D50 < 15 μm and a whiteness of > 96%.
Preferably, the plasticizer is any two of diglycerol, epoxidized soybean oil and carbamide.
The invention provides a preparation method of a low-carbon bio-based fully-degradable film material, which comprises the following steps:
s1: adding corn starch and a high molecular super-dispersion modifier JL-G02FX-P into a high-speed mixer, and mixing for 2min at a rotating speed of 200 rpm; then adding a plasticizer into the high-speed mixer, and mixing for 8min after the rotating speed of the high-speed mixer is increased to 600 rpm; then adding adipic acid into a high-speed mixer, reducing the rotating speed of the high-speed mixer to 200rpm, mixing for 1min, and plasticizing and modifying the corn starch to obtain a first mixture;
s2: adding talcum powder and an aluminum-titanium composite coupling agent JL-G08A/T/F into a high-speed mixer, stirring and mixing at a rotating speed of 500rpm, and simultaneously raising the temperature in the high-speed mixer to 80 ℃ to perform activation treatment on the talcum powder to obtain a mixture II;
s3: adding polylactic acid (PLA), polypropylene carbonate (PPC), hydroquinone dihydroxyethyl ether and white oil into a mixer, and mixing for 30 seconds at a rotating speed of 80 prm; then, continuously adding UV328, UV944, antioxidant BHT and antioxidant 168 into a mixer, and mixing for 30 seconds at the rotation speed of 80prm to prepare a mixture III;
s4: adding the second mixture prepared in the step S2 into the third mixture, and mixing for 1min at the rotating speed of 80 prm; then continuously adding the first mixture prepared in the step S1, mixing for 1min at the rotating speed of 80prm, and uniformly stirring to prepare master batch;
s5: setting the temperature of the 1-9 area of the screw extruder to be 130 ℃, 155 ℃, 150 ℃, 140 ℃ and the temperature of the machine head to be 140 ℃ in sequence, adding the master batch prepared in the step S4 into a parallel double screw extruder for melt blending, and performing air cooling granulation after extrusion by the machine head to obtain the low-carbon bio-based fully-degradable film material.
The invention provides a preparation method of a low-carbon bio-based full-degradable film, which comprises the following steps:
t1: setting the temperature of a 1-5 region of a film blowing machine to be 130 ℃, 150 ℃ and 155 ℃ and blowing the film of the low-carbon bio-based fully-degradable film material by adopting a high-pressure PE film blowing machine to obtain the low-carbon bio-based fully-degradable film.
The beneficial effects of the invention are as follows:
(1) The invention takes the multielement composite modification technology of the biodegradable material as the basis, selects the biodegradable resin PPC and PLA with lower carbon emission as the main base material, creatively selects the reactive auxiliary agent hydroquinone dihydroxyethyl ether to break through the problem of interfacial compatibility of PLA/PPC/starch, so as to ensure the mechanical strength of the composite material;
(2) The plasticizer with higher stability is added through the compounding of the high-mixing treatment process, and adipic acid is added for esterification reaction, so that the defect that the starch-based biodegradable film is easy to separate out is overcome, and the shelf life of the film is longer;
(3) The aluminum-titanium composite coupling agent JL-G08A/T/F is adopted to carry out surface activation treatment on talcum powder, so that efficient compounding of a PPC/PLA/starch/talcum powder multi-element system is realized, the hydrophobic property of the starch-based biodegradable film is improved, the defect of easy moisture absorption is overcome, and meanwhile, the processing temperature range of the material can be widened due to the addition of inorganic powder.
In summary, compared with the prior art, the bio-based content in the material can reach more than 40% at the highest, and the carbon emission is lower; the moisture absorption is not easy, the plasticizer is not easy to separate out, and the shelf life of the film is longer; the film has excellent mechanical properties, the transverse and longitudinal tensile strength can reach more than 20MPa, and the transverse and longitudinal elongation at break is more than 200 percent, thereby having very important significance for solving the problem of white pollution and promoting the popularization and application of the full-biodegradable material.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The following describes the present invention in detail with reference to specific examples:
example 1
The low-carbon bio-based full-degradable film material comprises the following materials in parts by weight:
polylactic acid (PLA, M) W 200000, optical purity 96% L) 5 portions;
20 parts of corn starch;
70 parts of polypropylene carbonate (PPC, melt flow rate MFR. Ltoreq.5 g/10 min);
5 parts of talcum powder (silicon content is more than 55%, D50 is less than 15 mu m, whiteness is more than 96%);
and (3) a plasticizer: comprises 2 parts of dimeric glycerol and 1 part of epoxidized soybean oil;
0.2 parts of adipic acid;
0.04 part of macromolecule super-dispersion modifier JL-G02 FX-P;
0.05 part of aluminum-titanium composite coupling agent JL-G08A/T/F;
0.5 part of hydroquinone dihydroxyethyl ether;
UV 328.5 parts;
UV 944.5 parts;
0.3 parts of antioxidant BHT;
168.2 parts of an antioxidant;
white oil 0.3 parts.
Example 2
The low-carbon bio-based full-degradable film material comprises the following materials in parts by weight:
polylactic acid (PLA, M) W 200000, optical purity 96% L) 10 portions;
25 parts of corn starch;
60 parts of polypropylene carbonate (PPC, melt flow rate MFR. Ltoreq.5 g/10 min);
5 parts of talcum powder (silicon content is more than 55%, D50 is less than 15 mu m, whiteness is more than 96%);
and (3) a plasticizer: comprises 2 parts of epoxidized soybean oil and 3 parts of carbamide;
0.25 parts of adipic acid;
0.04 part of macromolecule super-dispersion modifier JL-G02 FX-P;
0.05 part of aluminum-titanium composite coupling agent JL-G08A/T/F;
0.5 part of hydroquinone dihydroxyethyl ether;
UV 328.4 parts;
UV 944.3 parts;
0.3 parts of antioxidant BHT;
168.2 parts of an antioxidant;
white oil 0.3 parts.
Example 3
The low-carbon bio-based full-degradable film material comprises the following materials in parts by weight:
polylactic acid (PLA, M) W 200000, optical purity 96% L) 15 parts;
30 parts of corn starch;
50 parts of polypropylene carbonate (PPC, melt flow rate MFR. Ltoreq.5 g/10 min);
5 parts of talcum powder (silicon content is more than 55%, D50 is less than 15 mu m, whiteness is more than 96%);
and (3) a plasticizer: comprises 3 parts of dimeric glycerin and 3 parts of carbonamide;
0.3 parts of adipic acid;
0.06 parts of macromolecule super-dispersion modifier JL-G02 FX-P;
0.05 part of aluminum-titanium composite coupling agent JL-G08A/T/F;
0.5 part of hydroquinone dihydroxyethyl ether;
UV 328.2 parts;
UV 944.2 parts;
0.3 parts of antioxidant BHT;
168.2 parts of an antioxidant;
white oil 0.3 parts.
Example 4
The low-carbon bio-based full-degradable film material comprises the following materials in parts by weight:
polylactic acid (PLA, M) W 200000, optical purity 96% L) 10 portions;
35 parts of corn starch;
50 parts of polypropylene carbonate (PPC, melt flow rate MFR. Ltoreq.5 g/10 min);
5 parts of talcum powder (silicon content is more than 55%, D50 is less than 15 mu m, whiteness is more than 96%);
and (3) a plasticizer: comprises 5 parts of dimeric glycerin and 2 parts of carbonamide;
0.35 parts of adipic acid;
0.07 part of macromolecule super-dispersion modifier JL-G02 FX-P;
0.05 part of aluminum-titanium composite coupling agent JL-G08A/T/F;
0.5 part of hydroquinone dihydroxyethyl ether;
UV 328.2 parts;
UV 944.2 parts;
0.3 parts of antioxidant BHT;
168.2 parts of an antioxidant;
white oil 0.3 parts.
Example 5
The preparation method of the low-carbon bio-based fully-degradable film material comprises the following steps:
s1: adding corn starch and a high molecular super-dispersion modifier JL-G02FX-P into a high-speed mixer, and mixing for 2min at a rotating speed of 200 rpm; then adding a plasticizer into the high-speed mixer, and mixing for 8min after the rotating speed of the high-speed mixer is increased to 600 rpm; then adding adipic acid into a high-speed mixer, reducing the rotating speed of the high-speed mixer to 200rpm, mixing for 1min, and plasticizing and modifying the corn starch to obtain a first mixture;
s2: adding talcum powder and an aluminum-titanium composite coupling agent JL-G08A/T/F into a high-speed mixer, stirring and mixing at a rotating speed of 500rpm, and simultaneously raising the temperature in the high-speed mixer to 80 ℃ to perform activation treatment on the talcum powder to obtain a mixture II;
s3: adding polylactic acid (PLA), polypropylene carbonate (PPC), hydroquinone dihydroxyethyl ether and white oil into a mixer, and mixing for 30 seconds at a rotating speed of 80 prm; then, continuously adding UV328, UV944, antioxidant BHT and antioxidant 168 into a mixer, and mixing for 30 seconds at the rotation speed of 80prm to prepare a mixture III;
s4: adding the second mixture prepared in the step S2 into the third mixture, and mixing for 1min at the rotating speed of 80 prm; then continuously adding the first mixture prepared in the step S1, mixing for 1min at the rotating speed of 80prm, and uniformly stirring to prepare master batch;
s5: setting the temperature of the 1-9 area of the screw extruder to be 130 ℃, 155 ℃, 150 ℃, 140 ℃ and the temperature of the machine head to be 140 ℃ in sequence, adding the master batch prepared in the step S4 into a parallel double screw extruder for melt blending, and performing air cooling granulation after extrusion by the machine head to obtain the low-carbon bio-based fully-degradable film material.
The preparation method of the low-carbon bio-based full-degradable film comprises the following steps:
t1: setting the temperature of a 1-5 region of a film blowing machine to be 130 ℃, 150 ℃ and 155 ℃ and the temperature of a die head to be 155 ℃, and blowing the film of the air-cooled granulated low-carbon bio-based fully-degradable film material by adopting a high-pressure PE film blowing machine to obtain the low-carbon bio-based fully-degradable film.
Comparative example 1
The degradable film material comprises the following materials in parts by weight:
polylactic acid (PLA, M) W 200000, optical purity 96% L) 10 portions;
35 parts of corn starch;
50 parts of polypropylene carbonate (PPC, melt flow rate MFR. Ltoreq.5 g/10 min);
5 parts of talcum powder (silicon content is more than 55%, D50 is less than 15 mu m, whiteness is more than 96%);
and (3) a plasticizer: comprises 5 parts of dimeric glycerin and 2 parts of carbonamide;
0.35 parts of adipic acid;
0.07 part of macromolecule super-dispersion modifier JL-G02 FX-P;
0.05 part of aluminum-titanium composite coupling agent JL-G08A/T/F;
UV 328.2 parts;
UV 944.2 parts;
0.3 parts of antioxidant BHT;
168.2 parts of an antioxidant;
white oil 0.3 parts.
The material formulation of comparative example 1 was the same as in example 4, except that hydroquinone dihydroxyethyl ether was absent in comparative example 1.
The film material is prepared according to the material proportion of comparative example 1, and comprises the following steps:
s1: adding corn starch and a high molecular super-dispersion modifier JL-G02FX-P into a high-speed mixer, and mixing for 2min at a rotating speed of 200 rpm; then adding a plasticizer into the high-speed mixer, and mixing for 8min after the rotating speed of the high-speed mixer is increased to 600 rpm; then adding adipic acid into a high-speed mixer, reducing the rotating speed of the high-speed mixer to 200rpm, mixing for 1min, and plasticizing and modifying the corn starch to obtain a first mixture;
s2: adding talcum powder and an aluminum-titanium composite coupling agent JL-G08A/T/F into a high-speed mixer, stirring and mixing at a rotating speed of 500rpm, and simultaneously raising the temperature in the high-speed mixer to 80 ℃ to perform activation treatment on the talcum powder to obtain a mixture II;
s3: adding polylactic acid (PLA), polypropylene carbonate (PPC) and white oil into a mixer, and mixing for 30 seconds at a rotating speed of 80 prm; then, continuously adding UV328, UV944, antioxidant BHT and antioxidant 168 into a mixer, and mixing for 30 seconds at the rotation speed of 80prm to prepare a mixture III;
s4: adding the second mixture prepared in the step S2 into the third mixture, and mixing for 1min at the rotating speed of 80 prm; then continuously adding the first mixture prepared in the step S1, mixing for 1min at the rotating speed of 80prm, and uniformly stirring to prepare master batch;
s5: setting the temperature of the 1-9 area of the screw extruder to be 130 ℃, 155 ℃, 150 ℃, 140 ℃ and the temperature of the machine head to be 140 ℃ in sequence, adding the master batch prepared in the step S4 into a parallel double screw extruder for melt blending, and performing air cooling granulation after extrusion by the machine head to obtain the low-carbon bio-based fully-degradable film material.
The method for preparing the film by adopting the film material comprises the following steps:
t1: setting the temperature of a 1-5 region of a film blowing machine to be 130 ℃, 150 ℃ and 155 ℃ and the temperature of a die head to be 155 ℃, and blowing the film of the air-cooled granulated low-carbon bio-based fully-degradable film material by adopting a high-pressure PE film blowing machine to obtain the low-carbon bio-based fully-degradable film.
Comparative example 2
The degradable film material comprises the following materials in parts by weight:
polylactic acid (PLA, M) W 200000, optical purity 96% L) 10 portions;
35 parts of corn starch;
50 parts of polypropylene carbonate (PPC, melt flow rate MFR. Ltoreq.5 g/10 min);
5 parts of talcum powder (silicon content is more than 55%, D50 is less than 15 mu m, whiteness is more than 96%);
and (3) a plasticizer: comprises 7 parts of glycerol;
0.05 part of aluminum-titanium composite coupling agent JL-G08A/T/F;
0.5 part of hydroquinone dihydroxyethyl ether;
UV 328.2 parts;
UV 944.2 parts;
0.3 parts of antioxidant BHT;
168.2 parts of an antioxidant;
white oil 0.3 parts.
The material formulation of comparative example 2 was the same as that of example 4, except that adipic acid and a high molecular super-dispersion modifier JL-G02FX-P were absent in comparative example 2.
The film material is prepared according to the material proportion of comparative example 2, and comprises the following steps:
s1: adding corn starch into a high-speed mixer, and mixing for 2min at a rotating speed of 200 rpm; then adding a plasticizer into the high-speed mixer, increasing the rotating speed of the high-speed mixer to 600rpm, mixing for 8min, and plasticizing and modifying the corn starch to obtain a first mixture;
s2: adding talcum powder and an aluminum-titanium composite coupling agent JL-G08A/T/F into a high-speed mixer, stirring and mixing at a rotating speed of 500rpm, and simultaneously raising the temperature in the high-speed mixer to 80 ℃ to perform activation treatment on the talcum powder to obtain a mixture II;
s3: adding polylactic acid (PLA), polypropylene carbonate (PPC), hydroquinone dihydroxyethyl ether and white oil into a mixer, and mixing for 30 seconds at a rotating speed of 80 prm; then, continuously adding UV328, UV944, antioxidant BHT and antioxidant 168 into a mixer, and mixing for 30 seconds at the rotation speed of 80prm to prepare a mixture III;
s4: adding the second mixture prepared in the step S2 into the third mixture, and mixing for 1min at the rotating speed of 80 prm; then continuously adding the first mixture prepared in the step S1, mixing for 1min at the rotating speed of 80prm, and uniformly stirring to prepare master batch;
s5: setting the temperature of the 1-9 area of the screw extruder to be 130 ℃, 155 ℃, 150 ℃, 140 ℃ and the temperature of the machine head to be 140 ℃ in sequence, adding the master batch prepared in the step S4 into a parallel double screw extruder for melt blending, and performing air cooling granulation after extrusion by the machine head to obtain the low-carbon bio-based fully-degradable film material.
The method for preparing the film by adopting the film material comprises the following steps:
t1: setting the temperature of a 1-5 region of a film blowing machine to be 130 ℃, 150 ℃ and 155 ℃ and the temperature of a die head to be 155 ℃, and blowing the film of the air-cooled granulated low-carbon bio-based fully-degradable film material by adopting a high-pressure PE film blowing machine to obtain the low-carbon bio-based fully-degradable film.
Comparative example 3
The degradable film material comprises the following materials in parts by weight:
polylactic acid (PLA, M) W 200000, optical purity 96% L) 10 portions;
35 parts of corn starch;
50 parts of polypropylene carbonate (PPC, melt flow rate MFR. Ltoreq.5 g/10 min);
and (3) a plasticizer: comprises 5 parts of dimeric glycerin and 2 parts of carbonamide;
0.35 parts of adipic acid;
0.07 part of macromolecule super-dispersion modifier JL-G02 FX-P;
0.5 part of hydroquinone dihydroxyethyl ether;
UV 328.2 parts;
UV 944.2 parts;
0.3 parts of antioxidant BHT;
168.2 parts of an antioxidant;
white oil 0.3 parts.
The material formulation of comparative example 3 was the same as that of example 4, except that talc powder (silicon content > 55%, D50 < 15 μm, whiteness > 96%) and aluminum titanium composite coupling agent JL-G08A/T/F were absent in comparative example 3.
The film material is prepared according to the material proportion of the comparative example 3, and comprises the following steps:
s1: adding corn starch and a high molecular super-dispersion modifier JL-G02FX-P into a high-speed mixer, and mixing for 2min at a rotating speed of 200 rpm; then adding a plasticizer into the high-speed mixer, and mixing for 8min after the rotating speed of the high-speed mixer is increased to 600 rpm; then adding adipic acid into a high-speed mixer, reducing the rotating speed of the high-speed mixer to 200rpm, mixing for 1min, and plasticizing and modifying the corn starch to obtain a first mixture;
s2: adding polylactic acid (PLA), polypropylene carbonate (PPC), hydroquinone dihydroxyethyl ether and white oil into a mixer, and mixing for 30 seconds at a rotating speed of 80 prm; then, continuously adding UV328, UV944, antioxidant BHT and antioxidant 168 into a mixer, and mixing for 30 seconds at the rotation speed of 80prm to prepare a mixture II;
s3: adding the first mixture prepared in the step S1 into the second mixture, mixing for 1min at the rotating speed of 80prm, and uniformly stirring to prepare master batch;
s4: setting the temperature of the 1-9 area of the screw extruder to be 130 ℃, 155 ℃, 150 ℃, 140 ℃ and the temperature of the machine head to be 140 ℃ in sequence, adding the master batch prepared in the step S3 into a parallel double screw extruder for melt blending, and performing air cooling granulation after extrusion by the machine head to obtain the low-carbon bio-based fully-degradable film material.
The method for preparing the film by adopting the film material comprises the following steps:
t1: setting the temperature of a 1-5 region of a film blowing machine to be 130 ℃, 150 ℃ and 155 ℃ and the temperature of a die head to be 155 ℃, and blowing the film of the air-cooled granulated low-carbon bio-based fully-degradable film material by adopting a high-pressure PE film blowing machine to obtain the low-carbon bio-based fully-degradable film.
In summary, the preparation method of the low-carbon bio-based fully degradable films disclosed in example 5 was used for preparing the low-carbon bio-based fully degradable films with the thickness of 25 μm and the breadth of 400mm in examples 1 to 4.
Films for comparison experiments having a thickness of 25 μm and a breadth of 400mm were prepared according to the preparation methods of comparative examples 1 to 3, respectively.
And carrying out related performance parameter experiments on the prepared film to obtain the following experimental data and conclusions.
(1) The mechanical properties of the films of examples 1 to 4 and the films of comparative example 1 were evaluated, and the relevant tests were carried out on a universal tensile tester (CMT-4304, shenzhen Sansium Co., ltd.) according to GB/T1040.3-2006 at a test rate of 50mm/min, and the test results are shown in Table I.
The mechanical properties of the films are shown as follows
As can be seen from the data in Table I, the mechanical properties of the films prepared in examples 1-4 are increased and then decreased with the increase of the corn starch content in the formula system, and the mechanical properties of the films prepared are optimal when the corn starch addition amount in the formula system is 25 parts; the films prepared in examples 1-4 have transverse and longitudinal tensile strength exceeding 20MPa and transverse and longitudinal elongation at break exceeding 200%, and are obviously superior to those of films prepared in comparative experiment 1, mainly because the addition of the reactive auxiliary agent hydroquinone dihydroxyethyl ether in a formula system can break through the problem of interfacial compatibility of PLA/PPC/modified starch, the hydroquinone dihydroxyethyl ether is a symmetrical aromatic diol chain extender, the tail end of the hydroquinone dihydroxyethyl ether has a hydroxyl group with higher reactivity, the tail end of the starch has a large number of carboxyl groups after esterification reaction with adipic acid, polylactic acid and PPC molecular chain ends also have a large number of carboxyl groups, and the hydroxyl group with higher activity at the tail ends of the hydroquinone dihydroxyethyl ether can carry out esterification reaction with the carboxyl groups at the tail ends of PPC, polylactic acid and modified starch, so that the problem of three-phase interfacial compatibility is broken through the solution.
(2) The films of example 4 and comparative example 2 were evaluated for mechanical property change and precipitation state before and after accelerated aging, and the accelerated aging test was performed in a programmable constant temperature and humidity oven at a temperature of 85 ℃ and a relative humidity of 85% for 24 hours; the related detection of mechanical properties is carried out on a universal tensile tester (CMT-4304, shenzhen Sansium Co., ltd.) according to GB/T1040.3-2006, the test speed is 50mm/min, and the detection result is shown in Table II.
Performance variation of different films before and after accelerated aging
From the experimental data in Table II, the films of example 4 and comparative example 2 showed a significant decrease in mechanical properties after accelerated aging, wherein the decrease in mechanical properties of the film of comparative example 2 was significantly greater than that of the film of example 4, and the film of comparative example 2 showed significant oily precipitates on the film surface after accelerated aging. The synergistic effect of the polymer super-dispersion modifier JL-G02FX-P, the compound stability plasticizer and the adipic acid with esterification in the formula system of the embodiment 4 is mainly used for inhibiting the phenomenon of retrogradation of corn starch caused by precipitation of the plasticizer, so that the stability of the film performance is enhanced.
(3) The films produced in example 4 and comparative example 3 were evaluated for water absorption, and the two films were tested for water absorption at 23℃according to GB/T1034-2008, and the test results are shown in Table III.
The water absorption mass fractions of three different films are shown in the table
| Film type | Water absorption mass fraction/% |
| Example 4 | 0.12 |
| Comparative example 3 | 0.31 |
As can be seen from the experimental results in Table three, the water absorption mass fraction of the film prepared in example 4 is significantly smaller than that of the film prepared in comparative experiment 3, mainly because the addition of the activated talcum powder in the formulation system of example 4 can improve the hydrophobic property of the film, and the degradation of the performance caused by the too high water absorption of the film is avoided.
The invention has been described above with reference to preferred embodiments, but the scope of the invention is not limited thereto, and any and all technical solutions falling within the scope of the claims are within the scope of the invention. Various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict.
Claims (3)
1. The low-carbon bio-based fully-degradable film material is characterized by comprising the following materials in parts by weight:
5-15 parts of polylactic acid (PLA);
20-35 parts of corn starch;
50-70 Parts of Polypropylene Carbonate (PPC);
5 parts of talcum powder;
3-7 parts of plasticizer;
0.2-0.35 part of adipic acid;
0.04-0.07 part of macromolecule super-dispersion modifier JL-G02 FX-P;
0.05 part of aluminum-titanium composite coupling agent JL-G08A/T/F;
0.5 part of hydroquinone dihydroxyethyl ether;
UV3280.2-0.5 part;
UV9440.2-0.5 parts;
0.3 parts of antioxidant BHT;
168.2 parts of an antioxidant;
0.3 parts of white oil;
m of the polylactic acid (PLA) W 200000, optical purity 96%;
the melt flow rate MFR of the polypropylene carbonate (PPC) is less than or equal to 5g/10min;
the silicon content of the talcum powder is more than 55%, D50 is less than 15 mu m, and the whiteness is more than 96%;
the plasticizer is any two of diglycerol, epoxidized soybean oil and carbamide.
2. A method for preparing the low-carbon bio-based fully degradable film material as claimed in claim 1, comprising the following steps:
s1: adding corn starch and a high molecular super-dispersion modifier JL-G02FX-P into a high-speed mixer, and mixing for 2min at a rotating speed of 200 rpm; then adding a plasticizer into the high-speed mixer, and mixing for 8min after the rotating speed of the high-speed mixer is increased to 600 rpm; then adding adipic acid into a high-speed mixer, reducing the rotating speed of the high-speed mixer to 200rpm, mixing for 1min, and plasticizing and modifying the corn starch to obtain a first mixture;
s2: adding talcum powder and an aluminum-titanium composite coupling agent JL-G08A/T/F into a high-speed mixer, stirring and mixing at a rotating speed of 500rpm, and simultaneously raising the temperature in the high-speed mixer to 80 ℃ to perform activation treatment on the talcum powder to obtain a mixture II;
s3: adding polylactic acid (PLA), polypropylene carbonate (PPC), hydroquinone dihydroxyethyl ether and white oil into a mixer, and mixing for 30 seconds at a rotating speed of 80 prm; then, continuously adding UV328, UV944, antioxidant BHT and antioxidant 168 into a mixer, and mixing for 30 seconds at the rotation speed of 80prm to prepare a mixture III;
s4: adding the second mixture prepared in the step S2 into the third mixture, and mixing for 1min at the rotating speed of 80 prm; then continuously adding the first mixture prepared in the step S1, mixing for 1min at the rotating speed of 80prm, and uniformly stirring to prepare master batch;
s5: setting the temperature of the 1-9 area of the screw extruder to be 130 ℃, 155 ℃, 150 ℃, 140 ℃ and the temperature of the machine head to be 140 ℃ in sequence, adding the master batch prepared in the step S4 into a parallel double screw extruder for melt blending, and performing air cooling granulation after extrusion by the machine head to obtain the low-carbon bio-based fully-degradable film material.
3. The preparation method of the low-carbon bio-based full-degradable film is characterized by comprising the following steps of:
t1: setting the temperature of a 1-5 region of a film blowing machine to be 130 ℃, 150 ℃ and 155 ℃ and the temperature of a die head to blow and mold the low-carbon bio-based fully-degradable film material according to claim 1 by adopting a high-pressure PE film blowing machine to obtain the low-carbon bio-based fully-degradable film.
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| CN113698741A (en) * | 2021-08-03 | 2021-11-26 | 金旸（厦门）新材料科技有限公司 | Starch-based fully-degradable PBAT master batch capable of being mixed for use, and preparation method and application thereof |
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