CN113801448B - Biodegradable color master batch and preparation method thereof - Google Patents

Biodegradable color master batch and preparation method thereof Download PDF

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CN113801448B
CN113801448B CN202111259980.3A CN202111259980A CN113801448B CN 113801448 B CN113801448 B CN 113801448B CN 202111259980 A CN202111259980 A CN 202111259980A CN 113801448 B CN113801448 B CN 113801448B
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polylactic acid
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color master
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CN113801448A (en
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赵毅立
李艳秋
赵建伟
赵辰
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Luohe Ruibo Plastic Co ltd
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Abstract

The invention relates to a biodegradable color master batch and a preparation method thereof, wherein a polylactic acid material is modified, and nano diamond particles and kaolin tubular nano materials are added in the color master batch preparation process, so that a compact network structure is formed in the prepared color master batch material, and the strength, toughness, modulus and other properties of the color master batch material are improved. The nano antibacterial particles are added into the color master batch material, so that peripheral bacteria can be effectively killed, and the application range and the scene of the color master batch material are widened.

Description

Biodegradable color master batch and preparation method thereof
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a biodegradable color master batch and a preparation method thereof.
Background
With the continuous development of the plastic industry, the demand of plastics is also greatly increased. Because the plastic products are not easy to decompose and recycle, the wastes thereof also become harmful white garbage and pollute the environment.
The biodegradable plastic material has excellent biodegradability, and can be widely applied to various industries. The ideal biodegradable plastic is a high molecular material which has excellent service performance, can be completely decomposed by microorganisms in the environment after being discarded, and is finally decomposed into inorganic matters to become a component of carbon circulation in nature. At present, plastics capable of being completely biodegraded are mainly prepared from natural polymers (such as starch, cellulose and chitin) or agricultural and sideline products by microbial fermentation or synthesis of polymers with biodegradability, such as thermoplastic starch plastics, aliphatic polyester, polylactic acid, starch/polyvinyl alcohol and other plastic materials. Biodegradable plastics based on natural substances such as starch and the like mainly comprise the following types: polylactic acid, polyhydroxyalkanoate, starch plastic, bioengineering plastic, biological general plastic and the like.
The polylactic acid is thermoplastic aliphatic polyester, is one of the most widely used bioplastics at present, and has good processing performance and comprehensive mechanical property. Polylactic acid also has good biocompatibility, but has the disadvantages of poor toughness, slow degradation rate, strong hydrophobicity and lack of reactive side chain groups, thereby limiting the application of the polylactic acid in certain occasions. The method of polymer copolymerization, polymer compounding and polymer blending is a common method for overcoming the defects of polylactic acid materials at present, and the poly (butylene adipate-terephthalate) copolymer is completely degradable aliphatic aromatic copolyester, has good toughness and faster biodegradation rate, but has lower strength and modulus, and also limits the popularization and application of the poly (adipate-terephthalate) copolymer. Therefore, the polylactic acid and the polybutylene adipate-terephthalate copolymer are subjected to melt blending modification, so that the advantages of the polylactic acid and the polybutylene adipate-terephthalate copolymer can be fully obtained, and the mutual defects of the polylactic acid and the polybutylene adipate-terephthalate copolymer can be compensated.
Disclosure of Invention
Although the blend modification of polylactic acid by the polybutylene adipate-terephthalate copolymer can overcome the defects, the strength, modulus and the like of the modified material can not meet the requirements. Meanwhile, in the face of some specific requirements, the toughness, mechanical strength and single-performance plastic materials of the materials still cannot meet the requirements of people.
In order to overcome the technical defects in the prior art, the invention provides a biodegradable color master batch and a preparation method thereof, which improve the strength, modulus, toughness, thermal stability and other properties of the color master batch material on the basis of not influencing the original properties by modifying and adding a plastic material modified by blending poly (butylene adipate-terephthalate) copolymer and polylactic acid, and have good antibacterial and bacteriostatic properties.
In order to achieve the above object, the present invention provides a biodegradable color masterbatch material.
A biodegradable color master batch comprises the following components in percentage by weight: 40-60% of modified polylactic acid, 10-20% of polybutylene adipate-terephthalate, 5-10% of filler, 2-6% of pigment, 1-5% of compatilizer, 0.2-1.0% of nano antibacterial particles, 2-4% of plasticizer and/or lubricant and/or filler, and the sum of the weight ratios of the components of the biodegradable color master batch is 100%.
Preferably, the modified polylactic acid is aluminum oxide modified polylactic acid with a lamellar structure.
Preferably, the filler is a mixture of fluorosilane modified nano-diamond particles and a kaolin tubular nano-material, wherein the weight ratio of the fluorosilane modified nano-diamond particles to the kaolin tubular nano-material is (1-2): 1.
preferably, the particle size of the fluorosilane modified nano-diamond particles is 10-30 nanometers, the inner diameter of the kaolin tubular nano-material is 20-50 nanometers, and the length-diameter ratio is 20-30.
Preferably, the fluorosilane used by the fluorosilane modified nano-diamond particles is one or more of heptadecafluorodecyltrimethoxysilane, perfluorooctyltriethoxysilane and perfluorodecyltrimethoxysilane.
Preferably, the compatilizer is a silane coupling agent KH550.
Preferably, the nano antibacterial particles are nano titanium dioxide and/or nano silver particles, the particle diameters of the nano titanium dioxide and the nano silver particles are 20-40nm and 20-30nm respectively, and when a mixture of the nano titanium dioxide and the nano silver particles is adopted, the weight ratio of the nano titanium dioxide to the nano silver particles is (2-4): 1.
the preparation method of the modified polylactic acid adopts aluminum oxide with a lamellar structure for modification, and comprises the following steps:
(1) Placing the aluminum oxide with the lamellar structure in a drying box for drying treatment;
(2) Mixing the dried aluminum oxide with the lamellar structure and absolute alcohol according to a certain mass ratio, and placing the mixture in a container for ultrasonic dispersion to obtain uniformly dispersed aluminum oxide dispersion liquid;
(3) Mixing an aluminate coupling agent and n-butyl alcohol according to a certain mass ratio, adding the alumina dispersion liquid obtained in the step (2) into the mixed aluminate coupling agent and n-butyl alcohol solution, then uniformly stirring at a constant temperature, after finishing a modification reaction, carrying out reduced pressure filtration, centrifugal treatment and acetone washing on the obtained mixed solution, carrying out vacuum drying treatment on the obtained product, and finally carrying out grinding treatment to obtain the modified lamellar-structure alumina material;
(4) Mixing polylactic acid homopolymer and modified lamellar-structure alumina, heating to completely melt polylactic acid, and then carrying out polymerization reaction for a certain time under a reduced pressure condition to prepare the lamellar-structure alumina modified and modified polylactic acid.
Preferably, the drying temperature in the step (1) is 50-80 ℃, the drying time is 8-10 hours, and the average grain diameter of the lamellar structure alumina is 20-40 μm.
Preferably, the mass ratio of the alumina in the lamellar structure to the absolute alcohol in the step (2) is 1:1-2, the ultrasonic dispersion temperature is 30-40 ℃, and the time is 1-2 hours.
Preferably, the mass ratio of the aluminate coupling agent to the n-butanol in the step (3) is 1:2 to 3, the modification reaction temperature is 70 to 80 ℃, the stirring speed is 500 to 600r/min, and the reaction time is 2 to 3 hours.
Preferably, in the step (4), the mass ratio of the alumina with the lamellar structure to the mixture consisting of the polylactic acid homopolymer is 2-8%, the reaction temperature is 120-180 ℃, the reaction time is 12-18 hours, and the reaction pressure is 0.09-0.095MPa.
On the other hand, the invention also provides a preparation method of the biodegradable color master batch.
A preparation method of biodegradable color master batch specifically comprises the following steps:
(1) Respectively carrying out vacuum drying treatment on modified polylactic acid, poly (butylene adipate-terephthalate), filler and nano antibacterial particles in the raw materials;
(2) Weighing the raw materials of the components according to the mass ratio, and adding the raw materials into a mixer for uniform mixing;
(3) And (3) adding the uniformly mixed raw materials of the components in the step (2) into a three-screw extruder for melt blending, extruding, cooling, bracing, cutting and granulating to obtain the biodegradable color master batch material.
Preferably, the drying temperature of the polylactic acid and the polybutylene adipate-terephthalate modified in the step (1) is 50-70 ℃ for 4-6 hours, and the drying temperature of the filler and the nano-antibacterial particles is 60-80 ℃ for 3-5 hours.
Preferably, the mixing and stirring speed in the step (2) is 800-1200r/min, the mixing time is 5-10 minutes, and the mixing temperature is not higher than 80 ℃.
Preferably, the extrusion temperature in the step (3) is 180-200 ℃, and the rotation speed of the extruder is 80-100r/min.
Compared with the prior art, the biodegradable color master batch obtained by the invention has the technical advantages and beneficial effects that:
(1) The carrier resin polylactic acid and the poly (butylene adipate-terephthalate) selected by the invention are biodegradable materials, and the biodegradation rate of the obtained color master batch is more than 90 percent and is far higher than the requirement that the biodegradation rate of the biodegradable material specified in the national standard GB/T20197 needs to be more than or equal to 60 percent.
(2) According to the invention, the aluminum oxide with a lamellar structure is adopted to modify and modify the polylactic acid material in advance, so that on one hand, the strength and mechanical property of the color master batch material can be improved, the loss of the strength and mechanical property of the polylactic acid caused by adding the polybutylene adipate-terephthalate copolymer is compensated, and the storage modulus of the color master batch material can also be improved. On the other hand, the aluminum oxide with the lamellar structure is modified by the aluminate coupling agent, so that the surface of the aluminum oxide with the lamellar structure is functionalized, the aluminum oxide with the lamellar structure can be more uniformly dispersed in the color master batch material, the aluminum oxide with the lamellar structure can also play a role in improving the compatilizer, good interface interaction is formed on the surface between the interface of the polylactic acid and the polybutylene adipate-terephthalate copolymer, and the toughness and the elongation at break of the color master batch material are improved.
(3) The invention adopts the lamellar alumina to be added into the color master batch material, and compared with the traditional added granular reinforcing material, the lamellar alumina has lamellar structure and the aluminate coupling agent is modified, so that a network structure can be formed in the material after melt blending. The kaolin tubular nano material in the filler and the aluminum oxide with the lamellar structure also have good synergistic effect, on one hand, the kaolin tubular nano material can form new network connection between the network structures of the aluminum oxide textures with the lamellar structure, on the other hand, the kaolin tubular nano material can also be filled between the layers of the aluminum oxide materials with the lamellar structure with the micron size, and after the two effects are mutually superposed, the elastic modulus and the tensile fracture resistance of the color master batch material can be greatly improved.
(4) The nano diamond particles modified by the fluorosilane in the filler can play a role in improving the strength and the thermal stability of the color master batch material and increasing the storage modulus of the color master batch material, and have good hydrophobic property due to the modification treatment of the nano diamond particles by the fluorosilane. Meanwhile, the kaolin tubular nano material adopted by the invention also has certain hydrophobic property. Therefore, the color master batch material prepared by the invention has good hydrophobic property, can meet the use requirements of certain occasions, and widens the application scene of the color master batch material.
(5) The color master batch material prepared by the invention is also added with nano antibacterial particles, can effectively kill harmful bacteria such as escherichia coli and the like, and can be used for manufacturing packaging materials of various foods and foods.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. Other embodiments, which can be obtained by persons skilled in the art without any inventive work based on the embodiments in the present invention, are within the protection scope of the present invention.
The first embodiment is as follows:
a preparation method of modified polylactic acid specifically comprises the following steps:
(1) Drying the aluminum oxide with the lamellar structure in a drying oven at the drying temperature of 80 ℃ for 8 hours, wherein the particle size of the aluminum oxide with the lamellar structure is 40 mu m;
(2) Mixing the aluminum oxide of the lamellar structure after drying treatment with absolute alcohol according to a certain mass ratio, placing the mixture in a container for ultrasonic dispersion to obtain an aluminum oxide dispersion liquid with uniform dispersion, wherein the mass ratio of the aluminum oxide of the lamellar structure to the absolute alcohol is 1:2, the ultrasonic dispersion treatment temperature is 40 ℃, and the time is 2 hours;
(3) Mixing an aluminate coupling agent and n-butyl alcohol according to a certain mass ratio, adding the alumina dispersion liquid obtained in the step (2) into the mixed aluminate coupling agent and n-butyl alcohol solution, then uniformly stirring at constant temperature, after finishing the modification reaction, carrying out pressure reduction filtration, centrifugal treatment and acetone washing on the obtained mixed solution, carrying out vacuum drying treatment on the obtained product, and finally grinding to obtain the modified aluminum oxide material with a lamellar structure, wherein the mass ratio of the aluminate coupling agent to the n-butyl alcohol is 1:2, the modification reaction temperature is 80 ℃, the stirring speed is 600r/min, and the reaction time is 3 hours;
(4) Mixing polylactic acid homopolymer and modified aluminum oxide with a lamellar structure, heating to completely melt the polylactic acid, and then carrying out polymerization reaction for a certain time under a reduced pressure condition to prepare the aluminum oxide modified and modified polylactic acid with the lamellar structure, wherein the mass ratio of the aluminum oxide with the lamellar structure to the mixture consisting of the aluminum oxide with the polylactic acid homopolymer is 6%, the reaction temperature is 160 ℃, the reaction time is 16 hours, and the reaction pressure is 0.09MPa.
Example two:
a preparation method of biodegradable color master batch specifically comprises the following steps:
(1) Respectively carrying out vacuum drying treatment on modified polylactic acid, polybutylene adipate-terephthalate, a filler and nano antibacterial particles in raw materials, wherein the drying treatment temperature of the modified polylactic acid and the polybutylene adipate-terephthalate is 60 ℃ for 5 hours, and the drying treatment temperature of the filler and the nano antibacterial particles is 80 ℃ for 4 hours;
(2) Weighing the raw materials of the components according to the following mass ratio, adding the raw materials into a mixer for uniform mixing, wherein the modified polylactic acid is 60%, the polybutylene adipate-terephthalate is 20%, the filler is 6%, the pigment is 4%, the compatilizer is 5%, the nano antibacterial particles are 1.0%, the plasticizer and/or the lubricant and/or the filler are 4%, the mixing and stirring speed is 1000r/min, the mixing time is 8 minutes, and the mixing temperature is 80 ℃;
(3) And (3) adding the raw materials of the components uniformly mixed in the step (2) into a three-screw extruder for melt blending, extruding, cooling, bracing, cutting and granulating to obtain the biodegradable color master batch material, wherein the extrusion temperature is 180 ℃, and the rotating speed of the extruder is 100r/min.
This example uses the modified polylactic acid material prepared in the first example.
Comparative example one:
a preparation method of modified polylactic acid specifically comprises the following steps:
(1) Drying the alumina particles with the spherical structure in a drying box at the drying temperature of 80 ℃ for 8 hours, wherein the particle size of the alumina with the spherical structure is 40 mu m;
(2) Mixing the dried alumina with the spherical structure and the anhydrous alcohol according to a certain mass ratio, placing the mixture in a container for ultrasonic dispersion to obtain uniformly dispersed alumina dispersion liquid, wherein the mass ratio of the alumina with the spherical structure to the anhydrous alcohol is 1:2, the ultrasonic dispersion treatment temperature is 40 ℃, and the time is 2 hours;
(3) Mixing an aluminate coupling agent and n-butanol according to a certain mass ratio, adding the alumina dispersion liquid obtained in the step (2) into the mixed aluminate coupling agent and n-butanol solution, then uniformly stirring at a constant temperature, after finishing a modification reaction, carrying out reduced pressure filtration, centrifugal treatment and acetone washing on the obtained mixed solution, carrying out vacuum drying treatment on the obtained product, and finally carrying out grinding treatment to obtain the modified spherical alumina material, wherein the mass ratio of the aluminate coupling agent to the n-butanol is 1:2, the modification reaction temperature is 80 ℃, the stirring speed is 600r/min, and the reaction time is 3 hours;
(4) Mixing polylactic acid homopolymer and modified spherical alumina, heating to completely melt the polylactic acid, and then carrying out polymerization reaction for a certain time under a reduced pressure condition to prepare the spherical alumina modified and modified polylactic acid, wherein the mass ratio of the spherical alumina to the polylactic acid homopolymer is 6%, the reaction temperature is 160 ℃, the reaction time is 16 hours, and the reaction pressure is 0.09MPa.
Comparative example two:
a preparation method of modified polylactic acid specifically comprises the following steps:
(1) Drying the aluminum oxide with the lamellar structure in a drying oven at the drying temperature of 80 ℃ for 8 hours, wherein the particle size of the aluminum oxide with the lamellar structure is 40 mu m;
(2) Mixing a polylactic acid homopolymer with the dried aluminum oxide with the lamellar structure in the step (1), heating to completely melt the polylactic acid, and then carrying out polymerization reaction for a certain time under a reduced pressure condition to prepare the lamellar structure aluminum oxide modified and modified polylactic acid, wherein the mass ratio of the lamellar structure aluminum oxide to the polylactic acid homopolymer mixture is 6%, the reaction temperature is 160 ℃, the reaction time is 16 hours, and the reaction pressure is 0.09MPa.
Comparative example three:
a preparation method of biodegradable color master batch specifically comprises the following steps:
(1) Respectively carrying out vacuum drying treatment on modified polylactic acid, polybutylene adipate-terephthalate, a filler and nano antibacterial particles in raw materials, wherein the drying treatment temperature of the modified polylactic acid and the polybutylene adipate-terephthalate is 60 ℃ for 5 hours, and the drying treatment temperature of the filler and the nano antibacterial particles is 80 ℃ for 4 hours;
(2) Weighing the raw materials of the components according to the following mass ratio, adding the raw materials into a mixer for uniform mixing, wherein the modified polylactic acid is 60%, the polybutylene adipate-terephthalate is 20%, the filler is 6%, the pigment is 4%, the compatilizer is 5%, the nano antibacterial particles are 1.0%, the plasticizer and/or the lubricant and/or the filler are 4%, the mixing and stirring speed is 1000r/min, the mixing time is 8 minutes, and the mixing temperature is 80 ℃;
(3) And (3) adding the raw materials of the components uniformly mixed in the step (2) into a three-screw extruder for melt blending, extruding, cooling, bracing, cutting and granulating to obtain the biodegradable color master batch material, wherein the extrusion temperature is 180 ℃, and the rotating speed of the extruder is 100r/min.
The modified polylactic acid material prepared in the first comparative example is adopted in the embodiment.
Comparative example four:
a preparation method of biodegradable color master batch specifically comprises the following steps:
(1) Respectively carrying out vacuum drying treatment on modified polylactic acid, polybutylene adipate-terephthalate, a filler and nano antibacterial particles in raw materials, wherein the drying treatment temperature of the modified polylactic acid and the polybutylene adipate-terephthalate is 60 ℃ for 5 hours, and the drying treatment temperature of the filler and the nano antibacterial particles is 80 ℃ for 4 hours;
(2) Weighing the raw materials of the components according to the following mass ratio, adding the raw materials into a mixer for uniform mixing, wherein the modified polylactic acid is 60%, the polybutylene adipate-terephthalate is 20%, the filler is 6%, the pigment is 4%, the compatilizer is 5%, the nano antibacterial particles are 1.0%, the plasticizer and/or the lubricant and/or the filler are 4%, the mixing and stirring speed is 1000r/min, the mixing time is 8 minutes, and the mixing temperature is 80 ℃;
(3) And (3) adding the uniformly mixed raw materials of the components in the step (2) into a three-screw extruder for melt blending, extruding, cooling, bracing, cutting and granulating to obtain the biodegradable color master batch material, wherein the extrusion temperature is 180 ℃, and the rotating speed of the extruder is 100r/min.
The modified polylactic acid material prepared in the comparative example II is adopted in the embodiment.
The biodegradable color master batch prepared in the second embodiment, the third embodiment and the fourth embodiment is prepared into a film by adopting a film blowing machine, and the preparation method comprises the following specific steps: before film making, the biodegradable color master batch prepared in the embodiment and the comparative example is placed in an oven at 60 ℃ for drying treatment for 24 hours, then the color master batch material accounting for 4.0 percent of the total mass of the polylactic acid and the polybutylene adipate-terephthalate is added into mixed resin consisting of the polylactic acid and the polybutylene adipate-terephthalate according to mass percentage, three-layer co-extrusion film blowing machine is used for preparing three-layer co-extrusion films, the temperatures of 1-5 sections of an outer layer heating zone are 120 ℃, 124 ℃, 126 ℃, 128 ℃ and 130 ℃, the temperatures of 1-5 sections of a middle layer heating zone are 120 ℃, 125 ℃, the temperatures of 1-5 sections of an inner layer heating zone are 120 ℃, 125 ℃, 130 ℃, the temperatures of a splitter zone and a die body zone are 130 ℃, film materials with the thickness of 0.015mm are obtained by controlling the film blowing speed, and the prepared film materials are subjected to bag making treatment to obtain the biodegradable packaging bags.
For comparison, a blank film material without the color master batch prepared by the method is prepared, and is made into a packaging bag for detection as a blank test.
And (3) performance detection:
1. aging test under normal temperature and normal humidity conditions: the three packaging bag samples prepared by the method are placed in a shading packaging box, and are tested for 180 days under the conditions of normal temperature and normal humidity, and the specific time is 7-12 months.
2. And (3) testing mechanical properties: the tensile strength and the elongation at break are tested on an electronic universal tester according to the national standard GB/T1040-2006, and the tensile rate is 100mm/min.
Figure BDA0003325205480000071
As can be seen from the above examples and comparative test results, in both the second example and the comparative examples, the transverse and longitudinal tensile strengths of the material before aging and after aging were improved to different degrees compared to the blank material prepared without adding the color master batch material, because the color master batch material was added with alumina, fluorosilane-modified nanodiamond particles and kaolin tubular nanomaterial in different ways. The effect of improving the transverse and longitudinal tensile strength of the two pairs of wrapping materials of example two is more remarkable compared with the three and four of comparative examples, because: in the third comparative example, spherical alumina particles are adopted, do not have a lamellar structure, only can form a certain network structure, and cannot be intercalated with the kaolin tubular nano material under the coaction, so that a more compact network structure with higher strength and toughness is formed, and the synergistic effect between the spherical alumina particles and the kaolin tubular nano material is relatively weaker; in the comparative example four, although the alumina material with the lamellar structure is adopted, the alumina material is not modified by the aluminate coupling agent, the alumina with the lamellar structure can form intercalation compounding with the kaolin tubular nano material, but a compact network structure cannot be formed in the masterbatch material due to the fact that the alumina material is not modified by the aluminate coupling agent, and the effect of improving the tensile strength of the material is limited.
In addition, the tensile fracture test is carried out on the prepared packaging bag material, and the result shows that the transverse and longitudinal elongations before and after aging of the second embodiment are obviously improved compared with the third and fourth embodiments and the blank test, and the color master batch material prepared by the invention is used for the packaging bag material, so that the strength of the packaging bag material can be obviously improved.
3. Test of antibacterial Property
And sealing the cooked food by using the film packaging bag materials prepared in the second embodiment and the blank test respectively, sampling to detect the bacterial concentration, placing the food in the same environment for 24 hours, and sampling again to detect the bacterial concentration. The detected bacteria are Escherichia coli and Listeria monocytogenes which are common in food.
The detection results show that the concentrations of Escherichia coli and Listeria monocytogenes in the samples before sealing are respectively 4.48log 10 CFU/mL and 5.97log 10 CFU/mL. After 24 hours of storage, the concentrations of Escherichia coli and Listeria monocytogenes in the food sealed by the packaging materials of the blank test group were respectively increased to 9.83log 10 CFU/mL and 9.42log 10 CFU/mL, and the concentration of E.coli and Listeria monocytogenes in the food sealed with the packaging material prepared in example two was reduced to 3.52log 10 CFU/mL and 4.06log 10 CFU/mL. Test results show that the antibacterial and bactericidal properties of the film material can be remarkably improved by adding the nano antibacterial particles into the color master batch material; on the other hand, due to the hydrophobic property of the film material, the adhesion of moisture can be reduced, and the bacteriostatic effect is achieved to a certain extent.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation to the present invention. Having described the invention with reference to an exemplary embodiment, it is understood that the terms used are words of description and illustration, rather than words of limitation, and that changes may be made in the invention within the scope of the claims and the invention will be modified without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other equally functional means and applications.

Claims (7)

1. A biodegradable color master batch comprises the following components in percentage by weight: 40-60% of modified polylactic acid, 10-20% of polybutylene adipate-terephthalate, 5-10% of filler, 2-6% of pigment, 1-5% of compatilizer, 0.2-1.0% of nano antibacterial particles, 2-4% of plasticizer and/or lubricant and/or filler, and the sum of the weight ratios of all the components of the biodegradable color master batch is 100%;
wherein the filler is fluorine silane modified nano-diamond particles and kaolin tubular nano-material, and the weight ratio of the fluorine silane modified nano-diamond particles to the kaolin tubular nano-material is (1-2): 1, the fluorosilane is one or more of heptadecafluorodecyltrimethoxysilane, perfluorooctyltriethoxysilane and perfluorodecyltrimethoxysilane;
the particle size of the nano diamond particles is 10-30 nanometers, the inner diameter of the kaolin tubular nano material is 20-50 nanometers, and the length-diameter ratio is 20-30;
the specific preparation method of the modified polylactic acid comprises the following steps:
(1) Drying the lamellar structure alumina in a drying oven at 50-80 deg.C for 8-10 hr to obtain lamellar structure alumina with average particle diameter of 20-40 μm;
(2) Mixing the dried aluminum oxide with the lamellar structure and the anhydrous alcohol according to a certain mass ratio, placing the mixture in a container for ultrasonic dispersion to obtain uniformly dispersed aluminum oxide dispersion liquid, wherein the mass ratio of the aluminum oxide with the lamellar structure to the anhydrous alcohol is 1:1-2, wherein the ultrasonic dispersion temperature is 30-40 ℃, and the time is 1-2 hours;
(3) Mixing an aluminate coupling agent and n-butyl alcohol according to a certain mass ratio, adding the alumina dispersion liquid obtained in the step (2) into the mixed aluminate coupling agent and n-butyl alcohol solution, then uniformly stirring at a constant temperature, after finishing a modification reaction, carrying out reduced pressure filtration, centrifugal treatment and deionized water washing on the obtained mixed solution, carrying out vacuum drying treatment on the obtained product, and finally carrying out grinding treatment to obtain the modified aluminum oxide material with a lamellar structure, wherein the mass ratio of the aluminate coupling agent to the n-butyl alcohol is 1:2-3, the modification reaction temperature is 70-80 ℃, the stirring speed is 500-600r/min, and the reaction time is 2-3 hours;
(4) Mixing polylactic acid homopolymer and modified aluminum oxide with a lamellar structure, heating to completely melt the polylactic acid, and then carrying out polymerization reaction for a certain time under a reduced pressure condition to prepare the aluminum oxide modified and modified polylactic acid with the lamellar structure, wherein the mass ratio of the aluminum oxide with the lamellar structure to the mixture of the polylactic acid homopolymer is 2-8%, the reaction temperature is 120-180 ℃, the reaction time is 12-18 hours, and the reaction pressure is 0.09-0.095MPa.
2. Biodegradable color masterbatch according to claim 1, characterized in that: wherein the compatilizer is a silane coupling agent KH550;
the nano antibacterial particles are nano titanium dioxide and/or nano silver particles, the particle sizes of the nano titanium dioxide and the nano silver particles are 20-40nm and 20-30nm respectively, and when a mixture of the nano titanium dioxide and the nano silver particles is adopted, the weight ratio of the nano titanium dioxide to the nano silver particles is (2-4): 1.
3. a method for preparing a biodegradable color masterbatch according to claim 1 or 2, comprising the following steps:
(1) Respectively carrying out vacuum drying treatment on modified polylactic acid, poly (butylene adipate-terephthalate), filler and nano antibacterial particles in the raw materials;
(2) Weighing raw materials of each component according to the mass ratio of each component in the raw materials for preparing the color master batch, and adding the raw materials into a mixer for uniform mixing;
(3) And (3) adding the uniformly mixed raw materials of the components in the step (2) into a three-screw extruder for melt blending, extruding, cooling, bracing, cutting and granulating to obtain the biodegradable color master batch material.
4. The production method according to claim 3, characterized in that: the drying treatment temperature of the modified polylactic acid and the poly (butylene adipate-terephthalate) in the step (1) is 50-70 ℃ for 4-6 hours, and the drying treatment temperature of the filler and the nano antibacterial particles is 60-80 ℃ for 3-5 hours.
5. The production method according to claim 3 or 4, characterized in that: in the step (2), the mixing and stirring speed is 800-1200r/min, the mixing time is 5-10 minutes, and the mixing temperature is not higher than 80 ℃.
6. The production method according to claim 3 or 4, characterized in that: in the step (3), the extrusion temperature is 180-200 ℃, and the rotating speed of the extruder is 80-100r/min.
7. Use of a biodegradable color masterbatch according to any one of claims 1-2 and a biodegradable color masterbatch prepared according to the preparation method of any one of claims 3-6 in the field of food packaging.
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