CN113736232A - Modified biodegradable material and preparation method thereof - Google Patents
Modified biodegradable material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified biodegradable material and a preparation method thereof, wherein the modified biodegradable material is prepared from the following components in percentage by weight: biodegradable material, 50-90%, preferably 65-85%; starch, 5-40%, preferably 10-30%; high melting point solid dispersant, 1-10%, preferably 2-7%; 0.1-1% of opening agent. The invention can obtain the starch filling biodegradable material with no crystal point and non-stick surface.
Description
Technical Field
The invention relates to a biodegradable material, in particular to a modified biodegradable material and a preparation method thereof.
Background
Biodegradable materials refer to a class of plastics that can be degraded by the action of microorganisms that occur in nature, such as bacteria, molds (fungi), and algae. The ideal biodegradable material has excellent use performance and can be completely degraded in natural environment after being used. Currently, the common biodegradable materials include a copolymer (PBAT) of butylene adipate and butylene terephthalate, polylactic acid (PLA), polybutylene succinate (PBS), poly-beta-hydroxybutyrate (PHB), Polyhydroxyalkanoate (PHA) and the like. The common modification mode for the biodegradable material is to add a filling system, such as starch, talcum powder, calcium carbonate and the like, wherein the starch belongs to a material capable of being completely biodegraded, and the application prospect of the filling system as the biodegradable material is the most extensive. However, the main component of starch is glucose, which has strong intermolecular force and is easy to agglomerate, so that crystal points exist during product molding.
In order to solve the problem of starch dispersion, the most common method at present is to add glycerol as a dispersing agent, and the glycerol is permeated among starch particles, so that the intermolecular force of the starch is reduced, and the joint is easy to slide, thereby avoiding starch agglomeration. However, since glycerin is a liquid, and the amount of glycerin added is usually 25% of the weight of starch, a large amount of glycerin needs to be discharged during the addition process, the field smoke is large during the molding of the product, serious safety hazards exist, and the product has the problems of glycerin precipitation, surface stickiness and the like.
When the patent CN201810913075.7 is used for producing and processing a starch composite biodegradable polymer material, the surface of starch particles is firstly subjected to one or more types of ecologically safe acid or acid anhydride reaction treatment, and then the starch particles and the biodegradable polymer material are blended to prepare the starch/biodegradable polymer composite material. However, the method has large workload of modifying the surface of the starch, the operation steps are complicated, and the modified starch needs to be mixed with unmodified starch for use, so that the problem of starch dispersion cannot be completely solved.
Patent CN202010958714.9 discloses a method for preparing a completely biodegradable starch composite mulching film, which comprises preparing starch granules by amylase enzymolysis modification to form starch clusters and starch short chains with a cross-bottom degree of polymerization, and then processing and pasting to effectively improve the binding property of starch materials and resin matrix and improve the mechanical strength of the materials, but the enzyme treatment is not controllable on one hand, and on the other hand, the application field of the starch clusters is limited due to the existence of the starch clusters, so that the starch composite mulching film cannot be used as shopping bags, bubble films and the like.
In patent CN201310153446.3, starch, PBAT, a plasticizer, a compatilizer, an initiator, a hydrophobic modifier, a lubricant, an antioxidant and a filler are mixed, extruded and granulated to prepare starch master batches, and then a modified biodegradable material is prepared. However, the starch is extruded by two double screws to cause the color of the product to become dark, and the product is difficult to use as a white product.
The starch filled biodegradable material prepared by the patent technology has the problems of insufficient starch dispersion, complex preparation process, small product application range and the like, and a new solution is required to be found to realize the problems of dispersion, surface stickiness and the like of the starch filled biodegradable material.
Disclosure of Invention
In order to solve the technical problems, the invention provides a modified biodegradable material and a preparation method thereof, and the modified biodegradable material can be used for obtaining a starch-filled biodegradable material with no crystal point and no stickiness on the surface.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a modified biodegradable material is prepared from the following components in percentage by weight:
biodegradable material, 50-90%, preferably 65-85%;
starch, 5-40%, preferably 10-30%;
high melting point solid dispersant, 1-10%, preferably 2-7%;
0.1-1% of opening agent.
In some examples of the invention, the biodegradable material comprises some biodegradable material that can be added with starch to form a filled system, for example, can be one or more of butylene adipate and copolymer of butylene glycol (PBAT), polylactic acid (PLA), polybutylene succinate (PBS).
The butanediol adipate and butanediol ester copolymer preferably has a melt index range of 3-6g/10min (190 ℃, 2.16 kg); the melting range of the polylactic acid is preferably 3-10g/10min (190 ℃, 2.16 kg); the preferred melt index range of the poly (butylene succinate) is 3-15g/10min (190 ℃, 2.16 kg).
The starch has complete biodegradability in various environments and wide sources, and the starch is used as a filling material to be added into the biodegradable material to prepare the modified material based on the characteristics, so that the manufacturing cost of the product can be greatly reduced, and the biodegradation rate of the modified material can be improved. In theory, a starch-containing bio-based feedstock or any modified starch may be used in and accomplish the present invention. In some preferred examples, the starch is one or more of corn starch, sweet potato starch, tapioca starch, wheat starch.
In some examples of the present invention, the high melting point solid dispersant is a solid monomer with a melting point of 100-, boiling point 211 deg.C).
The invention adopts the high-melting-point solid dispersing agent to disperse the starch, the high-melting-point solid dispersing agent is in a liquid state at the temperature above the melting point, and can be mixed with the starch at high temperature to permeate into starch granules, so that the intermolecular acting force of the starch is reduced, the connected sections are easier to slide, and the modified biodegradable material with good starch dispersion and difficult agglomeration is formed, thereby solving the technical problems of crystal points and rough surface of the product. Meanwhile, the high-melting-point solid dispersing agent is in a solid state at the temperature below the melting point, and cannot migrate to the surface of a product in the normal-temperature storage process of the product after a modified biodegradable material is formed, so that the technical problems of precipitation and stickiness on the surface of the product are solved.
In some examples of the invention, the opening agent is one or more of stearic acids, mesoacid amides, oleamide, Ethylene Bis Stearamide (EBS), talc. The opening agent is a common additive used in the production and preparation process of plastic film products, and can effectively improve the opening performance of the film.
The invention also provides a preparation method of the modified biodegradable material, which comprises the following steps:
1) uniformly mixing starch, a high-melting-point solid dispersant and an opening agent in a high-speed mixer; the starch and the high-melting-point solid dispersing agent are blended at high temperature, so that the high-melting-point solid dispersing agent can penetrate into starch granules in a liquid state to improve the dispersibility of the starch, and partial water in the starch can be removed to slow down the hydrolysis of the biodegradable material in the processing process and ensure the mechanical property of the modified material;
2) and (3) premixing the mixture and the biodegradable material, and then extruding and granulating through a double-screw extruder to obtain the modified biodegradable material.
In some examples of the present invention, the mixing conditions of the high-speed mixer in step 1) are: the temperature is 100-;
preferably, the operating conditions of the twin-screw extruder in step 2) are: the screw temperature is 135 ℃ to 180 ℃, preferably 140 ℃ to 175 ℃; the rotation speed is 200-500rpm, preferably 250-400 rpm.
More preferably, the premixing conditions of the raw materials in the step 2) are as follows: the temperature is 20-45 deg.C, preferably 25-40 deg.C, the rotation speed is 20-100rpm, preferably 30-80rpm, and the mixing time is 2-8min, preferably 4-7 min.
In the present invention, "%" unless otherwise specified means mass percent "% by weight".
Compared with the prior art, the invention has the advantages that:
1) the invention solves the problem of starch dispersion in the starch filled biodegradable material, and simultaneously solves the problem of precipitation caused by the small molecular glycerol as a dispersant, so that the prepared workpiece is smooth and has no crystal point, and the surface is not sticky;
2) under the condition of high-temperature mixing, the moisture content in the starch is greatly reduced, the problem that the biodegradable material is degraded due to the influence of the moisture content in the processing process can be controlled, and the mechanical property of the material is ensured;
3) no liquid auxiliary agent is used, the field smog is less in the processing and forming stages, and the potential safety hazard is low;
4) the modified biodegradable material is extruded by a double-screw extruder only once in the preparation process, so that the product can be prevented from being darkened, and the application of the product in a white product is ensured;
5) preferably, an organic solid monomer containing at least one functional group of hydroxyl, carboxyl and fluorine atoms is used as a high-melting-point solid dispersant, so that the organic solid monomer can fully wrap starch particles in the high-temperature mixing process and simultaneously has stronger traction and fixation effects on starch molecules, thereby promoting the starch dispersion and avoiding the dispersant from migrating to the surface of a product;
6) the modified biodegradable material without crystal points and surface stickiness can be obtained by adopting a relatively simple preparation process;
7) the prepared modified biodegradable material can be widely applied to shopping bags, bubble membranes, mulching films and the like.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The raw material information used in the examples and comparative examples is shown in the table:
TABLE 1 raw material information
The test method and the rating standard adopted by the invention are as follows:
(1) testing crystal points: after the film is blown, the surface of the film is observed by naked eyes, no crystal point within the range of 10cm x 10cm is 1 grade, no more than 3 crystal points are 2 grades, no more than 5 crystal points are 3 grades, no more than 10 crystal points are 4 grades, and more than 10 crystal points are 5 grades;
(2) surface roughness test: the surface of the film is touched by hands with roughness, the surface is smooth and has no rough feeling of grade 1, the surface has slight rough feeling of grade 2, the rough feeling is obviously grade 3, and the rough feeling is obviously grade 4;
(3) surface tack testing: storing the film bag at 23 ℃ for 3 months, observing the surface of the film, and classifying the film into 1-4 grades according to the sticky condition, wherein the 1 grade surface is not sticky, the 2 grade surface is slightly sticky, the 3 grade surface has a relatively obvious sticky phenomenon, and the 4 grade surface is very serious in sticky phenomenon;
(4) tensile strength: the tensile strength is tested according to standard ISO 527, the sample bar size is 170mm multiplied by 10mm multiplied by 4mm, the tensile rate is 500 mm/min;
(5) color difference b value: the test equipment is a color measuring instrument of Hunterlab company, the model is UltraScan VIS, and the sample is product particles;
the equipment adopted by the invention is as follows:
high mixing machine: a 120L pan type high mixing machine, Suzhou Songyuan environmental protection science and technology Limited, with oil bath heating;
a double-screw extruder: the used double-screw extruder is a product of Kedoulong mechanical Co., Ltd, and the model is ZSK 32 Mc;
film blowing machine: the film blowing machine is a product of Zhejiang casting machine Co., Ltd, and the model is SJ-35600.
Example 1
Preparing raw materials with the total mass of 100KG according to the following formula:
PBAT TH801T，73.7％；
PLA L175，2％；
corn starch JYM001, 20%;
4% of ethyl 2, 4-dihydroxy-6-methylcarbamate;
0.3 percent of opening agent ER.
Uniformly mixing the weighed corn starch, 2, 4-dihydroxy-6-ethyl methyl formate and the opening agent in a high-speed mixer, wherein the operating temperature of the high-speed mixer is 150 ℃, the rotating speed is 300rpm, and the mixing time is 25min to obtain a starch mixture;
premixing the starch mixture and PBAT TH801T by using a high-speed mixer, wherein the premixing temperature is 35 ℃, the rotating speed is 50rpm, and the mixing time is 6 min; extruding and granulating by a double-screw extruder to obtain the modified biodegradable material, wherein the screw temperature is set to be 60 ℃, 100 ℃, 180 ℃, 160 ℃, 140 ℃ and 135 ℃ in a segmentation way from the feed inlet to the machine head, and the rotating speed is 300 rpm.
Comparative example 1
The modified biodegradable material was prepared according to the materials selected in example 1 (except that no ethyl 2, 4-dihydroxy-6-methylcarboxylate was added) and the amount (KG) used, and under the process conditions of example 1.
Example 2
Preparing raw materials with the total mass of 100KG according to the following formula:
PBAT KHB21，52.9％；
PLA LX575，10％；
30% of sweet potato starch;
7% of 2-fluoro-6-hydroxybenzoic acid;
opening agent 212, 0.1%.
Uniformly mixing the weighed sweet potato starch, 2-fluoro-6-hydroxybenzoic acid and the opening agent in a high-speed mixer, wherein the operating temperature of the high-speed mixer is 170 ℃, the rotating speed is 400rpm, and the mixing time is 35min, so as to obtain a starch mixture;
premixing the starch mixture, PBAT TH801T and PLA LX575 by using a high-speed mixer, wherein the premixing temperature is 40 ℃, the rotating speed is 80rpm, and the mixing time is 7 min; extruding and granulating by a double-screw extruder to obtain the modified biodegradable material, wherein the screw temperature is set to be 100 ℃, 135 ℃, 180 ℃, 170 ℃, 135 ℃ from the feed inlet to the machine head in a segmented manner, and the rotating speed is 400 rpm.
Comparative example 2
The modified biodegradable material was prepared according to the materials selected in example 2 (with the difference that glycerol was used instead of 2-fluoro-6-hydroxybenzoic acid) and the amount (KG) used, and under the process conditions of example 2.
Example 3
Preparing raw materials with the total mass of 100KG according to the following formula:
PBAT 2003，73.3％；
PBS FZ91PM，15％；
10% of potato starch;
1% of 3,3, 3-trifluoro-2-hydroxy-2-methylpropanoic acid;
0.7 percent of zinc stearate serving as an opening agent.
Uniformly mixing the weighed potato starch, 3,3, 3-trifluoro-2-hydroxy-2-methylpropanoic acid and the opening agent in a high-speed mixer, wherein the operating temperature of the high-speed mixer is 120 ℃, the rotating speed is 200rpm, and the mixing time is 20min to obtain a starch mixture;
premixing the starch mixture, PBAT TH801T and PBS FZ91PM by a high-speed mixer at 25 ℃ for 4min at the rotation speed of 30 rpm; extruding and granulating by a double-screw extruder to obtain the modified biodegradable material, wherein the screw temperature is set to be 100 ℃, 135 ℃, 180 ℃, 170 ℃, 160 ℃ and 135 ℃ in a segmented manner from the feed inlet to the machine head, and the rotating speed is 250 rpm.
Comparative example 3
Modified biodegradable materials were prepared according to the materials and amounts (KG) selected in example 3 and under the process conditions of example 3, with the only difference that: the high-speed mixer used for preparing the starch mixture is replaced by a double-screw extruder, and the screw temperature is set to be 100 ℃, 135 ℃, 180 ℃, 170 ℃, 160 ℃ and 135 ℃ from the feed inlet to the head section, and the rotating speed is 250 rpm.
Example 4
Preparing raw materials with the total mass of 100KG according to the following formula:
PBAT TH 801T，45.5％；
PBS B01，5％；
40% of cassava starch;
9% of 3-hydroxybenzylhydrazine dihydrochloride;
0.5% of an opening agent EBS.
Uniformly mixing the weighed cassava starch, 3-hydroxybenzylhydrazine dihydrochloride and the opening agent in a high-speed mixer, wherein the operating temperature of the high-speed mixer is 160 ℃, the rotating speed is 500rpm, and the mixing time is 40min to obtain a starch mixture;
premixing the starch mixture, PBAT TH801T and PLA LX575 by using a high-speed mixer, wherein the premixing temperature is 45 ℃, the rotating speed is 100rpm, and the mixing time is 8 min; extruding and granulating by a double-screw extruder to obtain the modified biodegradable material, wherein the screw temperature is set to be 100 ℃, 135 ℃, 180 ℃, 170 ℃, 150 ℃ from the feed inlet to the machine head in sections, and the rotating speed is 500 rpm.
Example 5
Preparing raw materials with the total mass of 100KG according to the following formula:
PBAT TH 801T，86％；
PBS 803，1％；
PLA LX975，2％；
5% of wheat starch;
5% of salicylic acid;
opening agent AH51210, 1%.
Uniformly mixing the weighed wheat starch, salicylic acid and the opening agent in a high-speed mixer, wherein the operating temperature of the high-speed mixer is 170 ℃, the rotating speed is 100rpm, and the mixing time is 15min to obtain a starch mixture;
premixing the starch mixture and PBAT TH801T by a high-speed mixer at 20 deg.C and 20rpm for 2 min; extruding and granulating by a double-screw extruder to obtain the modified biodegradable material, wherein the screw temperature is set to be 60 ℃, 100 ℃, 170 ℃, 160 ℃, 150 ℃ and the rotating speed is 200rpm from the feed inlet to the machine head in a sectional manner.
The modified biodegradable materials prepared in examples 1 to 5 and comparative examples 1 to 3 were blown to obtain film products, and the performance tests in table 2 were performed on the different film products, respectively, and the test results were as follows:
TABLE 2 film part Performance test results
| Grade of grain point | Grade of surface roughness | Surface tackiness rating | Tensile strength/MPa | b value | |
| Example 1 | 1 | 1 | 1 | 29 | 12 |
| Comparative example 1 | 5 | 4 | 1 | 23 | 16 |
| Example 2 | 1 | 1 | 1 | 32 | 11 |
| Comparative example 2 | 2 | 2 | 4 | 24 | 12 |
| Example 3 | 1 | 1 | 1 | 30 | 13 |
| Comparative example 3 | 3 | 2 | 1 | 25 | 28 |
| Example 4 | 1 | 1 | 1 | 31 | 12 |
| Example 5 | 1 | 1 | 1 | 28 | 11 |
As can be seen from the test results of various properties in Table 1, the film member prepared from the modified biodegradable material has the characteristics of no crystal point, smooth surface, no stickiness on the surface, low color difference b value, high tensile strength and excellent mechanical properties.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. The modified biodegradable material is characterized by being prepared from the following components in percentage by weight:
biodegradable material, 50-90%, preferably 65-85%;
starch, 5-40%, preferably 10-30%;
high melting point solid dispersant, 1-10%, preferably 2-7%;
0.1-1% of opening agent.
2. The modified biodegradable material according to claim 1, wherein the biodegradable material is one or more of butylene adipate/butylene glycol copolymer, polylactic acid, and polybutylene succinate.
3. The modified biodegradable material according to claim 1 or 2, characterized in that said starch is one or more of corn starch, sweet potato starch, tapioca starch, wheat starch.
4. The modified biodegradable material as claimed in claim 1, wherein the high melting point solid dispersant is a solid monomer with a melting point of 100-170 ℃ and a boiling point of more than 185 ℃.
5. The modified biodegradable material according to claim 4, wherein said high melting point solid dispersant is an organic solid monomer containing a functional group that has an intermolecular force with a hydroxyl group of starch.
6. The modified biodegradable material according to claim 5, wherein the high-melting-point solid dispersant is an organic solid monomer containing at least one functional group selected from hydroxyl group, carboxyl group and fluorine atom.
7. The modified biodegradable material according to claim 6, wherein said high melting solid dispersant is one or more of ethyl 2, 4-dihydroxy-6-methyl formate, 2-fluoro-6-hydroxybenzoic acid, 3,3, 3-trifluoro-2-hydroxy-2-methylpropionic acid, 3-hydroxybenzylhydrazine dihydrochloride, salicylic acid.
8. The modified biodegradable material according to any one of claims 1 to 7, wherein the opening agent is one or more of stearic acids, mesoacid amides, oleamide, ethylene bis stearamide, talc.
9. A method for preparing a modified biodegradable material according to any one of claims 1 to 8, characterized in that it comprises the following steps:
1) uniformly mixing starch, a high-melting-point solid dispersant and an opening agent in a high-speed mixer;
2) and (3) premixing the mixture and the biodegradable material, and then extruding and granulating through a double-screw extruder to obtain the modified biodegradable material.
10. The method for preparing the modified biodegradable material according to claim 9, wherein the mixing conditions of the high-speed mixer in step 1) are as follows: the temperature is 100-;
preferably, the operating conditions of the twin-screw extruder in step 2) are: the screw temperature is 135 ℃ to 180 ℃, preferably 140 ℃ to 175 ℃; the rotation speed is 200-500rpm, preferably 250-400 rpm.
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