CN113736232B - 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%; 1-10%, preferably 2-7% of a high melting point solid dispersant; 0.1 to 1 percent of opening agent. The invention can obtain the starch-filled biodegradable material with non-crystal points and non-sticky surfaces.
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 degrade under the action of microorganisms such as bacteria, mold (fungi) and algae that exist in nature. The ideal biodegradable material has excellent use performance and can be completely degraded in natural environment after being used. The biodegradable materials commonly used at present are polybutylene adipate and polybutylene terephthalate copolymer (PBAT), polylactic acid (PLA), polybutylene succinate (PBS), poly-beta-hydroxybutyrate (PHB), polyhydroxyalkanoate (PHA) and the like. Generally pure raw materials are difficult to directly use, the requirements of products on the properties of the raw materials can be met after the raw materials are modified, a common modification mode for biodegradable materials is to add a filling system, such as starch, talcum powder, calcium carbonate and the like, wherein the starch belongs to a completely biodegradable material, and the application prospect of the filling system as a biodegradable material is most extensive. However, because the main component of the starch is glucose, the intermolecular force is strong, and aggregation is easy, crystal points exist when the product is molded.
In order to solve the problem of starch dispersion, the most common method at present is to add glycerol as a dispersing agent, and permeate the glycerol between starch particles, so that the intermolecular acting force of the starch is reduced, and the linked segments are easy to slide, thereby avoiding starch aggregation. However, since glycerol is liquid, and the glycerol addition amount is usually 25% of the weight of starch, a large amount of glycerol needs to be discharged in the addition process, and the smoke on site is large when the product is formed, so that serious potential safety hazards exist, and the problems of precipitation of glycerol, stickiness on the surface and the like of the product exist.
In the process of producing and processing starch composite biodegradable polymer material, the surface of starch particles is treated by one or more ecologically safe acids or anhydrides, 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, complicated operation steps, 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 preparation method of a completely biodegradable starch composite mulch film, which comprises the steps of preparing starch granules by enzymolysis and modification of amylase to form starch short chains with starch clusters and polymerization degree, and then processing and gelatinizing the starch short chains to effectively improve the combination property of starch materials and resin matrixes and improve the mechanical strength of the materials, wherein the enzyme treatment is uncontrollable on one hand, and the application field of the starch granules is limited by the existence of the starch clusters, so that the starch granules cannot be used as shopping bags, bubble films and the like.
The patent CN201310153446.3 firstly mixes starch, PBAT, plasticizer, compatilizer, initiator, hydrophobic modifier, lubricant, antioxidant and filler, extrudes and granulates to prepare starch master batch, and then prepares the modified biodegradable material. However, the color of the product is darkened due to the two times of twin-screw extrusion of starch, and the starch is difficult to use as a white product.
The starch-filled biodegradable material prepared by the technology has the problems of insufficient dispersion of starch, complex preparation process, small application range of products and the like, and a new solution is needed 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 starch filled biodegradable material with no crystal points and non-sticky surface can be obtained.
In order to achieve the above 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%;
1-10%, preferably 2-7% of a high melting point solid dispersant;
0.1 to 1 percent of opening agent.
In some examples of the invention, the biodegradable material includes some biodegradable materials that can be added to starch to form a filling system, such as one or more of polybutylene adipate and polybutylene succinate (PBS), polylactic acid (PLA), and copolymers of butylene adipate and butylene succinate (PBAT).
The preferable melt index range of the copolymer of the butanediol adipate and the butanediol ester is 3-6g/10min (190 ℃,2.16 kg); the preferable melt finger range of the polylactic acid is 3-10g/10min (190 ℃,2.16 kg); the preferable melt index range of the polybutylene succinate is 3-15g/10min (190 ℃ C., 2.16 kg).
The starch has complete biodegradability in various environments and wide sources, and the starch is added into the biodegradable material as the filling 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, bio-based materials comprising starch or any modified starch may be used in the present invention and the present invention has been completed. 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 invention, the high melting point solid dispersant is one or more of a solid monomer having a melting point of 100-170 ℃, a boiling point of greater than 185 ℃, preferably an organic solid monomer containing a functional group capable of exerting intermolecular forces with the hydroxyl group of starch, more preferably an organic solid monomer containing at least one functional group of hydroxyl group, carboxyl group, fluorine atom, most preferably ethyl 2, 4-dihydroxy-6-methylformate (melting point 129-132 ℃, boiling point 349 ℃), 2-fluoro-6-hydroxybenzoic acid (melting point 159-163 ℃, boiling point 209 ℃), 3-trifluoro-2-hydroxy-2-methylpropanoic acid (melting point 110 ℃, boiling point 189 ℃), 3-hydroxybenzylhydrazine dihydrochloride (melting point 138-140 ℃, boiling point 357 ℃), salicylic acid (melting point 158-161 ℃, boiling point 211 ℃).
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 permeate between starch particles when being mixed with the starch at high temperature, so that the acting force between starch molecules is reduced, the linked segment is easier to slide, the starch is well dispersed, and the modified biodegradable material which is difficult to agglomerate is formed, thereby solving the technical problems of crystal points and rough surfaces of products. Meanwhile, the high-melting-point solid dispersing agent is in a solid state at a temperature below the melting point, and after the modified biodegradable material is formed, the high-melting-point solid dispersing agent cannot migrate to the surface of a product in the normal-temperature storage process of the product, 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 acid, a mesoporous acid amide, oleic acid amide, ethylene bis stearic acid amide (EBS), talc. The opening agent is an additive commonly used in the production and preparation process of plastic film material 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 dispersing agent and a pore 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 permeate among starch particles in a liquid state, the dispersibility of the starch is improved, part of water in the starch can be removed, the hydrolysis of the biodegradable material in the processing process is slowed down, and the mechanical property of the modified material is ensured;
2) Premixing the mixture and the biodegradable material, and extruding and granulating by a double-screw extruder to obtain the modified biodegradable material.
In some examples of the invention, the mixing conditions of the high-speed mixer in step 1) are: the temperature is 100-170deg.C, the rotation speed is 100-500rpm, preferably 200-400rpm, and the mixing time is 15-40min, preferably 20-35min;
preferably, the twin screw extruder in step 2) is operated under the following conditions: the screw temperature is 135-180 ℃, preferably 140-175 ℃; the rotation speed is 200-500rpm, preferably 250-400rpm.
More preferably, the premixing conditions of the raw materials in step 2) are: the temperature is 20-45deg.C, preferably 25-40deg.C, the rotation speed is 20-100rpm, preferably 30-80rpm, and the mixing time is 2-8min, preferably 4-7min.
In the present invention, "%" not specifically mentioned means "wt%".
Compared with the prior art, the invention has the following positive effects:
1) The invention solves the problem of starch dispersion in the starch-filled biodegradable material and the problem of precipitation caused by taking small molecular glycerol as a dispersing agent, so that the prepared product is smooth and has no crystal points and the surface is not sticky;
2) Under the high-temperature mixing condition, the moisture content in the starch is greatly reduced, so that 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 on-site smoke is less in the processing and forming stage, 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 color of the product is prevented from becoming deep, and the application of the product in white products 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 dispersing agent, so that the organic solid monomer fully wraps starch particles in a high-temperature mixing process, and simultaneously has strong traction and fixation effects on starch molecules, so that starch dispersion is promoted, and migration of the dispersing agent to the surface of a product is avoided;
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 films, mulching films and the like.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
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) Crystal point test: after film blowing, observing the surface of the film by naked eyes, wherein no crystal points are 1 level, less than or equal to 3 crystal points are 2 levels, less than or equal to 5 crystal points are 3 levels, less than or equal to 10 crystal points are 4 levels, and more than 10 crystal points are 5 levels within the range of 10 cm;
(2) Surface roughness test: the surface of the film is smooth and has no rough feeling of 1 level, the surface has rough feeling of 2 level, the rough feeling is obviously 3 level, and the rough feeling is obviously 4 level;
(3) Surface tack test: the film bag is stored for 3 months at 23 ℃, and then the surface of the film is observed, and the film bag is classified 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 obvious sticky phenomenon, and the 4 grade surface sticky phenomenon is serious;
(4) Tensile strength: tensile strength according to standard ISO 527, spline dimensions of 170mm by 10mm by 4mm, tensile rate 500mm/min;
(5) Color difference b value: the test equipment is a color meter of Hunterlab company, the model is UltraScan VIS, and the sample is product particles;
the invention adopts the following equipment:
high-speed mixer: 120L pot type high mixing machine, suzhou Song Yuan environmental protection technology Co., ltd, with oil bath heating;
twin screw extruder: the twin-screw extruder used was a product of Keplon mechanical Co., ltd, model ZSK 32Mc;
film blowing machine: the film blowing machine is manufactured by Zhejiang cast letter machinery Co., ltd, and the model is SJ-35 600.
Example 1
Raw materials with a total mass of 100KG were prepared according to the following recipe:
PBAT TH801T，73.7％；
PLA L175，2％；
corn starch JYM001, 20%;
2, 4-dihydroxy-6-methyl ethyl formate, 4%;
opening agent ER,0.3%.
Uniformly mixing the weighed corn starch, the 2, 4-dihydroxyl-6-ethyl methyl formate and the opening agent in a high-speed mixer, wherein the operation temperature of the high-speed mixer is 150 ℃, the rotating speed is 300rpm, and the mixing time is 25 minutes to obtain a starch mixture;
premixing the starch mixture and the PBAT TH801T by adopting a high-speed mixer, wherein the premixing temperature is 35 ℃, the rotating speed is 50rpm, and the mixing time is 6min; extruding by a double-screw extruder, granulating to obtain the modified biodegradable material, wherein the screw temperature is set to 60 ℃, 100 ℃, 180 ℃, 160 ℃, 140 ℃, 135 ℃ from the feed inlet to the machine head section by section, and the rotating speed is 300rpm.
Comparative example 1
The materials selected for example 1 (except that ethyl 2, 4-dihydroxy-6-methyl formate was not added) and the amount (KG) were used, and modified biodegradable materials were prepared under the process conditions of example 1.
Example 2
Raw materials with a total mass of 100KG were prepared according to the following recipe:
PBAT KHB21，52.9％；
PLA LX575，10％；
sweet potato starch, 30%;
2-fluoro-6-hydroxybenzoic acid, 7%;
212,0.1% of an opening agent.
Uniformly mixing the weighed sweet potato starch, 2-fluoro-6-hydroxybenzoic acid and a pore opening agent in a high-speed mixer, wherein the operation temperature of the high-speed mixer is 170 ℃, the rotating speed is 400rpm, and the mixing time is 35min to obtain a starch mixture;
premixing the starch mixture, the PBAT TH801T and the PLA LX575 by a high-speed mixer, wherein the premixing temperature is 40 ℃, the rotating speed is 80rpm, and the mixing time is 7min; extruding by a double-screw extruder, granulating to obtain the modified biodegradable material, the temperature of the screw rod is sectionally set to be 100 ℃, 135 ℃, 180 ℃ from the feed inlet to the machine head 170 ℃, 135 ℃, the rotation speed was 400rpm.
Comparative example 2
The materials selected for use in example 2 (except that glycerol was used instead of 2-fluoro-6-hydroxybenzoic acid) and the amount (KG) were used, and modified biodegradable materials were prepared under the process conditions of example 2.
Example 3
Raw materials with a total mass of 100KG were prepared according to the following recipe:
PBAT 2003，73.3％；
PBS FZ91PM，15％；
potato starch, 10%;
1% of 3, 3-trifluoro-2-hydroxy-2-methylpropanoic acid;
0.7% of opening agent zinc stearate.
Uniformly mixing the weighed potato starch, 3-trifluoro-2-hydroxy-2-methylpropanoic acid and a pore opening agent in a high-speed mixer, wherein the operation temperature of the high-speed mixer is 120 ℃, the rotating speed is 200rpm, and the mixing time is 20min, so as to obtain a starch mixture;
premixing the starch mixture, the PBAT TH801T and the PBS FZ91PM by adopting a high mixer, wherein the premixing temperature is 25 ℃, the rotating speed is 30rpm, and the mixing time is 4min; extruding by a double screw extruder, granulating to obtain the modified biodegradable material, wherein the screw temperature is set to be 100 ℃, 135 ℃, 180 ℃, 170 ℃, 160 ℃, 135 ℃ from the feed inlet to the machine head section by section, and the rotating speed is 250rpm.
Comparative example 3
The materials and amounts (KG) selected for use in example 3 were chosen and under the process operating conditions of example 3, modified biodegradable materials were prepared, with the only differences: the high-speed mixer used for preparing the starch mixture was replaced with a twin-screw extruder, and the screw temperature was set to 100 ℃, 135 ℃, 180 ℃, 170 ℃, 160 ℃, 135 ℃ from the feed inlet to the head section at a rotation speed of 250rpm.
Example 4
Raw materials with a total mass of 100KG were prepared according to the following recipe:
PBAT TH 801T，45.5％；
PBS B01，5％；
tapioca starch, 40%;
3-hydroxybenzylhydrazine dihydrochloride, 9%;
0.5% of opening agent EBS.
Uniformly mixing the weighed tapioca starch, 3-hydroxybenzylhydrazine dihydrochloride and a pore opening agent in a high-speed mixer, wherein the operation temperature of the high-speed mixer is 160 ℃, the rotating speed is 500rpm, and the mixing time is 40min, so as to obtain a starch mixture;
premixing the starch mixture, the PBAT TH801T and the PLA LX575 by a high-speed mixer, wherein the premixing temperature is 45 ℃, the rotating speed is 100rpm, and the mixing time is 8min; extruding by a double screw extruder, granulating 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 section by section, and the rotating speed is 500rpm.
Example 5
Raw materials with a total mass of 100KG were prepared according to the following recipe:
PBAT TH 801T，86％；
PBS 803，1％；
PLA LX975，2％；
wheat starch, 5%;
salicylic acid, 5%;
1% of an opening agent AH 51210.
Uniformly mixing the weighed wheat starch, salicylic acid and a shedding agent in a high-speed mixer, wherein the operation 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 the PBAT TH801T by adopting a high-speed mixer, wherein the premixing temperature is 20 ℃, the rotating speed is 20rpm, and the mixing time is 2min; extruding by a double-screw extruder, granulating to obtain the modified biodegradable material, wherein the screw temperature is set to 60 ℃, 100 ℃, 170 ℃, 160 ℃, 150 ℃ from the feed inlet to the machine head section by section, and the rotating speed is 200rpm.
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 of the film products in table 2 was tested, respectively, as follows:
TABLE 2 Performance test results of film products
| Crystal point grade | Surface roughness grade | Surface tack grade | 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 the properties in Table 1, the film prepared from the modified biodegradable material of the present invention has the characteristics of no crystal point, smooth surface, no stickiness on the surface, low color difference b value, and high tensile strength, which indicates that the film has excellent mechanical properties.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the 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%,
starch 5-40%,
1 to 10 percent of high-melting-point solid dispersing agent,
opening agent, 0.1-1%;
the high-melting-point solid dispersing agent is one or more of 2, 4-dihydroxyl-6-ethyl methyl formate, 2-fluoro-6-hydroxybenzoic acid, 3-trifluoro-2-hydroxy-2-methylpropanoic acid, 3-hydroxybenzylhydrazine dihydrochloride and salicylic acid.
2. The modified biodegradable material according to claim 1, characterized in that it is prepared from the following components in percentage by weight:
65-85% of biodegradable material;
starch 10-30%;
2-7% of high-melting-point solid dispersing agent;
0.1 to 1 percent of opening agent.
3. The modified biodegradable material according to claim 1, characterized in that said biodegradable material is one or more of a copolymer of adipic acid and terephthalic acid, polylactic acid, polybutylene succinate.
4. A modified biodegradable material according to any one of claims 1-3, characterized in that said starch is one or more of corn starch, sweet potato starch, tapioca starch, wheat starch.
5. A modified biodegradable material according to any one of claims 1-3, characterized in that said opening agent is one or more of stearic acid, mesoporous acid amide, oleic acid amide, ethylene bisstearamide, talc.
6. A method for producing the modified biodegradable material according to any one of claims 1 to 5, comprising the steps of:
1) Uniformly mixing starch, a high-melting-point solid dispersing agent and a pore opening agent in a high-speed mixer;
2) Premixing the mixture and the biodegradable material, and extruding and granulating by a double-screw extruder to obtain the modified biodegradable material.
7. The method for producing a modified biodegradable material according to claim 6, wherein the mixing conditions of the high-speed mixer in step 1) are: the temperature is 100-170 ℃, the rotating speed is 100-500rpm, and the mixing time is 15-40min.
8. The method for producing a modified biodegradable material according to claim 7, wherein the mixing conditions of the high-speed mixer in step 1) are: the rotation speed is 200-400rpm, and the mixing time is 20-35min.
9. The method for producing a modified biodegradable material according to claim 7, characterized in that the twin-screw extruder in step 2) is operated under the following conditions: the temperature of the screw rod is 135-180 ℃; the rotation speed is 200-500rpm.
10. The method for producing a modified biodegradable material according to claim 9, characterized in that the twin-screw extruder in step 2) is operated under the following conditions: the temperature of the screw is 140-175 ℃; the rotation speed is 250-400rpm.
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| JP2002129042A (en) * | 2000-10-24 | 2002-05-09 | Mitsubishi Rayon Co Ltd | Modifying agent for biodegradable resin and biodegradable resin composition |
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