CN113683875B - Degradable high-toughness heat-resistant polylactic acid-starch composite material and preparation method thereof - Google Patents
Degradable high-toughness heat-resistant polylactic acid-starch composite material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08L2201/06—Biodegradable
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention provides a degradable high-toughness heat-resistant polylactic acid-starch composite material, which comprises polylactic acid, PBAT, nylon 6, polycaprolactone, epoxycyclohexylethyl-POSS and starch. The POSS resin is epoxy cyclohexyl ethyl-POSS resin formed by copolymerizing epoxy cyclohexyl ethyl and POSS resin, contains more epoxy functional groups, is used for reacting with micromolecule lactic acid formed by decomposing polylactic acid to form stable POSS resin, prevents the polylactic acid from decomposing, and improves the heat resistance of the polylactic acid.
Description
Technical Field
The invention relates to the field of processing of high polymer materials, in particular to a degradable high-toughness heat-resistant polylactic acid-starch composite material and a preparation method thereof.
Background
With the stricter requirements on carbon emission, petroleum-based polymer materials are more and more seriously controlled in various countries in the world, and degradable biological materials are widely valued, wherein polylactic acid (PLA) has excellent biodegradability, biocompatibility, mechanical properties and processability, and has a wide application prospect in various fields such as biomedicine, textile clothing, plastic packaging, agriculture, forestry, animal husbandry and fishery. The PLA material has a glass transition temperature of 55-70 ℃, and can be used in products which are not sensitive to temperature. However, the injection molding parts of electric appliances with temperature resistance requirements and the application in the petrochemical field have the obvious defect of no temperature resistance, especially for the purpose of reducing the cost, the heat resistance of the material filled with the starch in the polylactic acid is further reduced, and the application range of the polylactic acid-starch composite material is severely limited.
Chinese patent No. 112409644A discloses a high temperature resistant PBAT/PLA fully biodegradable material, which mainly comprises 40% -50% of starch, 10% -15% of PBAT, 10% -15% of PLA, 5% -18% of plasticizer, 1% -5% of coupling agent, 3% -5% of antioxidant, 5% -10% of chain extender and 3% -5% of cross-linking agent, wherein the Vicat deformation temperature can reach 100 ℃, and the material is suitable for injection molding, but the patent contains the coupling agent, the cross-linking agent has large pollution to the environment, and the toughness of the material is still slightly insufficient.
Chinese patent CN111500061A discloses a high-temperature-resistant PLA material, which mainly comprises 0.1-5.0 parts of ethylene-vinyl acetate copolymer, 0.1-1.0 part of ADR chain extender, 0.1-0.3 part of antioxidant, 0.1-1.0 part of nucleating agent, 0.1-1.0 part of hydrolysis-resistant stabilizer, 0-0.2 part of low-melting-point white oil, 10-81.5 parts of PLA and 10-81.5 parts of PA, but the material has unstable temperature resistance and poor toughness, and the polylactic acid material is uncontrollably degraded in processing to influence the performance of the final material.
Disclosure of Invention
The invention aims to solve the problem that polylactic acid-starch composite materials are poor in heat resistance and toughness in the prior art, and provides a degradable high-toughness heat-resistant polylactic acid-starch composite material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
the invention provides a degradable high-toughness heat-resistant polylactic acid-starch composite material, which comprises polylactic acid, PBAT, nylon 6, polycaprolactone, epoxycyclohexylethyl-POSS and starch.
Preferably, the composite material is prepared from the following raw materials in parts by weight:
the POSS resin is epoxy cyclohexylethyl-POSS resin formed by copolymerizing epoxy cyclohexylethyl and POSS resin, contains more epoxy functional groups, is used for reacting with micromolecular lactic acid formed by decomposing polylactic acid to form stable POSS resin, prevents the polylactic acid from decomposing, improves the heat resistance of the polylactic acid, and does not utilize the heat resistance of the POSS resin; utilizes the epoxy cyclohexyl ethyl-POSS resin, PBAT and the soft molecular chain segment of polycaprolactone PCL can be inserted in the middle of the cage, and forms a whole with the epoxy cyclohexyl ethyl-POSS resin with a cage-shaped structure, thereby improving the toughness of polylactic acid PLA, and simultaneously utilizes the polycaprolactone PCL and the polylactic acid PLA
The feature of good compatibility, solves the problem of poor compatibility of polylactic acid PLA and epoxy cyclohexyl ethyl-POSS resin.
According to one embodiment of the invention, the polylactic acid is formed by mixing levorotatory polylactic acid PLLA, dextrorotatory polylactic acid PDLA and stereocomplex polylactic acid SC-PLA according to the ratio of 1. Because the levorotatory polylactic acid PLLA and the dextrorotatory polylactic acid PDLA are compounded according to the proportion of 1, namely the optical activity of PLA can be just eliminated, the proportion is different or one of the levorotatory polylactic acid PLLA and the dextrorotatory polylactic acid PDLA cannot be eliminated, the stereocomplex polylactic acid (SC-PLA) is formed by stereocomplex of two optical isomers of the levorotatory polylactic acid (PLLA) and the dextrorotatory polylactic acid (PDLA), the function of a compatilizer is achieved, a bridge is built between the levorotatory polylactic acid (PLLA) and the dextrorotatory polylactic acid (PDLA), the compatibility of the levorotatory polylactic acid (PLLA) and the dextrorotatory polylactic acid (PDLA) is promoted, and when the proportion of the levorotatory polylactic acid PLLA to the dextrorotatory polylactic acid PDLA is 1, the compatibilization effect of the SC-PLA is optimal, and the chain regularity degree is higher when the material is molded.
Preferably, the starch is an oxidized starch. The invention can not be realized by natural starch and other modified starch, the oxidized starch is oxidized by the oxidizing agent to obtain modified starch, and the oxidized layer on the surface of the modified starch has better heat resistance, aging resistance and yellowing resistance.
Further, the composite material also comprises 15-25 parts of glycerol and 5-15 parts of white oil in parts by weight. The heat resistance of the starch is improved by compounding the white oil and the glycerol.
Preferably, the degradable high-toughness heat-resistant polylactic acid-starch composite material is prepared from the following raw materials in parts by weight:
the PBAT has a melt index of 3 to 10g/10min (ASTM D1238).
The nylon 6 is high-flow PA6, and the melt index is 30-45cm3/g (ASTM D1238).
The melt index of the polycaprolactone is 1-3g/10min, and the test condition is 160 ℃ and 2.16kg.
The glycerol is industrial-grade glycerol with the purity of 95%, and the white oil is 26# industrial-grade white oil.
The invention also provides a preparation method of the composite material, which comprises the following specific steps:
s1, uniformly mixing polylactic acid (PLA), poly (PBAT), polycaprolactone (PCL) and nylon 6 in a high-speed mixer;
s2, adding the material mixed in the step S1 into a first section of a cylinder of a double-screw extruder, adding epoxy cyclohexyl ethyl-POSS into a sixth section of the extruder, setting the temperature of the extruder except the sixth section to be 250-350 ℃, controlling the temperature of other zones to be 150-200 ℃, and controlling the rotating speed to be 500-600r/min to perform extrusion granulation.
As another embodiment of the present invention, the method for preparing the composite material comprises the following specific steps:
(1) The starch, the white oil and the glycerol are uniformly mixed in a high-speed mixer for 30min and then packaged for later use.
(2) And (2) uniformly mixing the material prepared in the step (1) with polylactic acid (PLA), PBAT, polycaprolactone (PCL) and nylon 6 in a high-speed mixer.
(3) And (3) adding the mixed material in the step (2) into a first section of a cylinder of a double-screw extruder, adding epoxy cyclohexyl ethyl-POSS into a sixth section of the extruder, setting the temperature of the extruder except for 300 ℃ of the sixth section, controlling the temperature of other regions to be 160 ℃, and controlling the rotating speed to be 500-600r/min for extrusion granulation.
Compared with the prior art, the invention has the beneficial effects that:
1) When PLA is processed, PLA is easy to degrade to generate micromolecular lactic acid, so that a chain degradation reaction is caused, the molecular weight is reduced, the heat resistance of the material is reduced, and the material becomes brittle;
2) The starch is easy to degrade and yellow in processing, and the heat resistance of PLA is reduced, the oxidized starch is adopted in the invention, and the processing performance of the starch is improved by using glycerol and white oil, the oxidized starch has better heat resistance compared with common starch, and the heat resistance of the starch is improved by compounding the white oil and the glycerol, the compatibility of the starch and other components is improved, the integral structure of the material is more uniform and compact, so that the heat resistance and toughness are improved.
3) The PBAT, PCL and epoxy cyclohexylethyl-POSS with specific melt fingers are adopted in the invention, the epoxy cyclohexylethyl-POSS is cage type polysilsesquioxane, the shape of the cage type polysilsesquioxane is like a cage, PBAT and PCL molecular chain segments can be inserted in the middle of the cage during blending, and the PCL molecular chain segments and POSS resin with a cage type structure form a whole.
4) The adopted polylactic acid is levorotatory polylactic acid (PLLA), dextrorotatory polylactic acid (PDLA), and stereocomplex polylactic acid (SC-PLA) is compounded according to the proportion of 1. The stereocomplex polylactic acid (SC-PLA) is formed by stereocomplex two optical isomers of levorotatory polylactic acid (PLLA) and dextrorotatory polylactic acid (PDLA), the addition of the stereocomplex polylactic acid can play a role of a compatilizer, a bridge is built between the levorotatory polylactic acid (PLLA) and the dextrorotatory polylactic acid (PDLA), the compatibility of the levorotatory polylactic acid (PLLA) and the dextrorotatory polylactic acid (PDLA) is promoted, and the regularity of a molecular chain is higher during material forming. Meanwhile, the high melting point means that PA6 has excellent dispersibility in the processing process, the crystallization of PA6 is fast, and the melting point in the nylon variety is closest to that of PLA, so that the PA6 is compounded at the same time, and the crystallization property and the heat resistance of the material are improved.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
In the following examples:
the polylactic acid is prepared by compounding levorotatory polylactic acid (PLLA), dextrorotatory polylactic acid (PDLA) and stereocomplex polylactic acid (SC-PLA) according to the weight ratio of 1.
PBAT melt index is 3-10g/10min (ASTM D1238); selecting materials: kanghui fresh material KHB21AP11.
The nylon 6 is high-flow PA6, and the melt index is 30-45cm 3 /g (astm d 1238); selecting materials: south Asia plastic PA6 2100.
The melt index of polycaprolactone is 1-3g/10min, and the test condition is 160 ℃ by 2.16kg; selecting materials: and (3) poly (semen coicis) PCL-6800.
The starch is oxidized starch, and is modified starch obtained by oxidizing starch in acid, alkali and neutral medium.
The glycerol is industrial grade glycerol with a purity of 95%.
The white oil is 26# industrial grade white oil.
Examples 1 to 4
Examples 1 to 4 provide a degradable high-toughness heat-resistant polylactic acid-starch composite material, which is prepared according to the components and the content of each component in table 1.
TABLE 1 EXAMPLES 1-4 Components and component amounts
The preparation method of the degradable high-toughness heat-resistant polylactic acid-starch composite material of the embodiment 1-2 comprises the following steps:
uniformly mixing oxidized starch with polylactic acid (PLA), nylon 6 and Polycaprolactone (PCL) in a high-speed mixer, adding the mixture into a first section of a cylinder of a double-screw extruder, adding POSS material into a sixth section of the extruder, setting the temperature of the extruder except the sixth section to be 300 ℃, controlling the temperature of other areas to be 160 ℃, and controlling the rotating speed to be 500-600r/min to perform extrusion granulation.
The preparation method of the degradable high-toughness heat-resistant polylactic acid-starch composite material of the embodiment 3-4 comprises the following steps:
(1) Uniformly mixing oxidized starch, white oil and glycerol in a high-speed mixer for 30min, and bagging for later use;
(2) Uniformly mixing the material prepared in the step (1) with polylactic acid (PLA), nylon 6 and Polycaprolactone (PCL) in a high-speed mixer, adding the mixture into a first section of a cylinder of a double-screw extruder, adding the POSS material into a sixth section of the extruder, setting the temperature of the extruder except the sixth section to be 300 ℃, setting the temperature of other regions to be 160 ℃, and controlling the rotating speed to be 500-600r/min for extrusion granulation.
Comparative example 1
The raw material components and the preparation method of the comparative example are basically the same as those of example 3, except that: the POSS material is methacryloxypropyl polyhedral oligomeric silsesquioxane (MAP-POSS).
Comparative example 2
The raw material components and the preparation method of the comparative example are basically the same as those of example 3, except that: the POSS material is 4-acetoxystyrene-POSS (PAS-POSS).
Comparative example 3
The raw material components and the preparation method of the comparative example are basically the same as those of example 3, except that: the POSS material is p-hydroxystyrene-POSS (PHS-POSS).
Comparative example 4
The comparative example has substantially the same raw material composition and preparation method as example 3, except that: the polylactic acid is composed of l-polylactic acid (PLLA), d-polylactic acid (PDLA), and stereocomplex polylactic acid (SC-PLA) in a ratio of (1.
Comparative example 5
The raw material components and the preparation method of the comparative example are basically the same as those of example 3, except that: the polylactic acid was composed of l-polylactic acid (PLLA), d-polylactic acid (PDLA), and stereocomplex polylactic acid (SC-PLA) in a ratio of (2.
Comparative example 6
The raw material components and the preparation method of the comparative example are basically the same as those of example 3, except that: the polylactic acid is prepared by mixing levorotatory polylactic acid (PLLA) and dextrorotatory polylactic acid (PDLA) in a ratio of (1.
Comparative example 7
The comparative example has substantially the same raw material composition and preparation method as example 3, except that: the polylactic acid is prepared by mixing levorotatory polylactic acid (PLLA) and dextrorotatory polylactic acid (PDLA) in a ratio of (2.
Comparative example 8
The raw material components and the preparation method of the comparative example are basically the same as those of example 3, except that: the starch is natural starch.
Comparative example 9
The raw material components and the preparation method of the comparative example are basically the same as those of example 3, except that: the starch is grafted by maleic anhydride.
Comparative example 10
The raw material components and the preparation method of the comparative example are basically the same as those of example 3, except that: the starch is starch acetate.
Comparative example 11
The comparative example has substantially the same raw material composition and preparation method as example 3, except that: the starch is starch laurate.
Comparative example 12
The raw material components and the preparation method of the comparative example are basically the same as those of example 3, except that: the starch is acrylonitrile starch.
Comparative example 13
The raw material components and the preparation method of the comparative example are basically the same as those of example 3, except that: the starch is carboxymethyl starch.
Performance testing
The composite materials prepared in the examples and the comparative examples were subjected to performance tests.
TABLE 2 Performance testing of examples 1-4 and comparative examples 1-13
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (7)
1. A degradable high-toughness heat-resistant polylactic acid-starch composite material is characterized by comprising polylactic acid, PBAT, nylon 6, polycaprolactone, epoxycyclohexylethyl-POSS and starch;
the composite material is prepared from the following raw materials in parts by weight:
the polylactic acid is formed by mixing levorotatory polylactic acid PLLA, dextrorotatory polylactic acid PDLA and stereocomplex polylactic acid SC-PLA according to the ratio of 1;
the starch is oxidized starch.
2. The composite material of claim 1, further comprising 15-25 parts by weight of glycerin and 5-15 parts by weight of white oil.
3. The composite material of claim 1, characterized in that the PBAT has a melt index of 3-10g/10min.
4. The composite material of claim 1, wherein said nylon 6 is high flow PA6 with a melt index of 30-45cm 3 /g。
5. The composite material of claim 1, wherein the polycaprolactone melt index is 1-3g/10min, test condition 160 ℃ 121161g.
6. The composite material of claim 1, wherein the glycerol is 95% pure technical grade glycerol and the white oil is 26# technical grade white oil.
7. A method for preparing a composite material according to any one of claims 1 to 4, characterized in that the specific steps are as follows:
s11, uniformly mixing polylactic acid (PLA), poly (PBAT), polycaprolactone (PCL) and nylon 6 in a high-speed mixer;
s21, adding the mixed material in the step S1 into a first section of a cylinder of a double-screw extruder, adding epoxy cyclohexyl ethyl-POSS into a sixth section of the extruder, setting the temperature of the extruder except the sixth section to be 250-350 ℃, setting the temperature of other regions to be 150-200 ℃, controlling the rotating speed to be 500-600r/min, and carrying out extrusion granulation.
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