CN112592567B - Full-biodegradable material containing superfine stereocomplex polylactic acid - Google Patents
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- 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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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/06—Biodegradable
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- 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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Abstract
The invention discloses a full-biodegradable material containing superfine stereocomplex polylactic acid, which comprises the following raw materials: the weight ratio of the superfine stereocomplex polylactic acid to the biodegradable material is 15-35:65-85; wherein the superfine stereocomplex polylactic acid is: uniformly mixing the levorotatory polylactic acid and the dextrorotatory polylactic acid, mixing for 4-10 minutes at 120-180 ℃ by an internal mixer or a double screw extruder to obtain a stereoscopic compound polylactic acid solid, grinding, crushing at low temperature, and sieving to obtain powder, wherein the average particle diameter Dv (50) of the powder is less than 500 mu m, and the [ Dv (90) -Dv (10) ]/2 is less than 400 mu m; and the superfine stereocomplex polylactic acid and the biodegradable material are melt blended at a processing temperature lower than 200 ℃ to obtain the superfine stereocomplex polylactic acid-containing fully biodegradable material.
Description
Technical Field
The invention relates to a full-biodegradable material containing superfine stereocomplex polylactic acid.
Background
The traditional biodegradable material has the defects of low temperature resistance and poor strength, and is difficult to realize effective replacement under the existing use conditions. Therefore, the scheme for developing the high-performance biodegradable material is suitable for the market application requirements of the current mainstream, and becomes a problem to be solved by popularization and application of the biodegradable material.
The common biodegradable material has low melting point (50-150 ℃) and crystallinity and low thermal deformation temperature. In the application scene of daily temperature resistance (70-90 ℃), sufficient temperature resistance guarantee cannot be provided. Because the self crystallization capability of the biodegradable material is weaker, the processing procedure is generally complicated and the production cost is increased by promoting crystallization through an external process, so that the biodegradable material is unfavorable to be widely popularized and applied. The improvement of the heat resistance of the biodegradable material by adding the inorganic filler is a common material modification method, but the inorganic filler is easy to exceed the standard of heavy metal and specific element content when in use, and does not meet the composting degradation requirement.
CN201110207647.8 discloses a biodegradable polyethylene film and a preparation method thereof, wherein the biodegradable polyethylene film comprises the following components in percentage by weight: 40-55% of high-density polyethylene, 10-30% of polylactic acid stereocomplex, 3-25% of epoxy vegetable oil, 15-35% of starch and 3-15% of compatibilizer.
CN201510908115.5 discloses a biodegradable agricultural mulch film. The composition comprises the following components in parts by weight: 50-60 parts of high-density polyethylene, 30-40 parts of fumaric acid, 5-10 parts of polylactic acid stereocomplex, 3-15 parts of epoxy vegetable oil, 15-35 parts of corn starch, 3-8 parts of compatibilizer, 25-45 parts of starch-based biodegradable material, 0.3-0.8 part of light stabilizer, 0.3-0.5 part of thermal oxidative degradation accelerator, 0.1-0.3 part of catalyst and 30-40 parts of polyethylene wax. The biodegradable agricultural mulching film provided by the invention keeps the heat-preservation and moisture-preservation insecticidal efficacy of the mulching film in the plant growth stage.
CN201711263639.9 discloses a polylactic acid composite material and a preparation method thereof. The polylactic acid composite material and the preparation method thereof are as follows according to parts by weight: 100 parts of racemized polylactic acid copolymer and 10-40 parts of stereocomplex polylactic acid, wherein in the stereocomplex polylactic acid, the polylactic acid is 30-70 parts of polylactic acid and the polylactic acid is 30-70 parts of polylactic acid. The mechanical properties of the pure racemized polylactic acid resin are enhanced by blending the stereocomplex polylactic acid and the racemized polylactic acid.
However, in the above patents, there is no study on improvement of temperature resistance, and the blending processing of polyethylene and stereocomplex polylactic acid does not allow complete biodegradation of the material.
Disclosure of Invention
The invention mainly aims at providing a full-biodegradable material containing superfine stereocomplex polylactic acid.
The technical scheme adopted for solving the technical problems is as follows:
the fully biodegradable material comprises superfine stereocomplex polylactic acid and biodegradable material: the weight ratio of the superfine stereocomplex polylactic acid to the biodegradable material is 15-35:65-85;
wherein the superfine stereocomplex polylactic acid is: uniformly mixing the levorotatory polylactic acid and the dextrorotatory polylactic acid, mixing for 4-10 minutes at 120-180 ℃ by an internal mixer or a double screw extruder to obtain a stereoscopic compound polylactic acid solid, grinding, crushing at low temperature and sieving to obtain powder, wherein the mixing ratio of the levorotatory polylactic acid to the dextrorotatory polylactic acid is 4:6-6:4, the average particle diameter Dv (50) of the powder is less than 500um, and the [ Dv (90) -Dv (10) ]/2 is less than 400um;
wherein Dv (10), dv (50) and Dv (90) represent the corresponding particle sizes with particle size distribution of 10%, 50% and 90%, respectively. [ Dv (90) -Dv (10) ]/2 approximates the half-width value of the particle size distribution curve.
The superfine stereocomplex polylactic acid and the biodegradable material are melt blended at the processing temperature of 150-200 ℃ to obtain the superfine stereocomplex polylactic acid-containing fully biodegradable material.
The invention defines that the average grain diameter Dv (50) of the stereocomplex polylactic acid powder is less than 500um, and [ Dv (90) -Dv (10) ]/2 is less than 400um: the stereocomplex polylactic acid powder with uniform particle diameter and proper size is easier to disperse and process, and the overall performance of the material is improved. If Dv (50) is greater than 500um, the impact properties of the material are more degraded; in the present invention, if [ Dv (90) -Dv (10) ]/2 is greater than 400 μm, both the heat-resistant temperature and the physical properties of the material are lowered; the processing temperature of melt blending of the superfine stereocomplex polylactic acid and the biodegradable material is 150-200 ℃, the stereocomplex polylactic acid powder is not melted, the amorphous area part is continuously crystallized at the temperature, and the heat resistance can be maintained; if the processing temperature is higher than 200 ℃, after the stereocomplex polylactic acid powder is partially melted, the stereocomplex crystal is not formed any more, and the heat resistance of the blending material is affected.
In the invention, the biodegradable material comprises at least one of PBS (polybutylene succinate), PBAT (polybutylene terephthalate-adipate), PHA (polyhydroxyalkanoate), PPC (carbon dioxide-propylene oxide copolymer) and PCL (polycaprolactone).
In a preferred embodiment of the present invention, the mixing temperature of the stereocomplex polylactic acid solid is 140 to 170 ℃.
In a preferred embodiment of the present invention, the melt processing temperature of the ultra-fine stereocomplex polylactic acid and the biodegradable material is 160-180 ℃.
In the preferred embodiment of the invention, the blending ratio of the superfine stereocomplex polylactic acid to the PCL is 18-22:78-82, the melting temperature is 155-165 ℃, and the injection molding temperature is 160-170 ℃.
In a preferred embodiment of the invention, the ratio of the superfine stereocomplex polylactic acid to the PCL blend is 20:80 by weight, the melting temperature is 160 ℃, and the injection molding temperature is 165 ℃.
In a preferred embodiment of the invention, the blending ratio of the superfine stereocomplex polylactic acid/PBS is 13-17:83-87, the melting temperature is 155-165 ℃, and the injection molding temperature is 165-175 ℃.
In a preferred embodiment of the invention, the blending ratio of the superfine stereocomplex polylactic acid/PBS is 15:85 by weight, the melting temperature is 160 ℃, and the injection molding temperature is 170 ℃.
In the preferred embodiment of the invention, the blending ratio of the superfine stereocomplex polylactic acid/PBAT is 33-37:60-70 by weight, the melting temperature is 175-185 ℃, and the injection molding temperature is 170-180 ℃.
In a preferred embodiment of the invention, the ratio of the superfine stereocomplex polylactic acid to the PBAT blend is 35:65 by weight, the melting temperature is 180 ℃, and the injection molding temperature is 175 ℃.
The full-biodegradable material containing the stereocomplex polylactic acid has the following advantages:
(1) The superfine three-dimensional composite polylactic acid disclosed by the invention is easy to process and disperse uniformly in biodegradable materials due to small particle size and uniform distribution. Because the prepared stereocomplex polylactic acid has high melting point (220-240 ℃), the material can not be melted when being processed at 150-200 ℃, and meanwhile, the amorphous area part of the material can be continuously crystallized, so that the heat resistance of the blending material is promoted. Compared with the common inorganic filling material, the superfine three-dimensional composite polylactic acid has no problem of exceeding heavy metal content, and is safer and more environment-friendly to use.
(2) The prepared stereocomplex polylactic acid material has high melting point (220-240 ℃) and good temperature resistance, and the material temperature resistance can be improved by introducing the stereocomplex polylactic acid material into a biodegradable material, and the problem that the content of heavy metal and specific elements exceeds the standard is not worry due to the good biodegradability of the stereocomplex polylactic acid material.
(3) Can be repeatedly processed within 150-200 ℃ without affecting the heat resistance of the material.
Detailed Description
EXAMPLE 1 superfine stereocomplex polylactic acid/PCL blending
Firstly, preparing superfine stereocomplex polylactic acid: and after uniformly mixing the L-polylactic acid and the D-polylactic acid, mixing the mixture for 7 minutes at 150 ℃ by an internal mixer to obtain a three-dimensional composite polylactic acid solid, and grinding, low-temperature crushing and sieving the three-dimensional composite polylactic acid solid to obtain powder, wherein the mixing ratio of the L-polylactic acid to the D-polylactic acid is 1:1 by weight.
Grinding, low-temperature crushing and sieving to obtain superfine three-dimensional composite polylactic acid (Dv50=400 um, [ Dv (90) -Dv (10) ]/2=300 um) and PCL 6500, uniformly mixing according to the mass ratio of 20:80, then carrying out melt blending extrusion and granulation by a double-screw extruder at 160 ℃, and then carrying out sample preparation by an injection molding machine at 165 ℃.
EXAMPLE 2 ultra-fine stereocomplex polylactic acid/PBS blend
Firstly, preparing superfine stereocomplex polylactic acid: mixing the L-polylactic acid and the D-polylactic acid uniformly, mixing the mixture for 5 minutes at 160 ℃ by an internal mixer to obtain a three-dimensional composite polylactic acid solid, and grinding, low-temperature crushing and sieving the three-dimensional composite polylactic acid solid to obtain powder, wherein the mixing ratio of the L-polylactic acid to the D-polylactic acid is 1:1.
Uniformly mixing superfine stereocomplex polylactic acid (Dv50=200 um, [ Dv (90) -Dv (10) ]/2=320 um) and PBS FZ91 according to the mass ratio of 15:85, then carrying out melt blending extrusion and granulation by a double screw extruder at 160 ℃, and then carrying out sample preparation by an injection molding machine at 170 ℃.
EXAMPLE 3 ultra-fine stereocomplex polylactic acid/PBAT blending
Firstly, preparing superfine stereocomplex polylactic acid: and after uniformly mixing the L-polylactic acid and the D-polylactic acid, mixing the mixture for 5 minutes at 140 ℃ by an internal mixer to obtain a three-dimensional composite polylactic acid solid, and grinding, low-temperature crushing and sieving the three-dimensional composite polylactic acid solid to obtain powder, wherein the mixing ratio of the L-polylactic acid to the D-polylactic acid is 1:1.
Uniformly mixing superfine stereocomplex polylactic acid (Dv50=440 um, [ Dv (90) -Dv (10) ]/2=280 um) and PBAT TH801T according to a mass ratio of 35:65, then carrying out melt blending extrusion and granulation by a double screw extruder at 180 ℃, and then carrying out sample preparation by an injection molding machine at 175 ℃.
Comparative example 1 common polylactic acid/PCL blend
Polylactic acid 3001D and PCL 6500 are evenly mixed according to the mass ratio of 20:80, and then are subjected to melt blending extrusion and granulation through a double screw extruder at 160 ℃, and then are subjected to sample preparation through an injection molding machine at 165 ℃.
Comparative example 2 Large size stereocomplex polylactic acid/PBS blend
Uniformly mixing large-size stereocomplex polylactic acid (Dv50=1300 um, [ Dv (90) -Dv (10) ]/2=350 um) and PBS FZ91 according to the mass ratio of 15:85, then carrying out melt blending extrusion and granulation by a double screw extruder at 160 ℃, and then carrying out sample preparation by an injection molding machine at 170 ℃.
Comparative example 3 superfine stereocomplex polylactic acid/PBS was blended at 230 ℃.
Uniformly mixing superfine stereocomplex polylactic acid (Dv50=400 um, [ Dv (90) -Dv (10) ]/2=300 um) and PBS FZ91 according to the mass ratio of 15:85, then carrying out melt blending extrusion and granulation by a double screw extruder at 230 ℃, and then carrying out sample preparation by an injection molding machine at 220 ℃.
Comparative example 4 Small size Large Dispersion stereocomplex polylactic acid/PBAT blend
Uniformly mixing small-size large-dispersion stereocomplex polylactic acid (Dv50=460 um, [ Dv (90) -Dv (10) ]/2=600um) and PBAT TH801T according to a mass ratio of 35:65, then carrying out melt blending extrusion and granulation through a double screw extruder at 180 ℃, and then carrying out sample preparation through an injection molding machine at 175 ℃.
TABLE 1
Compared with comparative example 1, the heat-resistant temperature of the material is obviously improved by adopting the blending of the superfine stereocomplex polylactic acid material and PCL.
Comparative example 2 the impact performance of the material was much reduced by blending large-sized stereocomplex polylactic acid with PBS as compared to example 2.
Comparative example 3 was processed at a melting temperature of 230 ℃ to a melting point of the stereocomplex polylactic acid powder, and crystals were melted first and then cooled to crystallize to form less stereocomplex crystals, so that comparative example 3 did not have high temperature resistance.
Comparative example 4 compared with example 3, the heat-resistant temperature and physical properties of the material are reduced by blending the small-sized large-dispersion stereocomplex polylactic acid with PBAT.
The foregoing description is only illustrative of the preferred embodiments of the present invention, and therefore should not be taken as limiting the scope of the invention, for all changes and modifications that come within the meaning and range of equivalency of the claims and specification are therefore intended to be embraced therein.
Claims (6)
1. A fully biodegradable material comprising ultra-fine stereocomplex polylactic acid, characterized in that: the raw materials comprise superfine stereocomplex polylactic acid and a biodegradable material, wherein the biodegradable material comprises at least one of PBS, PHBV, PPC, PCL: the weight ratio of the superfine stereocomplex polylactic acid to the biodegradable material is 15-35:65-85;
wherein the superfine stereocomplex polylactic acid is: uniformly mixing the left-handed polylactic acid and the right-handed polylactic acid, and then mixing the mixture for 4-10 minutes at 120-180 ℃ by an internal mixer or a double-screw extruder to obtain a three-dimensional composite polylactic acid solid, wherein the mixing ratio of the left-handed polylactic acid to the right-handed polylactic acid is 4:6-6:4; grinding, pulverizing at low temperature, and sieving to obtain powder with average particle diameter Dv (50) smaller than 500um and [ Dv (90) -Dv (10) ]/2 smaller than 400um;
the superfine stereocomplex polylactic acid and the biodegradable material are melt blended at the processing temperature of 150-200 ℃ to obtain the superfine stereocomplex polylactic acid-containing fully biodegradable material.
2. The fully biodegradable material comprising ultra-fine stereocomplex polylactic acid according to claim 1, wherein: the proportion of the superfine stereocomplex polylactic acid to the PCL is 20:80 by weight, the melting temperature is 160 ℃, and after the full biodegradable material containing the superfine stereocomplex polylactic acid is obtained by melting and blending, the full biodegradable material is subjected to injection molding in an injection molding machine to prepare samples, and the injection molding temperature is 165 ℃.
3. The fully biodegradable material comprising ultra-fine stereocomplex polylactic acid according to claim 1, wherein: the proportion of the superfine stereocomplex polylactic acid/PBS is 15-17:83-85, the melting temperature is 155-165 ℃, and after the superfine stereocomplex polylactic acid-containing fully biodegradable material is obtained by melting and blending, the sample is injection molded in an injection molding machine, and the injection molding temperature is 165-175 ℃.
4. The fully biodegradable material comprising ultra-fine stereocomplex polylactic acid according to claim 1, wherein: the proportion of the superfine stereocomplex polylactic acid to the PBS is 15:85 by weight, the melting temperature is 160 ℃, and after the superfine stereocomplex polylactic acid-containing fully biodegradable material is obtained by melting and blending, the fully biodegradable material is subjected to injection molding in an injection molding machine to prepare samples, and the injection molding temperature is 170 ℃.
5. The fully biodegradable material comprising ultra-fine stereocomplex polylactic acid according to claim 1, wherein: the proportion of the superfine stereocomplex polylactic acid/PBAT blend is 33-35:65-67 by weight, the melting temperature is 175-185 ℃, and after the melt blending, the fully biodegradable material containing the superfine stereocomplex polylactic acid is obtained, the sample is injection molded in an injection molding machine, and the injection molding temperature is 170-180 ℃.
6. The fully biodegradable material comprising ultra-fine stereocomplex polylactic acid according to claim 1, wherein: the proportion of the superfine stereocomplex polylactic acid to the PBAT blend is 35:65 by weight, the melting temperature is 180 ℃, and after the fully biodegradable material containing the superfine stereocomplex polylactic acid is obtained by melt blending, the fully biodegradable material is subjected to injection molding in an injection molding machine to prepare samples, and the injection molding temperature is 175 ℃.
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