CN115304893B - Degradable starch-based plastic and preparation method thereof - Google Patents
Degradable starch-based plastic and preparation method thereof Download PDFInfo
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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
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Abstract
The invention provides a degradable starch-based plastic and a preparation method thereof, the plastic prepared by modifying corn starch, polylactic acid and montmorillonite and reacting with poly (butylene succinate) has excellent mechanical property, thermal stability, barrier property and water resistance while maintaining degradability; the corn starch is obtained by compounding high amylose corn starch and high amylopectin corn starch; modifying corn starch with dopamine and genipin; preparing amino-terminated polylactic acid; introducing epoxy groups into the montmorillonite; the epoxy groups on the modified montmorillonite have chemical reactions with the amino-terminated polylactic acid and the modified corn starch, so that polymer molecular chain intercalation is facilitated to enter a montmorillonite layer, the montmorillonite has the effect similar to an in-situ reaction compatibilizer, and the barrier property of the degradable plastic is effectively improved in a synergistic manner.
Description
Technical Field
The invention relates to the technical field of plastics, in particular to degradable starch-based plastic and a preparation method thereof.
Background
The polymer material is parallel to steel, wood and cement as four large pillar materials. However, the polymer material is difficult to naturally degrade due to the characteristics of stable performance, acid and alkali resistance and the like, and can generate white pollution, and the development of the biodegradable polymer material synthesized by the natural polymer material and a non-petroleum route is one of effective ways for solving the problem of the white pollution of plastics.
At present, the most studied industrialized biodegradable high polymer materials mainly comprise biodegradable aliphatic polyesters such as polylactic acid, polycaprolactone, polytrimethylene terephthalate, polybutylene succinate and the like, wherein the polybutylene succinate has excellent processability and mechanical properties, but has higher price; starch is a natural degradable polymer, has wide source and low price, but has poor mechanical property and water resistance and lower thermal stability; the starch and the poly (butylene succinate) are blended to hopefully prepare the degradable plastic with good performance, but the starch and the poly (butylene succinate) have poor compatibility, and the degradable plastic with excellent performance in all aspects cannot be obtained by directly blending.
Disclosure of Invention
The invention aims to provide a degradable starch-based plastic and a preparation method thereof, which aim to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the degradable starch-based plastic comprises the following components in parts by weight: 30-50 parts of modified corn starch, 5-10 parts of amino-terminated polylactic acid, 40-60 parts of poly butylene succinate and 2.8-6 parts of epoxy modified montmorillonite.
Further, the mass ratio of the sum of the mass of the amino-terminated polylactic acid and the modified corn starch to the mass of the epoxy-modified montmorillonite is 1: (8% -10%).
Further, the preparation of the modified corn starch comprises the following steps: the weight portion ratio is 2:1:0.05 of dopamine hydrochloride, corn starch and genipin, adding deionized water, stirring with ultrasonic waves, drying, grinding and sieving to obtain the modified corn starch.
Further, the preparation of the amino-terminated polylactic acid comprises the following steps:
(1) Mixing levorotatory lactide and ethyl acetate, stirring and dissolving at 55-60 deg.C, cooling to 2-4 deg.C, maintaining for 1-2h, filtering, drying, and repeating for 3-5 times to obtain recrystallized lactide;
(2) Recrystallizing lactide, stannous octoate and N- (tert-butyloxycarbonyl) ethanolamine, preserving the temperature for 2-3h at 115-120 ℃ under the protection of nitrogen, then dissolving the lactide, stannous octoate and N- (tert-butyloxycarbonyl) ethanolamine by using dichloromethane, precipitating by using absolute ethyl alcohol, and drying to obtain the amino-terminated polylactic acid.
Further, the mass ratio of the recrystallized lactide to the stannous octoate to the N- (tert-butoxycarbonyl) ethanolamine is 2000:5:2.
further, the preparation method of the epoxy modified montmorillonite comprises the following steps:
1) Mixing epichlorohydrin and methanol, heating to 60-65 deg.C in oil bath, adding octadecyl dimethyl tertiary amine under stirring, stirring for 4-5h, cooling, distilling under reduced pressure, washing with anhydrous ethanol for 3-5 times to obtain octadecyl dimethyl epoxy ammonium chloride;
2) Mixing sodium montmorillonite and deionized water, ultrasonically stirring for 15-20min to obtain suspension, adding octadecyl dimethyl epoxy ammonium chloride and deionized water, keeping the temperature at 50-60 deg.C for 3-5h, centrifuging, washing with anhydrous ethanol until no chloride ion exists, vacuum drying at 50-60 deg.C for 20-22h, grinding, and sieving to obtain epoxy montmorillonite.
Further, the mass ratio of the sodium montmorillonite to the octadecyl dimethyl epoxy ammonium chloride is 4:5.
further, the preparation method of the degradable starch-based plastic comprises the following steps:
s1: carrying out modification treatment on corn starch to obtain modified corn starch;
s2: mixing the modified corn starch, the amino-terminated polylactic acid and the polybutylene succinate for 6-8min by a torque rheometer, then adding the epoxy modified montmorillonite for mixing for 8-10min, and then performing die pressing by a flat-plate vulcanizing machine to obtain the degradable starch-based plastic.
Further, the corn starch is obtained by compounding high amylose corn starch and high amylopectin corn starch, and the mass ratio of the high amylose corn starch to the high amylopectin corn starch is 2:1.
further, the working conditions of the torque rheometer are as follows: the temperature is 165-175 ℃, and the rotating speed is 100-200r/min; the working condition of the plate vulcanizer is 165-175 ℃ and 10MPa.
The invention has the beneficial effects that:
the invention provides degradable starch-based plastic and a preparation method thereof.
The high amylose corn starch can increase the tensile strength of the plastic within a certain range, and the high amylopectin corn starch can reduce the tensile strength of the plastic within a certain range but can enhance the elongation at break;
the corn starch is modified by dopamine and genipin, so that the compatibility between the starch and the polyester is improved, and a glutaraldehyde structure is hidden in the genipin molecule and can be combined with an amino group in amino-terminated polylactic acid through a covalent bond, so that the complexity of macromolecular entanglement in the degradable starch-based plastic is effectively improved, and the barrier property and the water resistance of the plastic are further enhanced;
hydrophobic groups exist among molecules of polylactic acid, so that the barrier property of the plastic to water vapor can be effectively improved, but the polylactic acid has low toughness and poor high-temperature resistance, and has the problem of compatibility when directly copolymerized with polyester; the polylactic acid with the amino end capping prepared by the invention is added into degradable plastics, so that the compatibility with polyester is improved while the degradability is maintained;
the method synthesizes octadecyl dimethyl epoxy ammonium chloride through addition reaction, utilizes ion exchange organic modified sodium-based montmorillonite to introduce epoxy groups into the montmorillonite, increases the interlayer spacing of the montmorillonite, simultaneously enhances the affinity between the montmorillonite and polylactic acid and poly butylene succinate, realizes the compatibilization effect of a blending system through the intercalation of polymer molecular chains, and increases the interaction between the montmorillonite and a polymer matrix to further enhance the toughness of the degradable starch-based plastic;
and the epoxy groups on the modified montmorillonite have chemical reactions with the amino-terminated polylactic acid and the modified corn starch, so that polymer molecular chain intercalation is facilitated to enter a montmorillonite layer, the montmorillonite has an effect similar to that of an in-situ reaction compatibilizer, and the thermal stability and barrier property of the degradable starch-based plastic are effectively improved in a synergistic manner.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
It should be noted that, if the embodiment of the present invention relates to directional indications such as up, down, left, right, front, and back \8230, the directional indications are only used for explaining a specific posture such as relative positional relationship between components, motion situation, etc., and if the specific posture is changed, the directional indications are changed accordingly. In addition, technical solutions between the embodiments may be combined with each other, but must be based on the realization of the technical solutions by a person skilled in the art, and when the technical solutions are contradictory to each other or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The technical solutions of the present invention are further described in detail with reference to specific examples, which should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
A preparation method of degradable starch-based plastic comprises the following steps:
s1: modifying the corn starch to obtain modified corn starch;
the corn starch is obtained by compounding high amylose corn starch and high amylopectin corn starch, and the mass ratio of the high amylose corn starch to the high amylopectin corn starch is 2:1;
the plastic comprises the following components in parts by weight: 30 parts of modified corn starch, 5 parts of amino-terminated polylactic acid, 40 parts of polybutylene succinate and 2.8 parts of epoxy modified montmorillonite; the mass ratio of the sum of the mass of the amino-terminated polylactic acid and the modified corn starch to the mass of the epoxy-modified montmorillonite is 1:8 percent;
the preparation of the modified corn starch comprises the following steps: the weight portion ratio is 2:1:0.05, mixing dopamine hydrochloride, corn starch and genipin, adding deionized water, ultrasonically stirring, drying, grinding and sieving to obtain modified corn starch;
the preparation of the amino-terminated polylactic acid comprises the following steps:
(1) Mixing 4g of levorotatory lactide crystal powder and 6mL of ethyl acetate, stirring and dissolving at 55 ℃, cooling to 2 ℃, keeping for 1h, filtering, drying, and repeating the operation for 3 times to obtain recrystallized lactide;
(2) 2g of recrystallized lactide, 5mg of stannous octoate and 2mg of N- (tert-butyloxycarbonyl) ethanolamine, preserving the heat for 3 hours at 115 ℃ under the protection of nitrogen, dissolving the lactide by using dichloromethane, precipitating the lactide by using absolute ethyl alcohol, and drying the dissolved solution to obtain amino-terminated polylactic acid;
the preparation method of the epoxy modified montmorillonite comprises the following steps:
1) Mixing 100mL of epoxy chloropropane and 300mL of methanol, heating to 60 ℃ in an oil bath, adding 3g of octadecyl dimethyl tertiary amine under the stirring condition, stirring for 5 hours, cooling, distilling under reduced pressure, and washing for 3 times by absolute ethyl alcohol to obtain octadecyl dimethyl epoxy ammonium chloride;
2) Mixing 4g of sodium montmorillonite with 500mL of deionized water, ultrasonically stirring for 15min to obtain a suspension, adding 5g of octadecyl dimethyl epoxy ammonium chloride and 100mL of deionized water, keeping the temperature at 50 ℃ for 5h, centrifuging, washing with absolute ethanol until no chloride ions exist, drying in vacuum at 50 ℃ for 22h, grinding and sieving to obtain epoxy montmorillonite;
s2: mixing modified corn starch, amino-terminated polylactic acid and poly (butylene succinate) for 6min by a torque rheometer, then adding epoxy modified montmorillonite for mixing for 8min, and then performing mould pressing by a flat-plate vulcanizer to obtain degradable starch-based plastic;
the working conditions of the torque rheometer are as follows: the temperature is 165 ℃, and the rotating speed is 200r/min; the working condition of the plate vulcanizer is 165 ℃ and 10MPa.
Example 2
A preparation method of degradable starch-based plastic comprises the following steps:
s1: carrying out modification treatment on corn starch to obtain modified corn starch;
the corn starch is obtained by compounding high amylose corn starch and high amylopectin corn starch, and the mass ratio of the high amylose corn starch to the high amylopectin corn starch is 2:1;
the plastic comprises the following components in parts by weight: 44 parts of modified corn starch, 6 parts of amino-terminated polylactic acid, 55 parts of polybutylene succinate and 4.5 parts of epoxy modified montmorillonite; the mass ratio of the sum of the mass of the amino-terminated polylactic acid and the modified corn starch to the mass of the epoxy-modified montmorillonite is 1:9 percent;
the preparation of the modified corn starch comprises the following steps: the weight portion ratio is 2:1:0.05, mixing dopamine hydrochloride, corn starch and genipin, adding deionized water, ultrasonically stirring, drying, grinding and sieving to obtain modified corn starch;
the preparation of the amino-terminated polylactic acid comprises the following steps:
(1) Mixing 4g of levorotatory lactide crystal powder and 6mL of ethyl acetate, stirring and dissolving at 58 ℃, cooling to 3 ℃, keeping for 1.5h, filtering, drying, and repeating the operation for 4 times to obtain recrystallized lactide;
(2) 2g of recrystallized lactide, 5mg of stannous octoate and 2mg of N- (tert-butyloxycarbonyl) ethanolamine, preserving the heat for 2.5h at 118 ℃ under the protection of nitrogen, dissolving the lactide by using dichloromethane, precipitating the lactide by using absolute ethyl alcohol, and drying the dissolved solution to obtain amino-terminated polylactic acid;
the preparation method of the epoxy modified montmorillonite comprises the following steps:
1) Mixing 100mL of epoxy chloropropane and 300mL of methanol, heating to 62 ℃ in an oil bath, adding 3g of octadecyl dimethyl tertiary amine under the stirring condition, stirring for 4.5h, cooling, distilling under reduced pressure, and washing with absolute ethyl alcohol for 4 times to obtain octadecyl dimethyl epoxy ammonium chloride;
2) Mixing 4g of sodium montmorillonite with 500mL of deionized water, ultrasonically stirring for 18min to obtain a suspension, adding 5g of octadecyl dimethyl epoxy ammonium chloride and 100mL of deionized water, keeping the temperature at 55 ℃ for 4h, centrifuging, washing with absolute ethyl alcohol until no chloride ions exist, drying at 55 ℃ in vacuum for 21h, grinding and sieving to obtain epoxy montmorillonite;
s2: mixing modified corn starch, amino-terminated polylactic acid and polybutylene succinate for 7min by using a torque rheometer, then adding epoxy modified montmorillonite for mixing for 9min, and then performing mould pressing by using a flat-plate vulcanizing machine to obtain degradable starch-based plastic;
the working conditions of the torque rheometer are as follows: the temperature is 170 ℃, and the rotating speed is 150r/min; the working condition of the plate vulcanizer is that the temperature is 170 ℃ and the pressure is 10MPa.
Example 3
A preparation method of degradable starch-based plastic comprises the following steps:
s1: carrying out modification treatment on corn starch to obtain modified corn starch;
the corn starch is obtained by compounding high amylose corn starch and high amylopectin corn starch, and the mass ratio of the high amylose corn starch to the high amylopectin corn starch is 2:1;
the plastic comprises the following components in parts by weight: 50 parts of modified corn starch, 10 parts of amino-terminated polylactic acid, 60 parts of polybutylene succinate and 6 parts of epoxy modified montmorillonite; the mass ratio of the sum of the mass of the amino-terminated polylactic acid and the modified corn starch to the mass of the epoxy-modified montmorillonite is 1:10 percent;
the preparation of the modified corn starch comprises the following steps: the weight portion ratio is 2:1:0.05, mixing dopamine hydrochloride, corn starch and genipin, adding deionized water, ultrasonically stirring, drying, grinding and sieving to obtain modified corn starch;
the preparation of the amino-terminated polylactic acid comprises the following steps:
(1) Mixing 4g of levorotatory lactide crystal powder and 6mL of ethyl acetate, stirring and dissolving at 60 ℃, cooling to 4 ℃, keeping for 2 hours, filtering, drying, and repeating the operation for 5 times to obtain recrystallized lactide;
(2) 2g of recrystallized lactide, 5mg of stannous octoate and 2mg of N- (tert-butoxycarbonyl) ethanolamine, keeping the temperature of 120 ℃ for 2 hours under the protection of nitrogen, dissolving the mixture by using dichloromethane, precipitating the solution by using absolute ethyl alcohol, and drying the precipitate to obtain amino-terminated polylactic acid;
the preparation method of the epoxy modified montmorillonite comprises the following steps:
1) Mixing 100mL of epoxy chloropropane and 300mL of methanol, heating to 65 ℃ in an oil bath, adding 3g of octadecyl dimethyl tertiary amine under the stirring condition, stirring for 5 hours, cooling, distilling under reduced pressure, and washing for 5 times by using absolute ethyl alcohol to obtain octadecyl dimethyl epoxy ammonium chloride;
2) Mixing 4g of sodium montmorillonite with 500mL of deionized water, ultrasonically stirring for 20min to obtain a suspension, adding 5g of octadecyl dimethyl epoxy ammonium chloride and 100mL of deionized water, keeping the temperature at 60 ℃ for 5h, centrifuging, washing with absolute ethanol until no chloride ions exist, drying in vacuum at 60 ℃ for 20h, grinding and sieving to obtain epoxy montmorillonite;
s2: mixing modified corn starch, amino-terminated polylactic acid and poly (butylene succinate) for 8min by a torque rheometer, then adding epoxy modified montmorillonite for mixing for 10min, and then performing mould pressing by a flat-plate vulcanizer to obtain degradable starch-based plastic;
the working conditions of the torque rheometer are: the temperature is 175 ℃, and the rotating speed is 200r/min; the working condition of the plate vulcanizer is 175 ℃ and 10MPa.
Comparative example 1
Taking example 3 as a control group, the mass ratio of the high amylose corn starch to the high amylopectin corn starch is 1:1, other procedures are normal.
Comparative example 2
The control group of example 3 was used, the corn starch was high amylose corn starch, and the other steps were normal.
Comparative example 3
The control group of example 3 was used, the corn starch was high amylopectin corn starch, and other procedures were normal.
Comparative example 4
In example 3 as a control, the corn starch was not modified, and other steps were normal.
Comparative example 5
The amino-terminated polylactic acid was replaced with polylactic acid as a control in example 3, and the other steps were normal.
Comparative example 6
And (3) taking the example 3 as a control group, replacing epoxy modified montmorillonite with montmorillonite, and enabling other procedures to be normal.
Comparative example 7
Taking the example 3 as a control group, 6.6 parts of epoxy modified montmorillonite, and the mass ratio of the sum of the mass of the amino-terminated polylactic acid and the modified corn starch to the mass of the epoxy modified montmorillonite is 1:11%, the other steps are normal.
Comparative example 8
Taking the embodiment 3 as a control group, 4.2 parts of epoxy modified montmorillonite, and the mass ratio of the sum of the mass of the amino-terminated polylactic acid and the modified corn starch to the mass of the epoxy modified montmorillonite is 1:7%, the other steps are normal.
Sources of raw materials used in the above examples and comparative examples:
dopamine hydrochloride: shanghai xiandin Biotechnology Co., ltd; genipin: wako pure chemical industries, ltd; high amylose corn starch (AM = 65%) and high amylopectin corn starch (AP = 99%): kangbiologicals products, inc., USA; stannous octoate: merck reagent; n- (tert-butoxycarbonyl) ethanolamine N802367 (95%), l-lactide (98%), epichlorohydrin E808937, octadecyl dimethyl tertiary amine N830648 (97%), polybutylene succinate P909171 (injection molding grade), polylactic acid P905787: shanghai Michelin Biochemical technology, inc.; sodium-based montmorillonite: brand PGN, nanocor corporation, usa; methanol, ethyl acetate, absolute ethyl alcohol and dichloromethane, and is analytically pure, national drug group chemical reagent limited.
And (3) performance testing: the degradable starch-based plastics prepared in examples 1-3 and comparative examples 1-8 are subjected to performance tests, and the tensile strength tests are carried out according to GB/T1040.1-2018: sample size: the length is 26mm, the width is 2mm, and the thickness is 2mm; the sample is dried and kept stand for 24 hours before testing, the testing temperature is 25 ℃, and the stretching speed is 2mm/min; taking 10 samples in each group, and taking the average value of the test results; when the sample is placed in the clamp, the long axis of the sample and the axis of the testing machine form a straight line, so that the sample in the test is stably and firmly prevented from sliding and the clamp is prevented from moving; after the prestress is set, installing the calibrated extensometer on the gauge length of the sample and adjusting;
water vapor permeability is measured with reference to ISO2528-2017, gravimetric determination: weighing 5g of anhydrous CaCl 2 Placing the conical flask in a conical flask, sealing the mouth of the conical flask by using prepared plastic, weighing the initial mass of the conical flask, placing the conical flask in a constant temperature and humidity box with the temperature of 25 ℃ and the RH of 50 percent for 4 days, then taking out the conical flask and weighing the conical flask, and calculating the water vapor permeability WVTR = m/(A.t), wherein m is the water vapor migration volume, A is the membrane area, and t is the time; the oxygen permeability is tested by adopting an electric method with reference to YBB 00082003-2015;
thermal stability: measuring the heat resistance of the starch-based biodegradable plastic by using a synchronous thermal analyzer, wherein the sample amount is 10mg, the temperature is increased from 30 ℃ to 600 ℃ at the temperature increase rate of 10 ℃/min, and the initial thermal decomposition temperature is recorded;
the water absorption test is carried out with reference to GB/T1034-2008: drying at 50 ℃ for 24h, cooling to 25 ℃, weighing each sample (mass m 1), soaking in distilled water at 25 ℃ for 48h, taking out the sample, wiping to dry, weighing each sample again (mass m 2), wherein the water absorption rate is = (m 2-m 1)/m 1 × 100%, and the mass is accurate to 0.1mg; specific data are shown in table 1;
TABLE 1
The invention provides degradable starch-based plastic and a preparation method thereof.
Comparing the example 3 with the comparative examples 1, 2 and 3, it can be known that the high amylose corn starch can increase the tensile strength of the plastic within a certain range, and the high amylopectin corn starch can reduce the tensile strength of the plastic within a certain range, but can enhance the elongation at break;
comparing the example 3 with the comparative example 4, it can be seen that the compatibility between the starch and the polyester is improved by modifying the corn starch with dopamine and genipin, and the genipin has a glutaraldehyde structure in the molecule, and can be covalently bonded with the amino group in the amino-terminated polylactic acid, so that the complexity of macromolecule entanglement in the plastic is effectively improved, and the water resistance and the barrier property of the plastic are enhanced;
comparing example 3 with comparative example 5, it can be seen that the hydrophobic groups exist between the molecules of polylactic acid, which can effectively improve the water vapor barrier property of plastics, but the toughness is low, the high temperature resistance is poor, and the compatibility problem also exists when the polylactic acid is directly copolymerized with polyester; the polylactic acid with the end capped by the amino group prepared by the invention is added into the degradable plastic, so that the compatibility with the polyester is improved while the degradability is maintained;
comparing the embodiment 3 with the comparative example 6, it can be seen that the octadecyl dimethyl epoxy ammonium chloride is synthesized by addition reaction, the ion exchange organic modified sodium-based montmorillonite is utilized to introduce epoxy groups into the montmorillonite, the interlayer spacing of the montmorillonite is increased, the affinity between the montmorillonite and polylactic acid and polybutylene succinate is enhanced, the compatibilization effect of a blending system is realized by intercalation of polymer molecular chains, and the interaction between the montmorillonite and a polymer matrix is increased, so that the toughness of the degradable plastic is further enhanced;
comparing the embodiment 3 with the comparative examples 7 and 8, it can be seen that chemical reactions exist between the epoxy group on the modified montmorillonite, the amino-terminated polylactic acid and the modified corn starch, which are beneficial for the polymer molecular chain intercalation to enter the montmorillonite layer, so that the montmorillonite has the effect similar to that of an in-situ reaction compatibilizer, and the water resistance of the degradable plastic is effectively improved in a synergistic manner.
The above description is only an example of the present invention, and is not intended to limit the scope of the present invention, and all modifications, equivalents and applications made by the present invention or directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (5)
1. The preparation method of the degradable starch-based plastic is characterized by comprising the following steps:
s1: the weight portion ratio is 2:1:0.05, mixing dopamine hydrochloride, corn starch and genipin, adding deionized water, ultrasonically stirring, drying, grinding and sieving to obtain modified corn starch;
s2: mixing modified corn starch, amino-terminated polylactic acid and poly (butylene succinate) for 6-8min by a torque rheometer, then adding epoxy modified montmorillonite for mixing for 8-10min, and then performing mould pressing by a flat-plate vulcanizer to obtain degradable starch-based plastic;
the corn starch is obtained by compounding high amylose corn starch and high amylopectin corn starch, and the mass ratio of the high amylose corn starch to the high amylopectin corn starch is 2:1;
the degradable starch-based plastic comprises the following components in parts by weight: 30-50 parts of modified corn starch, 5-10 parts of amino-terminated polylactic acid, 40-60 parts of poly (butylene succinate) and 2.8-6 parts of epoxy modified montmorillonite; the mass ratio of the sum of the mass of the amino-terminated polylactic acid and the modified corn starch to the mass of the epoxy-modified montmorillonite is 1: (8% -10%);
the preparation of the amino-terminated polylactic acid comprises the following steps:
(1) Mixing levorotatory lactide and ethyl acetate, stirring and dissolving at 55-60 deg.C, cooling to 2-4 deg.C, maintaining for 1-2h, filtering, drying, and repeating for 3-5 times to obtain recrystallized lactide;
(2) Mixing the recrystallized lactide, stannous octoate and N- (tert-butyloxycarbonyl) ethanolamine under the protection of nitrogen, keeping the temperature at 115-120 ℃ for 2-3h, dissolving the mixture by using dichloromethane, precipitating the dissolved solution by using absolute ethyl alcohol, and drying the precipitated solution to obtain amino-terminated polylactic acid;
the preparation method of the epoxy modified montmorillonite comprises the following steps:
1) Mixing epichlorohydrin and methanol, heating to 60-65 deg.C in oil bath, adding octadecyl dimethyl tertiary amine under stirring, stirring for 4-5h, cooling, distilling under reduced pressure, and washing with anhydrous ethanol for 3-5 times to obtain octadecyl dimethyl epoxy ammonium chloride;
2) Mixing sodium montmorillonite and deionized water, ultrasonically stirring for 15-20min to obtain suspension, adding octadecyl dimethyl epoxy ammonium chloride and deionized water, keeping the temperature at 50-60 deg.C for 3-5h, centrifuging, washing with anhydrous ethanol until no chloride ion exists, vacuum drying at 50-60 deg.C for 20-22h, grinding, and sieving to obtain epoxy montmorillonite.
2. The method for preparing the degradable starch-based plastic according to claim 1, wherein the working conditions of the torque rheometer are as follows: the temperature is 165-175 ℃, and the rotating speed is 100-200r/min; the working conditions of the plate vulcanizer are as follows: the temperature is 165-175 ℃ and the pressure is 10MPa.
3. The method for preparing the degradable starch-based plastic according to claim 1, wherein the mass ratio of the recrystallized lactide to the stannous octoate to the N- (tert-butoxycarbonyl) ethanolamine is 2000:5:2.
4. the method for preparing degradable starch-based plastic according to claim 1, wherein the mass ratio of sodium-based montmorillonite to octadecyl dimethyl epoxy ammonium chloride is 4:5.
5. a degradable starch-based plastic, which is prepared by the preparation method according to any one of claims 1 to 4.
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| CN1858114A (en) * | 2006-04-25 | 2006-11-08 | 邓国权 | Preparation of biological degradation resin composite and modified special resin and product forming process |
| JP2011074114A (en) * | 2009-09-29 | 2011-04-14 | Yamato Esuron Kk | Biodegradable resin composition |
| CN103992517A (en) * | 2014-06-10 | 2014-08-20 | 华东理工大学 | Continuously-produced full-degradable starch-based plastic alloy and preparation method thereof |
| CN105017731A (en) * | 2014-11-26 | 2015-11-04 | 江苏天仁生物材料有限公司 | Fully biodegradable material taking polylactic acid/polybuthylenesuccinate as basic material and preparation method of fully biodegradable material |
| CN105670248A (en) * | 2014-12-04 | 2016-06-15 | 河南青源天仁生物技术有限公司 | Full-degradable seedling breeding plate with PLA/PBS as base material and preparation method thereof |
| CN109825049A (en) * | 2019-03-14 | 2019-05-31 | 宁波钜亿新材料科技有限公司 | A kind of high amylose starches/lactic acid composite material mother material production technology |
| CN113214620A (en) * | 2021-05-25 | 2021-08-06 | 湖北工业大学 | Preparation method and application of epoxy group organic modified montmorillonite |
| CN113234307A (en) * | 2021-06-29 | 2021-08-10 | 山东农业大学 | Full-degradable antibacterial food packaging film and preparation method thereof |
| CN114106541A (en) * | 2022-01-28 | 2022-03-01 | 北京禾易和科技有限公司 | Environment-friendly food packaging material, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1858114A (en) * | 2006-04-25 | 2006-11-08 | 邓国权 | Preparation of biological degradation resin composite and modified special resin and product forming process |
| JP2011074114A (en) * | 2009-09-29 | 2011-04-14 | Yamato Esuron Kk | Biodegradable resin composition |
| CN103992517A (en) * | 2014-06-10 | 2014-08-20 | 华东理工大学 | Continuously-produced full-degradable starch-based plastic alloy and preparation method thereof |
| CN105017731A (en) * | 2014-11-26 | 2015-11-04 | 江苏天仁生物材料有限公司 | Fully biodegradable material taking polylactic acid/polybuthylenesuccinate as basic material and preparation method of fully biodegradable material |
| CN105670248A (en) * | 2014-12-04 | 2016-06-15 | 河南青源天仁生物技术有限公司 | Full-degradable seedling breeding plate with PLA/PBS as base material and preparation method thereof |
| CN109825049A (en) * | 2019-03-14 | 2019-05-31 | 宁波钜亿新材料科技有限公司 | A kind of high amylose starches/lactic acid composite material mother material production technology |
| CN113214620A (en) * | 2021-05-25 | 2021-08-06 | 湖北工业大学 | Preparation method and application of epoxy group organic modified montmorillonite |
| CN113234307A (en) * | 2021-06-29 | 2021-08-10 | 山东农业大学 | Full-degradable antibacterial food packaging film and preparation method thereof |
| CN114106541A (en) * | 2022-01-28 | 2022-03-01 | 北京禾易和科技有限公司 | Environment-friendly food packaging material, preparation method and application |
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