CN117720803A - Full-biodegradable polymer alloy material and preparation method thereof - Google Patents
Full-biodegradable polymer alloy material and preparation method thereof Download PDFInfo
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- CN117720803A CN117720803A CN202311762717.5A CN202311762717A CN117720803A CN 117720803 A CN117720803 A CN 117720803A CN 202311762717 A CN202311762717 A CN 202311762717A CN 117720803 A CN117720803 A CN 117720803A
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- 239000000956 alloy Substances 0.000 title claims abstract description 68
- 229920002988 biodegradable polymer Polymers 0.000 title claims abstract description 43
- 239000004621 biodegradable polymer Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 76
- 229920000728 polyester Polymers 0.000 claims abstract description 62
- 239000003292 glue Substances 0.000 claims abstract description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 13
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 45
- 239000004626 polylactic acid Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 10
- -1 polybutylene terephthalate-adipate Polymers 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims description 4
- 229920000229 biodegradable polyester Polymers 0.000 claims 4
- 239000004622 biodegradable polyester Substances 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 31
- 229920000379 polypropylene carbonate Polymers 0.000 description 29
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 12
- 238000002464 physical blending Methods 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 7
- 230000002779 inactivation Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 229920001896 polybutyrate Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the technical field of polymer alloy materials, and provides a full-biodegradable polymer alloy material and a preparation method thereof, wherein the full-biodegradable polymer alloy material comprises the following steps: s1, introducing carbon dioxide gas to react propylene oxide, phthalic anhydride and a catalyst to obtain PPC polymer glue solution; s2, adding a degradable bio-polyester solution and a catalyst into the polymer glue solution to perform transesterification reaction to obtain a degradable bio-polyester compatibilized polymer glue solution; s3, adding water into the degradable bio-polyester compatibilizing polymer glue solution, and separating the glue solution to obtain the degradable bio-polyester compatibilizing polymer; s4, adding the degradable biological polyester into the degradable biological polyester compatilizer, blending, and extruding to obtain the full-biodegradable polymer alloy material. By the technical scheme, the problems of poor heat resistance, low tensile strength and low elongation at break of the material in the prior art are solved, and the high-efficiency and low-cost preparation of the full-biodegradable polymer alloy is realized.
Description
Technical Field
The invention relates to the technical field of polymer alloy materials, in particular to a full-biodegradable polymer alloy material and a preparation method thereof.
Background
The fully biodegradable polypropylene carbonate PPC alloy material is prepared into a modified plastic alloy by a physical blending method through a double screw extruder by PPC/PBAT or PPC/PLA, and a certain amount of additives such as compatilizer, lubricant and the like are added in the process to improve the mechanical and thermal properties of the alloy material. For example, in CN101735587B, CN202010450163.5, a capping agent, a compatilizer, modified light calcium carbonate and the like are added into a blend of PPC and PBAT and PLA, and a direct physical blending method is adopted to prepare the biodegradable resin. However, physical blending cannot effectively improve the interfacial compatibility of alloy materials, so that the material performance is limited, stress defects and compatilizer migration are easy to occur in the processing process, the heat resistance, tensile strength and elongation at break of the material are reduced, cracks are easy to occur in the material, surface defects of the material are caused, and further application of the material is affected.
Except that the physical blending method is adopted to prepare the fully biodegradable polypropylene carbonate PPC alloy material, different functional monomers are adopted in the CN111378101A, CN114573799A patent, and the alloy material is prepared by a chemical modification method in a polymerization kettle, so that the aim of improving the performance of the alloy material is fulfilled, but the cost and the technical difficulty of chemical modification are high, and the broad-spectrum and definite modification effect of the polymer alloy is difficult to achieve.
Disclosure of Invention
The invention provides a full-biodegradable polymer alloy material and a preparation method thereof, which solve the problems of poor heat resistance, low tensile strength and low elongation at break of the full-biodegradable polymer alloy material in the related technology.
The technical scheme of the invention is as follows:
a preparation method of a full-biodegradable polymer alloy material comprises the following steps:
s1, introducing carbon dioxide gas into propylene oxide, phthalic anhydride and a catalyst to perform polymerization reaction, and obtaining PPC polymer glue solution;
s2, adding a degradable bio-polyester solution and an ester exchange catalyst into the PPC polymer glue solution to carry out ester exchange reaction to obtain a degradable bio-polyester compatibilizing polymer glue solution;
s3, mixing the degradable bio-polyester compatibilizing polymer glue solution with water, and separating the glue solution to obtain the degradable bio-polyester compatibilizing polymer;
s4, blending the degradable bio-polyester compatilizer polymer and the degradable bio-polyester, and extruding to obtain the full-biodegradable polymer alloy material.
As a further technical scheme, S4 is to blend and extrude the degradable bio-polyester compatilizer and the degradable bio-polyester by a double screw extruder to obtain the full-biodegradable polymer alloy material.
As a further technical scheme, the catalyst in the S1 consists of a triethylboron solution and one of tetra-n-butyl ammonium chloride, bis (triphenylphosphine) ammonium chloride and tetramethyl ammonium chloride.
As a further technical scheme, the concentration of triethylboron in the triethylboron solution is 10wt%, and the solvent is tetrahydrofuran.
As a further technical scheme, the transesterification catalyst in the S2 comprises one or more of triethylamine, pyridine, sodium ethoxide and other organic bases.
As a further technical scheme, the mass ratio of the epoxy propane to the phthalic anhydride in the S1 is 12:35.
As a further technical scheme, the reaction temperature in the S1 is 70-90 ℃, the reaction time is 1-6 h, and the reaction pressure is 1-5 MPa.
As a further technical scheme, the degradable biopolyester in the degradable biopolyester solution in S2 and the degradable biopolyester in S4 respectively independently comprise one or two of polylactic acid and polybutylene terephthalate-adipate.
As a further technical scheme, the concentration of the degradable bio-polyester in the degradable bio-polyester solution in the S2 is 5-35 wt%.
As a further technical scheme, the solvent in the degradable bio-polyester solution in the step S2 is propylene oxide.
As a further technical scheme, the temperature of the transesterification reaction in the S2 is 70-95 ℃, and the reaction time is 0.5-0.2 h.
As a further technical scheme, the mass of the degradable bio-polyester in the degradable bio-polyester solution in the S2 is 0.5-2% of the mass of the PPC polymer glue solution.
As a further technical scheme, the mass sum of the degradable bio-polyester in the S4 and the degradable bio-polyester in the S2 degradable bio-polyester solution is 5% -50% of the mass sum of the PPC polymer glue solution.
The invention also comprises the full-biodegradable polymer alloy material prepared by the preparation method of the full-biodegradable polymer alloy material.
The working principle and the beneficial effects of the invention are as follows:
1. according to the invention, the principle of transesterification is skillfully utilized, phthalic anhydride monomers are added into a kettle, and simultaneously, in-situ compatibilization reaction is completed in the transesterification kettle in two steps, PPC and a part of degradable bio-polyester (in the form of solution) are firstly subjected to in-situ in-kettle in-situ modification to perform in-situ compatibilization, and then another part of the degradable bio-polyester is added to perform alloy modification through physical blending (as shown in figure 1), so that the conditions of the reaction kettle are reduced, the reaction time is shortened, in-situ compatibilization reaction can be completed under the condition of not changing the original process, and the energy consumption is saved while the modification effect is provided through on-line physical blending. The degradable bio-polyester compatibilizer polymer obtained by in-situ kettle modification and compatibilization of the PPC and the degradable bio-polyester contains the same components as the main components of the alloy, has better compatibility, and is a macromolecular substance and can not cause migration problems.
2. In the invention, the heat resistance, the tensile strength and the elongation at break of the degradable polymer alloy material are further improved by limiting the addition amount of the degradable bio-polyester added during in-situ compatibilization and physical blending alloy modification.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a flowchart of the preparation of the fully biodegradable polymer alloy material according to examples 1 to 8 of the present invention;
FIG. 2 is a comparative polymer GPC chart of example 1 and comparative example 1 of the present invention;
FIG. 3 is a comparative plot of polymer DSC of inventive example 1, comparative examples 1-4.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples: the concentration of triethylboron in the triethylboron solution was 10% by weight, and the solvent used was tetrahydrofuran.
Example 1
A preparation method of a full-biodegradable polymer alloy material comprises the following steps:
s1, adding 12kg of propylene oxide, 35kg of phthalic anhydride, 95.3g of tetra-n-butyl ammonium chloride and 2.3L of triethylboron solution into a reaction kettle under the condition of stirring at the temperature of 75 ℃, introducing carbon dioxide gas to the pressure of 1MPa, and reacting for 3 hours to obtain 53kg of PPC polymer glue solution;
s2, transferring the PPC polymer glue solution into a transesterification reaction kettle, adding 6kg of 10wt% polylactic acid solution and 34.7g of triethylamine, and reacting for 1h at 80 ℃ to obtain the degradable bio-polyester compatibilizer polymer glue solution; wherein the solvent in the polylactic acid solution is propylene oxide;
s3, transferring the degradable bio-polyester compatibilizer polymer glue solution into an inactivation desolventizing kettle, adding 85 ℃ water, and obtaining the degradable bio-polyester compatibilizer polymer through a water-glue separation device;
s4, conveying the degradable bio-polyester compatibilized polymer to double-screw devolatilization equipment, adding 10kg of polylactic acid for blending, and then bracing and granulating to obtain the full-biodegradable polymer alloy material.
Example 2
A preparation method of a full-biodegradable polymer alloy material comprises the following steps:
s1, adding 12kg of propylene oxide, 35kg of phthalic anhydride, 953g of tetra-n-butyl ammonium chloride and 22.6L of triethylboron solution into a reaction kettle under the stirring condition, introducing carbon dioxide gas to the pressure of 2MPa, and reacting for 5 hours to obtain 58kg of PPC polymer glue solution;
s2, transferring the PPC polymer glue solution into a transesterification reaction kettle, adding 24kg of 5wt% polylactic acid solution and 208g of triethylamine, and reacting for 2 hours at 70 ℃ to obtain degradable bio-polyester compatibilizer polymer glue solution; wherein the solvent in the polylactic acid solution is propylene oxide;
s3, transferring the degradable bio-polyester compatilizer into an inactivation desolventizing kettle, adding 85 ℃ water, and passing through a water gel separation device to obtain the degradable bio-polyester compatilizer;
s4, conveying the degradable bio-polyester compatibilized polymer to double-screw devolatilization equipment, adding 27.8kg of polylactic acid to blend, and then bracing and granulating to obtain the fully biodegradable polymer alloy material.
Example 3
A preparation method of a full-biodegradable polymer alloy material comprises the following steps:
s1, adding 12kg of propylene oxide, 35kg of phthalic anhydride, 572g of solution containing tetra-n-butyl ammonium chloride and 18L of triethylboron into a reaction kettle under the condition of stirring, introducing carbon dioxide gas to the pressure of 5MPa, and reacting for 1h to obtain 55kg of PPC polymer glue solution;
s2, transferring the PPC polymer glue solution into a transesterification reaction kettle, adding 3kg of 10wt% polylactic acid solution and 208g of triethylamine, and reacting for 0.5h at 95 ℃ to obtain degradable bio-polyester compatibilizer polymer glue solution; wherein the solvent in the polylactic acid solution is propylene oxide;
s3, transferring the degradable bio-polyester compatibilizer polymer glue solution into an inactivation desolventizing kettle, adding 85 ℃ water, and obtaining the degradable bio-polyester compatibilizer polymer through a water-glue separation device;
s4, conveying the degradable bio-polyester compatibilized polymer to double-screw devolatilization equipment, adding 2.45kg of polylactic acid to blend, and then bracing and granulating to obtain the fully biodegradable polymer alloy material.
Example 4
This example differs from example 1 in that the polylactic acid solution in S2 was 50kg and the polylactic acid in S4 was 5.6kg.
Example 5
This example differs from example 1 in that the 10wt% polylactic acid solution in S2 was replaced with an equivalent 10wt% polybutylene terephthalate-adipate solution (propylene oxide as the solvent) and the polylactic acid in S2 was replaced with an equivalent polybutylene terephthalate-adipate.
Example 6
This example differs from example 5 in that the 10wt% polybutylene terephthalate-adipate solution in S2 was 50kg and the polybutylene terephthalate-adipate in S4 was 5.6kg.
Example 7
This example differs from example 1 in that the polylactic acid solution in S2 was 0.26kg and the polylactic acid in S4 was 10.34kg.
Example 8
This example differs from example 1 in that the polylactic acid solution in S2 was 1.1kg and the polylactic acid in S4 was 9.5kg.
Comparative example 1
A method of preparing a polymer alloy material comprising the steps of:
s1, adding 12kg of propylene oxide, 35kg of phthalic anhydride, 95.3g of tetra-n-butyl ammonium chloride and 2.3L of triethylboron solution into a reaction kettle under the condition of stirring at the temperature of 75 ℃, introducing carbon dioxide gas to the pressure of 1MPa, and reacting for 3 hours to obtain 53kg of PPC polymer glue solution;
s2, transferring the PPC polymer glue solution into an inactivation desolventizing kettle, adding 85 ℃ water, and passing through a water-glue separation device to obtain a PPC polymer;
s3, conveying the PPC polymer to double-screw devolatilization equipment, and bracing and granulating to obtain the polymer alloy material.
Comparative example 2
A method of preparing a polymer alloy material comprising the steps of:
s1, adding 12kg of propylene oxide, 35kg of phthalic anhydride, 95.3g of tetra-n-butyl ammonium chloride and 2.3L of triethylboron solution into a reaction kettle under the condition of stirring at the temperature of 75 ℃, introducing carbon dioxide gas to the pressure of 1MPa, and reacting for 3 hours to obtain 53kg of PPC polymer glue solution;
s2, transferring the PPC polymer glue solution into an inactivation desolventizing kettle, adding 85 ℃ water, and passing through a water-glue separation device to obtain a PPC polymer;
s3, adding 10.6kg of polylactic acid into the PPC polymer, blending, and then bracing and granulating to obtain the polymer alloy material.
Comparative example 3
A method of preparing a polymer alloy material comprising the steps of:
s1, adding 12kg of propylene oxide, 35kg of phthalic anhydride, 95.3g of tetra-n-butyl ammonium chloride and 2.3L of triethylboron solution into a reaction kettle under the condition of stirring at the temperature of 75 ℃, introducing carbon dioxide gas to the pressure of 1MPa, and reacting for 3 hours to obtain 53kg of PPC polymer glue solution;
s2, cooling the reaction kettle to room temperature, releasing the pressure of carbon dioxide, adding 106kg of 10wt% polylactic acid solution into the reaction kettle, and reacting at 70 ℃ for 12 hours to obtain degradable bio-polyester solubilizing polymer glue solution; wherein the solvent in the polylactic acid solution is propylene oxide;
s3, transferring the degradable bio-polyester compatibilizer polymer glue solution into an inactivation desolventizing kettle, adding 85 ℃ water, and obtaining the degradable bio-polyester compatibilizer polymer through a water-glue separation device;
s4, conveying the degradable bio-polyester compatibilized polymer to double-screw devolatilization equipment, and bracing and granulating to obtain a polymer alloy material.
Comparative example 4
A preparation method of a full-biodegradable polymer alloy material comprises the following steps:
s1, under the condition of 75 ℃ and stirring, 106kg of 10wt% polylactic acid solution, 12kg of propylene oxide, 35kg of phthalic anhydride, 95.3g of tetra-n-butyl ammonium chloride and 2.3L of triethylboron solution are added into a reaction kettle, carbon dioxide gas is introduced to the pressure of 1MPa, and the reaction is carried out for 6 hours, so that 159kg of degradable biopolyester polymer glue solution is obtained; wherein the solvent in the polylactic acid solution is propylene oxide;
s2, transferring the degradable bio-polyester polymer glue solution into an inactivation desolventizing kettle, adding 85 ℃ water, and obtaining the degradable bio-polyester polymer through a water-glue separation device;
s3, conveying the degradable bio-polyester polymer to double-screw devolatilization equipment, and bracing and granulating to obtain a polymer alloy material.
Test examples
(1) Determination of the molecular weight and molecular weight distribution of the Polymer in example 1 and comparative example 1 by gel permeation chromatography
As can be seen from fig. 2, in comparative example 1, the molecular weight Mn:93180 Da; in example 1, the molecular weight Mn:109576 Da. Compared with comparative example 1, the high molecular weight peak ratio of example 1 was increased, the peak pattern was widened, and the low molecular weight peak was advanced.
Therefore, the invention modifies the biodegradable polymer alloy material in a chemical grafting mode, enhances the binding force between the matrix and the additive, and improves the physical properties of the alloy material.
(2) The glass transition temperatures of the polymer alloy materials in example 1 and comparative examples 1 to 3 were measured by a differential scanning calorimetric test method, which comprises the following steps: the sample was first rapidly warmed to 190 ℃ for 3min to eliminate the heat history, then cooled to 10 ℃ at 20 ℃/min for 2min, then warmed to 190 ℃ at 10 ℃/min, and finally analyzed for glass transition temperature thermal performance parameters according to the experimental results, as shown in fig. 3.
Comparative example 1 polylactic acid was not added, comparative example 2 polylactic acid was directly subjected to physical blending, comparative example 3 "one pot two step" polymerization, polylactic acid was added as a second step in the form of a polylactic acid solution in the absence of a transesterification catalyst, and comparative example 4 "one pot" polymerization, polylactic acid was added as a polylactic acid solution in the absence of a transesterification catalyst. As can be seen from FIG. 3, in comparative examples 1 to 4, the glass transition temperature of the polymer was reduced slightly as compared with example 1, and in comparative examples 2 and 4, the crystallization temperature was also slightly reduced, and in comparative example 3, no melting crystallization peak was present. Therefore, the preparation method of the full-biodegradable polymer alloy material can obviously improve the glass transition temperature and the crystallization temperature of the full-biodegradable polymer alloy material.
Specifically, compared with example 1, the glass transition temperature of the degradable bio-polyester compatibilising polymer formed by adding polylactic acid in comparative example 3 is obviously improved; compared with comparative example 2, the glass transition temperature and the crystallization temperature of the fully biodegradable polymer alloy material formed by blending the degradable bio-polyester compatibilising polymer and the unreacted polylactic acid solution in comparative example 4 are higher, and the fully biodegradable polymer alloy material formed by blending the degradable bio-polyester compatibilising polymer and the polylactic acid solid in example 1 has higher glass transition temperature and higher crystallization temperature; example 1 exhibited a melting crystallization peak while also having a higher glass transition temperature than comparative example 3.
(3) The tensile strength, the microcard softening temperature and the elongation at break of each material in examples 1 to 8 and comparative examples 1 to 4 were measured as follows:
tensile strength was measured according to the measurement method in ASTM D638; determining the microcard softening temperature according to the determination method in ASTM D1525; elongation at break was measured according to the measurement method in ASTM D882, and the measurement results are shown in table 1.
Table 1 results of measuring the properties of Polymer alloy materials in examples 1 to 8 and comparative examples 1 to 4
Compared with the embodiment 1, the polylactic acid is not added in the comparative example 1, the polylactic acid in the comparative example 2 is directly subjected to physical blending, the polylactic acid in the comparative example 3 is added in the form of a polylactic acid solution for the second step in the absence of a transesterification catalyst, the polylactic acid in the comparative example 4 is added in the form of a polylactic acid solution in the absence of a transesterification catalyst, and as a result, the tensile strength, the microcard softening temperature and the elongation at break of the polymer alloy material in the comparative examples 1-4 are lower than those in the embodiment 1, which indicates that the preparation method of the fully biodegradable polymer alloy material in the invention can improve the tensile strength, the microcard softening temperature and the elongation at break of the fully biodegradable polymer alloy material.
Compared with the embodiment 1, the embodiment 7-8 changes the addition amount of the polylactic acid in the polylactic acid solution in the S2, and the comparison shows that the tensile strength, the microcard softening temperature and the elongation at break of the fully biodegradable polymer alloy material in the embodiment 1 are all higher than those of the embodiment 7-8, so that the tensile strength, the microcard softening temperature and the elongation at break of the fully biodegradable polymer alloy material can be better improved when the addition amount of the polylactic acid in the polylactic acid solution in the S2 is 1% of that of the PPC polymer glue solution.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the full-biodegradable polymer alloy material is characterized by comprising the following steps of:
s1, introducing carbon dioxide gas into propylene oxide, phthalic anhydride and a catalyst to perform polymerization reaction, and obtaining PPC polymer glue solution;
s2, adding a degradable bio-polyester solution and an ester exchange catalyst into the PPC polymer glue solution to carry out ester exchange reaction to obtain a degradable bio-polyester compatibilizing polymer glue solution;
s3, mixing the degradable bio-polyester compatibilizing polymer glue solution with water, and separating by using the water glue to obtain the degradable bio-polyester compatibilizing polymer;
s4, blending the degradable bio-polyester compatilizer polymer and the degradable bio-polyester, and extruding to obtain the full-biodegradable polymer alloy material.
2. The method for preparing the fully biodegradable polymer alloy material according to claim 1, wherein the mass ratio of the epoxy propane to the phthalic anhydride in the S1 is 12:35.
3. The method for preparing the fully biodegradable polymer alloy material according to claim 1, wherein the reaction temperature in the step S1 is 70-90 ℃, the reaction time is 1-6 hours, and the reaction pressure is 1-5 MPa.
4. The method for preparing a fully biodegradable polymer alloy according to claim 1, wherein the biodegradable polyester in the solution of the biodegradable polyester in S2 and the biodegradable polyester in S4 each independently comprises one or two of polylactic acid and polybutylene terephthalate-adipate.
5. The method for preparing the fully biodegradable polymer alloy material according to claim 1, wherein the concentration of the degradable bio-polyester in the degradable bio-polyester solution in the S2 is 5-35 wt%.
6. The method for preparing a fully biodegradable polymer alloy material according to claim 1, wherein the solvent in the biodegradable polyester solution in S2 is propylene oxide.
7. The method for preparing a fully biodegradable polymer alloy material according to claim 1, wherein the temperature of the transesterification reaction in S2 is 70-95 ℃ and the reaction time is 0.5-2 hours.
8. The method for preparing the fully biodegradable polymer alloy material according to claim 1, wherein the mass of the degradable bio-polyester in the degradable bio-polyester solution in the step S2 is 0.5-2% of the mass of the PPC polymer glue solution.
9. The preparation method of the full-biodegradable polymer alloy material according to claim 1, wherein the mass sum of the degradable bio-polyester in the S4 and the degradable bio-polyester in the S2 degradable bio-polyester solution is 5% -50% of the mass sum of the PPC polymer glue solution.
10. The fully biodegradable polymer alloy material prepared by the method for preparing a fully biodegradable polymer alloy material according to any one of claims 1 to 9.
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| CN202311762717.5A CN117720803A (en) | 2023-12-20 | 2023-12-20 | Full-biodegradable polymer alloy material and preparation method thereof |
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