CN114149668A - Preparation method of PBAT (poly (butylene adipate-co-terephthalate)) based material with enhanced rigidity and toughness of mesomorphic phase - Google Patents
Preparation method of PBAT (poly (butylene adipate-co-terephthalate)) based material with enhanced rigidity and toughness of mesomorphic phase Download PDFInfo
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Abstract
The invention provides a preparation method of a rigidity-toughness balanced PBAT-based material based on mesomorphic phase enhancement, belonging to the technical field of biodegradable high polymer materials. It has solved the problem that prior art has had intensity to hang down. The preparation method of the PBAT-based material with enhanced rigidity and toughness based on the mesomorphic phase is characterized by comprising the following steps: (1) drying PBAT and polylactic acid (PLA) particles, mixing the PBAT and the PLA particles with a chain extender according to a certain mass percentage, and then melting and extruding the mixture; (2) the PBAT/PLA blend particles are melted and hot-pressed into a film in a plate vulcanizing machine, and the melt is quickly transferred to a drying oven with a certain temperature for isothermal crystallization. The preparation method of the PBAT-based material with enhanced rigidity and toughness based on the mesomorphic phase can improve the strength of the material.
Description
Technical Field
The invention relates to the technical field of biodegradable high polymer materials, in particular to a preparation method of a rigidity-toughness balance poly (butylene adipate/terephthalate) -based material based on mesomorphic phase enhancement.
Background
In the last hundred years, human beings are increasingly plagued by the problem of environmental pollution caused by traditional petroleum-based plastics. The search for biodegradable polymeric materials as alternatives has been recognized as an important task for sustainable development in human society. The poly (butylene adipate terephthalate) (PBAT) has the excellent biodegradability of aliphatic polyester and the excellent mechanical property and high temperature resistance of aromatic polyester, and can be prepared into sheet or film materials by processing modes such as injection molding, extrusion, blow molding and the like, and the market demand of the poly (butylene adipate terephthalate) (PBAT) is increasing day by day.
Although PBAT has been used in degradable agricultural mulching films, packaging films, etc., it has limited its wider application due to its low modulus, low yield strength, and low hardness. These drawbacks of PBAT can be overcome by blending with other degradable polymers, such as polylactic acid (PLA). Because PLA has higher strength and modulus, the PBAT material modified by PLA blending has higher mechanical strength while the biodegradability is kept. However, because the solubility parameters of PBAT and PLA are greatly different and incompatible, phase separation occurs in the blend, and the toughness of the material is greatly reduced.
Previous studies have reported many methods to try to increase the compatibility of the two to improve the toughness of the blended material, for example, chinese patent CN111378259A discloses that the blending compatibility is improved by using a reactive compatibilizer containing epoxy groups to react with the terminal hydroxyl groups of PBAT and PLA and then linking the molecular chains of the two; chinese invention patent CN110079065A discloses a compatibilizer prepared by using PLA-PBAT-PLA block copolymer as a blend; the Chinese invention patent CN105778449A discloses that a multi-block copolymer obtained by ester exchange reaction is used as a compatibilizer of a blend by adding an ester exchange catalyst in the process of blending PBAT and PLA.
However, the compatibility of PBAT and PLA is improved by changing the chemical structure in the above methods, the steps are complicated, the reaction is not easy to control, and the introduction of a large amount of compatibilizer with other chemical components not only increases the processing cost of the raw materials, but also may affect the degradability, biocompatibility, etc. of the materials. Compared with chemical modification, the physical modification is simpler and more convenient to realize by means of heat treatment and the like and by controlling processing conditions. The PBAT and the PLA can form aggregation state structures with different order degrees in the heat treatment process at different temperatures, such as an amorphous phase, a mesomorphic phase and crystallization phase, and the mechanical properties are different, so that the mechanical properties of the material can be expected to be further optimized by reasonably regulating the phase state structure of the PBAT/PLA blend, however, the method is not reported in the toughening research of the PBAT/PLA blend, and the method for preparing the PBAT-based material with balanced rigidity and toughness by providing the simple and easy physical modification method has important industrial value.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a preparation method of a rigidity-toughness balanced PBAT-based material based on mesophase enhancement.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the PBAT-based material based on mesomorphic phase enhanced rigidity-toughness balance comprises the following steps:
(1) drying PBAT and PLA particles, mixing the PBAT and the PLA particles with a chain extender according to a certain mass percentage, and then melting and extruding the mixture;
(2) the PBAT/PLA blend particles are melted and hot-pressed into a film in a plate vulcanizing machine, and the melt is quickly transferred to a drying oven preheated to a certain temperature for isothermal crystallization.
In the invention, the mass percentage in the step (1) is as follows: 70-90 parts of PBAT, 10-30 parts of PLA and 0.5-2 parts of chain extender.
In the invention, the melting extrusion in the step (1) is to melt and plasticize the raw materials at 180-200 ℃ by adopting a single-screw extruder or a double-screw extruder, extrude the raw materials through a die, and cut the raw materials into particles after air cooling.
In the invention, the temperature of the isothermal crystallization in the step (2) is 50-60 ℃, and the time of the isothermal crystallization is 2-6 h.
Description of the inventive principles:
PBAT and PLA are both crystalline polymers, and the crystallization conditions (such as crystallization temperature and crystallization time) have great influence on the mechanical properties of the PBAT and the PLA. For example, for PBAT, samples with different isothermal crystallization temperatures exhibit different tensile modulus and yield characteristics, with higher crystallization temperatures providing more perfect platelets and greater stability under stress. Higher crystallization temperature also increases the crystallinity of PBAT, crystallizing boneThe scaffold is more dense and therefore the material exhibits a higher modulus. For PLA, its glass transition temperature (T)g) When the temperature of the PLA melt is reduced to be higher than T at about 60 DEG CgAfter the temperature of (2), crystals can be formed; when the crystallization temperature is far lower than TgWhen the polylactic acid is used, the movement of molecular chains is greatly inhibited, so that crystallization is difficult to form, and the PLA keeps an amorphous state; when the crystallization temperature is TgIn the vicinity (e.g. 50-60 ℃), the molecular chain may move a small amount, but the slip capability is still low, thereby limiting the polymer chain to form stable crystals, and possibly forming a mesophase with an order degree between the amorphous and crystalline phases.
The modulus of the PLA mesophase is higher than that of the amorphous phase but lower than that of the crystalline phase, so that in the PBAT/PLA blend, the PLA containing the mesophase has higher mechanical strength than that of the amorphous phase, and has better deformability than that of the crystalline phase, thereby being beneficial to stress dissipation in the stretching process. In addition, the mechanical properties of PBAT/PLA as an incompatible blending system are obviously influenced by the phase separation structure of the blend, the phase separation behavior is also influenced by crystallization, and the crystallization process of one component in the polymer blending system excludes the amorphous chain of the other component, thereby promoting the micro-phase separation. From this point of view, when PLA does not crystallize, the compatibility between PBAT and PLA two phases is better, and the phase interface adhesion is stronger. The synergistic effect of enhanced PLA deformability and better interfacial adhesion makes it less likely to phase separate during stretching to form voids. Therefore, by regulating the crystallization temperature of the PBAT/PLA blend to an optimal range (about 50-60 ℃), PLA can form a mesomorphic phase and avoid further crystallization, and simultaneously the crystallinity of PBAT can be improved, thereby further realizing the optimization of the mechanical property of the blend material and obtaining the PBAT-based material with balanced rigidity and toughness.
At present, no patent literature discloses a method for optimizing the mechanical property of PBAT/PLA blend material by regulating and controlling crystallization conditions.
Compared with the prior art, the invention has the following technical advantages:
1. based on reasonable control of crystallization conditions, the crystallization degree of PBAT is improved, and a PLA mesophase is formed at the same time, and the PLA mesophase has higher modulus and better deformation capability in stretching, thereby being beneficial to improving the strength of a blend material.
2. The invention avoids the obvious phase separation of PBAT and PLA caused by the crystallization of PLA based on the reasonable control of the crystallization condition, improves the compatibility of the PBAT and the PLA to a certain extent, further optimizes the mechanical property of the PBAT/PLA blend and realizes the balance of rigidity and toughness.
3. The material has the advantages of simple preparation process, no complex requirements on equipment and process, low production cost, easy large-scale industrial production and no pollution.
Drawings
FIG. 1 is an X-ray diffraction pattern of example 2 and comparative example 2;
FIG. 2 is a uniaxial tensile stress-strain curve for examples 2, 4, 5 and comparative examples 1, 2;
FIG. 3 is a cross-sectional view taken by a scanning electron microscope before and after stretching in example 2 and comparative example 2.
Detailed Description
The invention is described in further detail below with reference to the following detailed description and accompanying drawings:
as shown in fig. 1 and fig. 2 and 3, the raw materials used in the present invention are explained as follows: PBAT is available from Zhejiang Xin rich pharmaceutical Co., Ltd, and has a butanediol terephthalate unit molar content of 45% and a weight average molecular weight of 71.2 kg/mol. PLA was purchased from Pond Poulak, and had a weight average molecular weight of 150-200kg/mol and an optical purity of greater than 98%. The chain extender was purchased from basf, germany under the designation Joncryl ADR 4368.
The preparation method of the PBAT-based material with balanced rigidity and toughness comprises the following steps:
(1) drying PBAT and PLA particles, adding a chain extender according to a certain mass percentage, mixing, and melting and extruding;
(2) the PBAT/PLA blend particles are melted and hot-pressed into a film in a plate vulcanizing machine, and the melt is quickly transferred to an oven preheated to a certain temperature for isothermal crystallization.
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
In examples 1 to 8, the amount of PLA added, the isothermal crystallization temperature and the isothermal crystallization time were changed in this order, and the isothermal crystallization temperature was in the range of 50 to 60 ℃ and was lower than the glass transition temperature of PLA. In comparative example 1, a PBAT/PLA blend material was used which was naturally cooled after melting, i.e. with an isothermal crystallization temperature of 25 ℃. In comparative example 2, an isothermal crystallization temperature higher than the glass transition temperature of PLA was used.
Specific embodiments of examples 1 to 8 and comparative examples 1 and 2 are shown in Table 1.
Table 1: PLA content, isothermal crystallization temperature and crystallization time of examples 1-8 and comparative examples 1, 2
In the present invention, the material properties can be characterized by the following analytical instruments, specifically including:
wide angle X-ray diffraction (WAXD): the sample was tested using the WAXD apparatus at the shanghai synchrotron radiation light source BL16B1 line station. The wavelength of the X-rays was 0.124 nm. Data were acquired using a Rayonix SX-165CCD detector with a resolution of 2048 × 2048 pixels, the sample to detector distance being 90 cm.
Infrared spectrometer (FTIR, usa, seemer feishire nis 50 FTIR): in the transmission measurement mode, the isothermally crystallized sample was subjected to a spectrum acquisition at 25 ℃. The number of spectral scans was 32, and the resolution was 2cm-1。
Universal material testing machine (Shenzhen Sansi SANS-UTM 4204): and (3) carrying out unidirectional tensile test on the samples at room temperature to obtain a stress-strain curve and mechanical property data, wherein the initial distance between the clamps is 15mm, the tensile rate is 10mm/min, and each group of samples is repeatedly subjected to tensile test for at least 5 times to obtain an average result.
Field emission scanning electron microscope (SEM, hitachi SU-8010, japan): and quenching the stretched PBAT/PLA blend sample in liquid nitrogen along the stretching direction to obtain a section parallel to the stretching direction, fully drying, spraying gold on the surface for 60s, and observing the section morphology after stretching by using an SEM. The acceleration voltage was 5kv at the time of the test.
And (3) analyzing experimental data:
from the results of X-ray diffraction (fig. 1), comparative example 2, which crystallized at 70 ℃, showed characteristic diffraction peaks of both PBAT and PLA, indicating that both PBAT and PLA formed crystals at this time. Whereas example 2, crystallized at 55 ℃, showed only characteristic diffraction peaks of PBAT, indicating that PLA contains no crystalline phase. It was also found by IR spectroscopy that the sample crystallized at 50-60 ℃ and appeared at 918cm-1The characteristic absorption band of the PLA mesophase on the left and right, which does not appear in samples at other crystallization temperatures, demonstrates the formation of the mesophase.
From the results of the uniaxial tensile test (fig. 2 and table 2), comparative example 1 had an elongation at break of 900%, but its young's modulus and yield strength were low, and were only 32.3MPa and 6.1MPa, respectively. Examples 4, 2, 5 in turn have higher young's modulus and yield strength as the crystallization temperature is gradually increased from 25 ℃ to 60 ℃ when the PLA content and crystallization time are kept constant, and remain above 750% despite their reduced elongation at break. When the crystallization temperature was further increased to 70 ℃ (comparative example 2), PLA crystallized, significantly reducing the elongation at break of the blend material by only 610% compared to comparative example 1 by 32%, indicating a large loss of material toughness. Among the above samples, example 2 containing the PLA mesophase achieved more satisfactory values in young's modulus, yield strength, and elongation at break, 37.8MPa, 7.0MPa, and 850%, respectively, and the young's modulus and yield strength were improved by 17% and 15%, respectively, compared to the sample (comparative example 1) in which PLA was in the amorphous phase, and the elongation at break was improved by 39% compared to the sample (comparative example 2) in which PLA was in the crystalline phase, thereby achieving the balance of stiffness and toughness. If the crystallization temperature is kept at 55 ℃ and the crystallization time is 4h, the Young's modulus and yield strength of the material increase and the elongation at break decreases as the PLA content increases (examples 1-3), and when the PLA content is 30%, the elongation at break is only 540%. If the PLA content is kept at 20% and the crystallization temperature is kept at 55 ℃, the Young's modulus and yield strength of the material gradually increase with the increase of the crystallization time (examples 2 and 6-8), and the increase of the Young's modulus and yield strength is slowed down after the crystallization time is prolonged from 4h to 6h, so that the production cost is not saved for too long time.
As can be seen from the results of the scanning electron microscope test (FIG. 3), the cross-sectional morphologies of comparative example 2 and example 2 were not significantly different before stretching, and it was observed that the spherical PLA phase was not uniformly dispersed in the PBAT matrix, and the size thereof was in the range of 0.1 to 1.0 μm, exhibiting a "sea-island" phase separation structure. When stretched to 400% strain, large amounts of elongated voids (the drawing direction is horizontal) appear in the SEM image of comparative example 2 due to interfacial separation of PLA and PBAT phases, and the formation of these large cracks will eventually lead to fracture of the sample. Whereas such voids did not appear in the SEM image of example 2, it was observed that the PLA particles were stretch-oriented. This is because PLA containing no crystalline phase is more flexible and easily deformed by stretching, and the deformation of PLA inhibits the formation of voids at the phase interface.
Table 2: young's modulus, yield strength and elongation at break of examples 1-8 and comparative examples 1-2
The results show that the mechanical property of the PBAT/PLA blend material can be effectively improved by reasonably regulating and controlling the crystallization condition of the PBAT/PLA blend material, so that the balance of rigidity and toughness is realized, and the PBAT/PLA blend material has potential application values in the fields of film processing, product packaging and the like.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (5)
1. The preparation method of the PBAT-based material based on mesomorphic phase enhanced rigidity-toughness balance is characterized by comprising the following steps:
(1) drying PBAT and polylactic acid (PLA) particles, mixing the PBAT and the PLA particles with a chain extender according to a certain mass percentage, and then melting and extruding the mixture;
(2) the PBAT/PLA blend particles are melted and hot-pressed into a film in a plate vulcanizing machine, and the melt is quickly transferred to a drying oven with a certain temperature for isothermal crystallization.
2. The method for preparing the PBAT-based material based on the mesomorphic phase enhanced stiffness-toughness balance according to claim 1, wherein the stiffness-toughness balance is achieved by controlling the crystallization conditions and the crystallization structure of the material.
3. The method for preparing the PBAT-based material based on the mesomorphic phase enhanced rigidity-toughness balance according to claim 1, wherein the mass percentages in the step (1) are as follows: 70-90 parts of PBAT, 10-30 parts of PLA and 0.5-2 parts of chain extender.
4. The method for preparing the PBAT-based material with the rigidity and toughness balance based on the mesomorphic phase enhancement as claimed in claim 1, wherein the melt extrusion in the step (1) is to melt and plasticize the raw materials at 180 ℃ and 200 ℃ by using a single screw extruder or a double screw extruder, extrude the raw materials through a die, and cut the raw materials into particles after air cooling.
5. The method for preparing the PBAT-based material based on the mesomorphic phase enhanced rigidity-toughness balance according to claim 1, wherein the isothermal crystallization temperature in the step (2) is 50-60 ℃ and the isothermal crystallization time is 2-6 h.
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| CN115746525A (en) * | 2022-11-29 | 2023-03-07 | 浙江金晟环保股份有限公司 | Low-crystallinity rapidly-degradable PLA/PBAT composite material and preparation method thereof |
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| US20050136271A1 (en) * | 2003-12-18 | 2005-06-23 | Germroth Ted C. | High clarity films with improved thermal properties |
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| CN104262917A (en) * | 2014-09-18 | 2015-01-07 | 浙江大学 | Preparation method of high-molecular polylactic acid (PLA) three-dimensional composite material capable of being crystallized rapidly |
| CN113861636A (en) * | 2021-10-27 | 2021-12-31 | 佳易容聚合物(上海)有限公司 | High-stiffness high-toughness fully-degradable PBAT/PLA resin composition and preparation method thereof |
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| US20050136271A1 (en) * | 2003-12-18 | 2005-06-23 | Germroth Ted C. | High clarity films with improved thermal properties |
| CN101157793A (en) * | 2007-09-20 | 2008-04-09 | 浙江海正生物材料股份有限公司 | Heat-proof polylactic acid blend and preparation method thereof |
| CN104262917A (en) * | 2014-09-18 | 2015-01-07 | 浙江大学 | Preparation method of high-molecular polylactic acid (PLA) three-dimensional composite material capable of being crystallized rapidly |
| CN113861636A (en) * | 2021-10-27 | 2021-12-31 | 佳易容聚合物(上海)有限公司 | High-stiffness high-toughness fully-degradable PBAT/PLA resin composition and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115746525A (en) * | 2022-11-29 | 2023-03-07 | 浙江金晟环保股份有限公司 | Low-crystallinity rapidly-degradable PLA/PBAT composite material and preparation method thereof |
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