CN110564124B - A composite material for improving PLLA/PMMA compatibility and crystallinity and preparation method thereof - Google Patents
A composite material for improving PLLA/PMMA compatibility and crystallinity and preparation method thereof Download PDFInfo
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Abstract
本发明提供了一种提高PLLA/PMMA相容性及结晶度的复合材料及其制备方法，该复合材料包括以下重量份数的原料：左旋聚乳酸30~70份、聚甲基丙烯酸甲酯30~70份和聚乙烯基甲基醚5~25份。本发明通过向PLLA/PMMA共混物中添加PVME，使共混组分变得微细，提高了共混组分的分散均匀性，从而降低了共混组分从相分离转变为均相结构的温度，还会促进体系的结晶速率和提高结晶组分的结晶度，从而解决了PLLA/PMMA共混体系存在的缺陷。本发明制备方法简单易控，原料简单易得，无助剂添加，生产成本低、污染少，可实现大规模工业化生产，同时也为聚合物共混提供了新的思路，具有一定的理论研究指导意义。The invention provides a composite material for improving the compatibility and crystallinity of PLLA/PMMA and a preparation method thereof. The composite material comprises the following raw materials in parts by weight: 30-70 parts of L-polylactic acid, 30 parts of polymethyl methacrylate ~70 parts and 5~25 parts of polyvinyl methyl ether. In the present invention, by adding PVME to the PLLA/PMMA blend, the blended components become fine, and the dispersion uniformity of the blended components is improved, thereby reducing the transition of the blended components from phase separation to homogeneous structure. The temperature can also promote the crystallization rate of the system and improve the crystallinity of the crystalline components, thereby solving the defects of the PLLA/PMMA blend system. The preparation method of the invention is simple and easy to control, the raw materials are simple and easy to obtain, no additives are added, the production cost is low, and the pollution is low, and large-scale industrial production can be realized. Guiding significance.
Description
Technical Field
The invention relates to the technical field of polymer blending modification, in particular to a preparation method of a material for promoting the compatibility and crystallinity of a PLLA/PMMA blending material by using a PVME modifier.
Background
PLA (polylactic acid) has the advantages of good mechanical property, wide source, no toxicity, harmlessness, degradability and the like, and has important application in the fields of biomedicine, packaging, fiber, electronic industry and the like. But the disadvantages of larger molecular polarity, narrower molecular weight distribution, poor processability, low melt strength and the like limit the development and application of polylactic acid to a certain extent. PMMA is a petroleum-based non-degradable high polymer material, but can be recycled, thereby being beneficial to environmental protection and sustainable development. PMMA has higher glass transition temperature and transparency, and the heat resistance and transparency of polylactic acid can be effectively improved after PMMA and PLLA are blended and modified, which has important significance for widening the industrial application field of bio-based polylactic acid materials.
However, PMMA is less compatible with PLLA blends, resulting in phase separation. In addition, since PMMA has a high glass transition temperature and a slow molecular chain movement, which can restrict the molecular chain movement of PLLA, resulting in a decrease in its crystallization property, it is difficult to prepare a high molecular weight crystalline composite material in a general molding process.
For compatibility and crystallinity of PLLA/PMMA blend material, researchers at home and abroad carry out a series of research works, for example Lin and the like find that when PMMA/PLA samples with different blending ratios are subjected to SEM analysis, a 'cavity' structure in a cross section can be observed in the research of blending performance of mPOE reactive compatibilized polylactic acid and polymethyl methacrylate. The cavity structure shows that the surface tension between the two raw materials is large, the compatibility is poor, and the adhesive force is weak. In the cross-section of the PLA/PMMA blend with 40% PLA, it can be seen that the cross-section has a large number of "cavity" structures and no obvious cross-linked structure appears. When the PLA content is increased to 50%, although the number of the "cavities" in the cross section is reduced, a plurality of granular micro-particles still exist, the dispersibility is poor, and the compatibility of the composite material is not ideal. Eguiburu et al studied a blend of crystalline polylactic acid (PLLA) and PMMA, and from DSC experimental results, the blend system had two glass transition temperatures close to each other, thereby obtaining a blend system in which PLLA/PMMA is partially compatible. Li et al found that the introduction of PMMA eliminated the crystallization peak of PLLA in the DSC first temperature rise curve. Indicating that PLLA crystallization is limited by amorphous PMMA during temperature rise, making PLLA less time to crystallize. Zhang states that it is only possible to observe crystallization and melting of PLLA crystals in the second DSC temperature rise curve when the PLLA content in the PLLA/PMMA blend is above 90%. Fan finds that the Avrami index n of the blended material is between 3 and 4 when the content of PMMA is less when the crystallization performance of the PLLA/PMMA blended material is researched, and the addition of PMMA does not change the nucleation mechanism and the crystal growth mode of the PLLA. Whereas the Avrami index n of the blended material is greater than 4 when the PMMA content is higher, because the impact of PMMA on the PLLA nucleation rate is greater than the impact on the crystal growth rate, and when the PMMA content is higher, the crystallization induction time of the blended material is long, resulting in a larger Avrami index. When PMMA is blended with PLA material, although composite material with excellent performance can be obtained, the problems of poor compatibility between materials, low crystallinity and the like still exist during blending. Therefore, a method for promoting the compatibility and crystallinity of the blend system of polylactic acid and PMMA is still needed.
In the past, the research on PLLA/PMMA blending system mainly researches the phase behavior in the two blending systems. UCST behavior was found to exist with PLLA/PMMA blends. When the blending system is heated to a certain temperature, the blending system is transformed from a phase separation structure to a homogeneous structure. Since PMMA is an amorphous polymer and has a high glass transition temperature, when PMMA is blended with PLLA, the crystallization of PLLA in a blending system is also obviously inhibited. Therefore, the compatibility and crystallinity of the PLLA/PMMA blending system are problems to be solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a composite material for improving the compatibility and the crystallinity of PLLA/PMMA and a preparation method thereof, and solves the problems of poor compatibility, slow crystallization speed and low crystallinity of the conventional PLLA/PMMA blend.
In order to achieve the purpose, the invention adopts the following scheme: a composite material for improving the compatibility and crystallinity of PLLA/PMMA comprises the following raw materials in parts by weight: 30-70 parts of levorotatory polylactic acid (PLLA), 30-70 parts of polymethyl methacrylate (PMMA) and 5-25 parts of polyvinyl methyl ether (PVME).
When PLLA and PMMA are blended according to a certain proportion, the blend system has a phase separation structure at room temperature. When the blend system is heated to a certain temperature, the blend system is transformed from a phase separation structure to a homogeneous structure. The glass transition temperature of PMMA is about 114 ℃, the glass transition temperature of PLLA is about 65 ℃, in a compatible system of PMMA and PLLA, when the temperature is reduced to the crystallization temperature of PLLA and isothermal crystallization is started, the glass transition temperature of the blend is increased by the amorphous component PMMA, the moving capacity of a chain segment is slowed, and the growth power of a crystal phase in the blend is reduced. The polyvinyl methyl ether (PVME) is an amorphous polymer, the glass transition temperature of the polymer is-20 ℃, the addition of the PVME can enhance the acting force between PLLA/PMMA molecules and improve the dispersion uniformity of the blending component, thereby reducing the temperature of the blending component for converting from phase separation to a homogeneous structure; and because PVME has a lower glass transition temperature, its presence lowers the glass transition temperature of the blend and can also act as a nucleating agent during crystallization of the crystalline phase, thereby accelerating the crystallization rate of the crystalline phase. The PVME has certain viscosity, and the addition of the PVME can also increase the storage modulus of a blending system, so that the mechanical property of the blending system is improved to a certain degree.
Preferably, the composite material for improving the compatibility and the crystallinity of PLLA/PMMA comprises the following raw materials in parts by weight: 40-60 parts of levorotatory polylactic acid (PLLA), 40-60 parts of polymethyl methacrylate (PMMA) and 5-25 parts of polyvinyl methyl ether (PVME).
Since PMMA has a high glass transition temperature, if it is added in an excessive amount, it inhibits crystallization of the crystalline component in the blending system and causes deterioration of compatibility of the blending system when blended with PLLA. On the other hand, if the amount of PMMA added is too small, the high temperature resistance of the PLLA material cannot be improved. When the addition amount of PVME is too small, the compatibility and crystallinity of a blending system cannot be promoted and improved; when the PVME is excessively added, although the compatibility and crystallinity of a blending system are obviously promoted and improved, the PVME is easy to degrade at high temperature due to the low glass transition temperature and certain viscosity of the PVME, so that the blend is yellow.
Preferably, the molecular weight range of the L-polylactic acid is 104~105g/mol。
Preferably, the polymethyl methacrylate has a molecular weight in the range of 103~104g/mol。
Preferably, the molecular weight of the polyvinyl methyl ether is in the range of 104~105g/mol。
Too low or too high molecular weight may cause changes in physical parameters of the material, such as glass transition temperature, melting point, etc., thereby changing compatibility and crystallinity between the two.
The preparation method of the composite material for improving the compatibility and the crystallinity of the PLLA/PMMA comprises the following steps:
1) accurately weighing levorotatory polylactic acid, polymethyl methacrylate and polyvinyl methyl ether, adding into a container filled with chloroform, and uniformly stirring to obtain a mixed solution;
2) spin-coating the mixed solution obtained in the step 1) on a quartz substrate, placing a film obtained by spin-coating at a ventilated place for natural volatilization for more than 24 hours, and placing the film subjected to natural volatilization in a vacuum oven for vacuumizing at least 24 hours at room temperature to obtain the composite material.
Preferably, the spin coating speed is 500r/min to 2000r/min, and the spin coating time is 20s to 40 s.
Compared with the prior art, the invention has the following beneficial effects:
1. in the modified PLLA/PMMA composite material, PVME is used as a modifier, so that the intermolecular acting force in a blending system is enhanced, the size among blending components is reduced, the dispersion uniformity of the blending components is improved, and the temperature of UCST behavior of the blending system can be effectively reduced. The PVME reduces the glass transition temperature of the blending system, and simultaneously plays a role of serving as a nucleating agent of a crystallization component in the blending system, so that the crystallization rate of a crystal phase in the blending system is accelerated. Thereby solving the problems of poor compatibility, slow crystallization speed and low crystallinity of a PLLA/PMMA blending system.
2. According to the invention, the third component amorphous polymer PVME with lower glass transition temperature is added into the blend of PLLA and PMMA, so that the bonding force between PLLA/PMMA molecules can be enhanced, the blend components become fine, the crystallinity of the crystalline components in the blend system is improved, the modified blend material has better compatibility, higher crystallinity, high crystallization speed and improved storage modulus, and the blend material has a good application prospect. Meanwhile, a new thought is provided for polymer blending, and certain theoretical research and guidance significance is achieved.
3. The polymer composite material is prepared by taking PLLA, PMMA and PVME as raw materials in a spin coating mode, the preparation method is simple and easy to control, the raw materials are simple and easy to obtain, no auxiliary agent is added, the production cost is low, the pollution is less, and the large-scale industrial production can be realized.
Drawings
FIG. 1 is a microscopic topography during temperature increase for composites prepared in example 1 and comparative example;
FIG. 2 is a DSC curve during a 10 deg.C/min temperature increase for the composites prepared in example 1 and comparative example;
FIG. 3 is a microscopic morphology of the composites prepared in example 1 and comparative example during isothermal crystallization;
FIG. 4 is a DMA curve during a 4 deg.C/min ramp for composites prepared in example 1 and comparative example.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials in the following examples are all commercially available without specific reference.
Example 1
A composite material for improving the compatibility and crystallinity of PLLA/PMMA is composed of the following raw materials in parts by weight: 50 parts of PLLA, 50 parts of PMMA and 20 parts of PVME. Wherein the molecular weight of PLLA is in the range of 104~105g/mol, PMMA molecular weight range is 103~104g/mol, PVME molecular weight range of 104~105g/mol, comprising the following steps:
(1) adding PLLA, PMMA and PVME into a beaker filled with chloroform, and magnetically stirring for 4 hours to obtain a mixed solution;
(2) spin-coating the mixed solution obtained in the step 1) on a quartz substrate at a speed of 2000r/min for 30s, placing the film obtained by spin-coating at a ventilated place for natural volatilization for more than 24h, and placing the film subjected to natural volatilization in a vacuum oven for vacuumizing at least 24h at room temperature to obtain the composite material.
Example 2
A composite material for improving the compatibility and crystallinity of PLLA/PMMA is composed of the following raw materials in parts by weight: 50 parts of PLLA, 50 parts of PMMA and 5 parts of PVME. Wherein the molecular weight of PLLA is in the range of 104~105g/mol，PMMA molecular weight in the range of 103~104g/mol, PVME molecular weight range of 104~105g/mol, comprising the following steps:
(1) adding PLLA, PMMA and PVME into a beaker filled with chloroform, and magnetically stirring for 4 hours to obtain a mixed solution;
(2) spin-coating the mixed solution obtained in the step 1) on a quartz substrate at the speed of 500r/min for 30s, placing the film obtained by spin-coating at a ventilated place for natural volatilization for more than 24h, and placing the film subjected to natural volatilization in a vacuum oven for vacuumizing at least 24h at room temperature to obtain the composite material.
Example 3
A composite material for improving the compatibility and crystallinity of PLLA/PMMA is composed of the following raw materials in parts by weight: 50 parts of PLLA, 50 parts of PMMA and 10 parts of PVME. Wherein the molecular weight of PLLA is in the range of 104~105g/mol, PMMA molecular weight range is 103~104g/mol, PVME molecular weight range of 104~105g/mol, comprising the following steps:
(1) adding PLLA, PMMA and PVME into a beaker filled with chloroform, and magnetically stirring for 4 hours to obtain a mixed solution;
(2) spin-coating the mixed solution obtained in the step 1) on a quartz substrate at a speed of 1500r/min for 30s, placing the film obtained by spin-coating at a ventilated place for natural volatilization for more than 24h, and placing the film subjected to natural volatilization in a vacuum oven for vacuumizing at least 24h at room temperature to obtain the composite material.
Comparative example
The other steps were the same as in example 1, without the addition of PVME.
Second, performance detection
1. The microstructures of the composite materials prepared in examples 1 to 3 and comparative example were observed in situ by heating using an optical microscope (POM), and the results are shown in fig. 1.
As can be seen from FIG. 1, the PLLA/PMMA composite prepared by the comparative example has a phase separation structure at room temperature, and when heated to 250 ℃, the phase separation structure disappears and the system becomes a compatible system. The phase separation structure is also adopted in the embodiments 1-3 at room temperature, but the phase separation effect of the composite material is obviously improved, and the temperature of the blending system changing from the phase separation structure to the homogeneous structure is lower and lower along with the increase of the content of PVME in the blending system. In example 1, the phase transition temperature had dropped to 210 ℃. Therefore, in the blending system, PVME plays a role similar to a compatibilizer, the increase of the content of PVME promotes the continuous enhancement of the intermolecular force of PLLA/PMMA, the dispersion uniformity among blends is gradually improved, and the temperature of the blending system reaching UCST behavior is reduced.
2. The composite materials prepared in example 1 and comparative example were tested for compatibility using a Differential Scanning Calorimeter (DSC), and the DSC scans the composite material at an elevated temperature under nitrogen atmosphere for 10 ℃/min, the results are shown in fig. 2.
As can be seen from the figure, the PLLA/PMMA composite of the comparative example has two different glass transition temperatures, and the glass transition temperature values are relatively close to those of PLLA and PMMA, indicating that the two systems should be incompatible systems. The composite material of example 1 shows a cold crystallization peak, which indicates that although PVME acts like a "compatibilizer" in the blend system, phase separation occurs in the micro-domains of the blend during heating. The addition of PVME, while not preventing phase separation of the blended system, can improve the uniformity of dispersion between blends. As can be further seen from the graph, the enthalpy change values of the comparative example and example 1 at 140 ℃ to 180 ℃ are 5.74J/g and 11.35J/g, respectively, thereby calculating the crystallinity of PLLA in the blend system to be 12.26% and 29.10%, respectively, which is about 1-fold improved compared to the comparative example without PVME. Indicating that the addition of PVME did improve the crystallinity of PLLA in the blended system.
3. The composite materials prepared in example 1 and comparative example were subjected to a crystallization test at the same temperature, and the microstructure of the blend material was observed in situ at a constant temperature using a light microscope (POM) during the crystallization process, and the result is shown in fig. 3.
Generally, in a compatible system, an amorphous component will significantly inhibit crystallization of a crystalline component if the glass transition temperature of the amorphous component is higher than that of the crystalline component. As can be seen from the figure, the composite of the comparative example had slow crystal nucleation and a low crystal growth rate, just indicating that PMMA in the blended system inhibited the crystallization of PLLA. In the embodiment 1 of the invention, due to the addition of PVME with a low glass transition temperature, the function similar to that of a nucleating agent is realized, so that the chain segment movement of a blending system is accelerated, and the crystal growth is rapid. The crystallization starting time of the invention is changed from 5h to 1h of the comparative example, the crystallization time is shortened to about 1/5, the growth rate is obviously accelerated after the crystal is nucleated, and the crystal size is larger.
4. The mechanical properties of the composites prepared in example 1 and comparative example were tested using dynamic thermo-mechanical analysis (DMA) with a temperature scan of 4 ℃/min, the results of which are shown in figure 4.
As can be seen from FIG. 4, the composite material of PLLA/PMMA in the comparative example has a tan delta of about 0.31, the composite material of example 1 has a tan delta of about 0.27, and the tan delta is the ratio of loss modulus to storage modulus, which is an important physical quantity for characterizing the modulus of a substance. The tan delta value of the composite material in example 1 is reduced compared with that of the composite material in the comparative example, which shows that the storage modulus of the blend can be improved to a certain extent by adding PVME into a PLLA/PMMA blending system.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, although the applicant has described the present invention in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention and shall be covered by the claims of the present invention.
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