CN110564124A - Composite material for improving compatibility and crystallinity of PLLA/PMMA and preparation method thereof - Google Patents
Composite material for improving compatibility and crystallinity of PLLA/PMMA and preparation method thereof Download PDFInfo
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- CN110564124A CN110564124A CN201911039377.7A CN201911039377A CN110564124A CN 110564124 A CN110564124 A CN 110564124A CN 201911039377 A CN201911039377 A CN 201911039377A CN 110564124 A CN110564124 A CN 110564124A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
the invention provides a composite material for improving the compatibility and crystallinity of PLLA/PMMA and a preparation method thereof, wherein the composite material comprises the following raw materials, by weight, 30 ~ 70 parts of levorotatory polylactic acid, 30 ~ 70 parts of polymethyl methacrylate and 5 ~ 25 parts of polyvinyl methyl ether.
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.
when the temperature rise of the PLLA/PMMA blend material is higher than that of the PLGA/PMMA blend material, the temperature rise of the PLLA/PMMA blend material is higher than that of the PLGA/PMMA blend material when the temperature rise of the PLGA/PMMA blend material is higher than that of the PLGA/PMMA blend material, and the PMMA blend material has a high temperature rise of the temperature of the PLGA/PMMA, and PMMA blend material.
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 composite material for improving the compatibility and the crystallinity of PLLA/PMMA comprises the following raw materials, 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, 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 ~ 2000r/min, and the spin coating time is 20s ~ 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 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 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 material prepared by the comparative example is in a phase separation structure at room temperature, when the temperature is heated to 250 ℃, the phase separation structure disappears, and the system is changed into a compatible system, examples 1 to 3 are also in the phase separation structure 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, wherein the phase transition temperature in example 1 is reduced to 210 ℃.
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.
it can be seen from the figure that the PLLA/PMMA composite material in the comparative example has two different glass transition temperatures and is relatively close to the glass transition temperature values of PLLA and PMMA, which indicates that the two systems are incompatible systems, the composite material in the example 1 has a cold crystallization peak, which indicates that PVME plays a role similar to a compatibilizer in the blending system, but phase separation still occurs in the micro-domain of the blend during heating, the addition of PVME can not prevent the phase separation of the blending system, but can improve the dispersion uniformity among the blends, the enthalpy change values of the comparative example and the example 1 at 140-180 ℃ are respectively 5.74J/g and 11.35J/g, so that the crystallinity of PLLA in the blending system is calculated to be respectively 12.26% and 29.10%, and compared with the comparative example without the addition of PVME, the crystallinity of the invention is improved by about 1 time.
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 of the original crystallization time, the growth rate of the crystal after nucleation is obviously accelerated, 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.
Claims (7)
1. the composite material for improving the compatibility and the crystallinity of PLLA/PMMA is characterized by comprising the following raw materials, by weight, 30 ~ 70 parts of levorotatory polylactic acid, 30 ~ 70 parts of polymethyl methacrylate and 5 ~ 25 parts of polyvinyl methyl ether.
2. the composite material for improving the compatibility and the crystallinity of PLLA/PMMA according to claim 1, which is characterized by comprising the following raw materials, by weight, 40 ~ 60 parts of levorotatory polylactic acid, 40 ~ 60 parts of polymethyl methacrylate and 5 ~ 25 parts of polyvinyl methyl ether.
3. the composite material of claim 1, wherein the L-polylactic acid has a molecular weight in the range of 104~105g/mol。
4. The composite material of claim 1, wherein the polymethylmethacrylate has a molecular weight in the range of 103~104g/mol。
5. The composite material of claim 1, wherein the molecular weight of the polyvinylmethylether is in the range of 104~105g/mol。
6. A method for preparing a composite material for improving the compatibility and crystallinity of PLLA/PMMA according ~ any one of claims 1 ~ 5, comprising 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.
7. the method of claim 6, wherein the spin-coating speed is 500r/min ~ 2000r/min, and the spin-coating time is 20s ~ 40 s.
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| CN113097391A (en) * | 2021-03-15 | 2021-07-09 | 西安交通大学 | Method for optimizing morphology and performance of active layer of organic solar cell |
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