CN113444348A - Polylactic acid stereocomplex, preparation method and application - Google Patents
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Abstract
The invention belongs to the technical field of high polymer materials, relates to a polylactic acid material, and discloses a preparation method of a polylactic acid stereocomplexn‑b‑PDMSm‑b‑PDLAn) And preparing a polylactic acid stereocomplex; applications are also disclosed. The invention utilizes the flexible PDMS chain segment as the macromolecule initiating agent to synthesize the triblock copolymer PDLA by ring-opening polymerization of the D-lactiden‑b‑PDMSm‑b‑PDLAnAnd the PDLA is prepared by melt blendingn‑b‑PDMSm‑b‑PDLAnDispersed in PLLA matrix of L-polylactic acid, because PDLA chain segment in triblock polymer can generate strong stereo composite effect with PLLA matrixThe PDMS serving as the toughening chain segment can be uniformly dispersed in the matrix, and macroscopic phase separation and migration to the surface of the matrix due to poor compatibility of the PDMS and the polylactic acid matrix are avoided, so that the obvious toughening effect on the polylactic acid matrix is realized under the condition of low content of the triblock copolymer.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to a polylactic acid material, and particularly relates to a polylactic acid stereocomplex, a preparation method and application thereof.
Background
Facing the current global problems of petroleum resources being gradually exhausted and environmental pollution, the plastic industry also faces the double challenges of getting rid of the dependence on petroleum and oil resources and reducing the generation of white pollutants. Under the background of 'forbidden plastic orders' issued by various countries at present, the way of finding renewable green biomass resources as raw materials of plastics becomes the most promising development prospect.
Renewable plant resources such as corn straws, starch and the like are used as raw materials, lactic acid is prepared by fermentation, lactide is obtained by cyclization reaction, and then the polylactic acid can be obtained by polymerization under the catalytic action of stannous octoate. As a green plastic, polylactic acid has good biodegradability, can be degraded into carbon dioxide and water in the environment, cannot pollute the environment, and has good biocompatibility, excellent barrier property, transparency and mechanical strength, so that the polylactic acid has wide application prospects in the fields of biomedical materials, packaging materials, 3D printing materials and the like. However, since polylactic acid itself has high brittleness (elongation at break is generally less than 5%), its application expansion is limited to a great extent, at present, toughening agents such as rubber and polyurethane are added into the polylactic acid by a physical blending method or a chemical copolymerization modification method to toughen and modify the polylactic acid, but the mechanical strength of the polylactic acid is obviously reduced by phase separation caused by poor compatibility between the polylactic acid and the toughening agent along with the increase of the content of the toughening agent.
Polylactic acid includes three types of L-polylactic acid (PLLA), D-polylactic acid (PDLA) and racemic polylactic acid (PDLLA), and the L-polylactic acid and the D-polylactic acid can generate stereocomplex action, and the melting point of the formed polylactic acid stereocomplex is about 50 ℃ higher than that of the L-or D-polylactic acid (Macromolecules, 20(1987): 904-. Therefore, the inventors have developed a polylactic acid stereocomplex, a preparation method and an application using the characteristics.
Disclosure of Invention
Based on the problems, the invention provides a polylactic acid stereocomplex, a preparation method and application thereof, and the invention synthesizes triblock copolymer (PDLA) with Polydimethylsiloxane (PDMS) containing flexible siloxane main chainn-b-PDMSm-b-PDLAn) And a triblock copolymer PDLAn-b-PDMSm-b-PDLAnThe PDLA is dispersed in a PLLA matrix, and chain segments at two ends of a triblock copolymer can form a strong stereo composite effect with the PLLA matrix, so that on one hand, phase separation and emigration caused by poor compatibility of a PDMS toughening chain segment and the matrix can be avoided, and on the other hand, the formed stereo composite can improve the thermal stability of the PLLA matrix.
In order to solve the technical problems, the invention provides a preparation method of a polylactic acid stereocomplex, which comprises the following steps:
s1: synthesis of triblock copolymer PDLAn-b-PDMSm-b-PDLAn
Adding 2g of PDMS with aminopropyl groups at two ends into 120ml of anhydrous toluene, adding 0.4ml of stannous octoate and 2-6 g of dextrorotatory lactide monomer under the protection of nitrogen, heating to 120 ℃ for ring-opening polymerization, stopping the reaction after 24h, precipitating in methanol, filtering, washing and drying in vacuum at 60 ℃ to obtain the triblock copolymer PDLAn-b-PDMSm-b-PDLAn；
S2: preparation of polylactic acid stereocomplex
Using a melt blending method with PLLA and the triblock copolymer PDLA synthesized in step S1n-b-PDMSm-b-PDLAnPreparing polylactic acid stereocomplex.
Further, the number average molecular weight of the PDMS having aminopropyl groups at both ends in step S1 was 2500.
Further, the melt blending method is specifically as follows: taking 100 parts by mass of PLLA and 1-4 parts by mass of the PDLA prepared in the step S1n-b-PDMSm-b-PDLAnThe above PLLA and PDLAn-b-PDMSm-b-PDLAnPre-drying the polylactic acid in an oven at 80 ℃ for 24 hours respectively to remove the water absorbed by the polylactic acid and prevent the degradation of the polylactic acid during high-temperature mixing to cause the reduction of mechanical properties; then melt blending is carried out in a micro double-screw mixing roll at the temperature of 190 ℃ to obtain the polylactic acid stereocomplex.
In order to solve the technical problems, the invention also provides a polylactic acid stereocomplex.
In order to solve the technical problems, the invention also provides the application of the polylactic acid stereocomplex in preparing plastic products.
Compared with the prior art, the invention has the beneficial effects that: the polylactic acid stereocomplex prepared by the invention has strong toughness and excellent mechanical property, and the invention utilizes the flexible Polydimethylsiloxane (PDMS) chain segment as the macroinitiator to synthesize the triblock copolymer PDLA by ring-opening polymerization of the D-lactiden-b-PDMSm-b-PDLAnAnd melt blending the three-block copolymer PDLAn-b-PDMSm-b-PDLAnThe polymer is dispersed in a PLLA matrix, and a PDLA chain segment in a triblock polymer can generate strong stereo composite action with the PLLA matrix, so that PDMS serving as a toughening chain segment can be uniformly dispersed in the matrix, macroscopic phase separation and migration to the surface of the matrix caused by poor compatibility of the PDMS and the polylactic acid matrix are avoided, and a good toughening effect is achieved under the condition of low concentration of a toughening agent, so that the triblock copolymer has an obvious toughening effect on the polylactic acid matrix under the condition of low content, and the tensile strength is only slightly reduced.
Drawings
FIG. 1 shows the synthesis of a triblock copolymer PDLA according to the present inventionn-b-PDMSm-b-PDLAnAnd a process diagram for preparing a stereocomplex of polylactic acid;
FIG. 2 is a three-block copolymer PDLA of example 2 of the present inventionn-b-PDMSm-b-PDLAnNuclear magnetic resonance hydrogen spectrum of (1H NMR) pattern;
FIG. 3 is a three-block copolymer PDLA of example 2 of the present inventionn-b-PDMSm-b-PDLAnGel Permeation Chromatography (GPC) profile of (a);
FIG. 4 is a Differential Scanning Calorimetry (DSC) profile of example 2 of the present invention;
fig. 5 is a Scanning Electron Microscope (SEM) image of example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to examples and drawings, wherein the raw materials used in the examples are all commercially available products, and the exemplary embodiments and descriptions thereof of the present invention are only used for explaining the present invention and are not intended to limit the present invention.
Example 1:
the embodiment provides a preparation method of a polylactic acid stereocomplex, which comprises the following steps:
s1: synthesis of triblock copolymer PDLAn-b-PDMSm-b-PDLAn
Adding 2g of PDMS with aminopropyl groups at two ends into 120ml of anhydrous toluene, adding 0.4ml of stannous octoate and 2-6 g of dextrorotatory lactide monomer under the protection of nitrogen, heating to 120 ℃ for ring-opening polymerization, stopping the reaction after 24h, precipitating in methanol, filtering, washing and drying in vacuum at 60 ℃ to obtain the triblock copolymer PDLAn-b-PDMSm-b-PDLAn(ii) a The number average molecular weight of PDMS having aminopropyl groups at both ends in this example was 2500; because the activity of the amido hydrogen is obviously higher than that of water molecule hydrogen, the polymerization of the dextrorotatory lactide monomer is more easily initiated to obtain a target triblock copolymer, and the phenomenon that trace water in a polymerization system initiates polymerization to obtain homopolymer PDLA is avoided, so that the triblock copolymer is difficult to purify; the preparation method of the embodiment is obviously different from the reported preparation of PLLA-b-PDMS-b-PLLA (Macromolecular Symposia, 239 (2006): 91-96) by initiating L-lactide polymerization by PDMS with hydroxyl at both ends, and the prepared copolymer is reported to have too wide molecular weight distribution (Mw/Mn is 2.1) and no GPC spectrogram is provided, and whether the product contains a homopolymerization byproduct caused by trace amount of water initiation cannot be known;
s2: preparation of polylactic acid stereocomplex
Using a melt blending method with PLLA and the triblock copolymer PDLA synthesized in step S1n-b-PDMSm-b-PDLAnPreparing polylactic acid stereocomplex.
The melt blending method described in this example is as follows: taking 100 parts by mass of PLLA and 1-4 parts by mass of the PDLA prepared in the step S1n-b-PDMSm-b-PDLAnThe above PLLA and PDLAn-b-PDMSm-b-PDLAnPre-drying the polylactic acid in an oven at 80 ℃ for 24 hours respectively to remove the water absorbed by the polylactic acid and prevent the degradation of the polylactic acid during high-temperature mixing to cause the reduction of mechanical properties; then melt blending is carried out in a micro double-screw mixing roll at the temperature of 190 ℃ to obtain the polylactic acid stereocomplex.
The polylactic acid stereocomplex prepared by the embodiment can be used for preparing plastic products, such as biomedical materials, packaging materials, 3D printing materials and the like, and has a toughening effect.
Example 2:
PDLA prepared in this and the following examplesn-b-PDMSm-b-PDLAnTriblock copolymers, all by1H NMR was used to determine its chemical composition, GPC was used to determine its molecular weight and molecular weight distribution, DSC was used to determine its thermal properties, electronic universal tester was used to determine its mechanical properties, and SEM was used to observe the morphology of its fracture surface.
Referring to FIG. 1, in this example, 2g PDMS, which is purchased from Sigma and has aminopropyl groups at both ends, was added to 120ml of anhydrous toluene, and 0.4ml of stannous octoate and 6g of D-lactide monomer (see
Purity of 99.5 percent), then heating to 120 ℃ for ring-opening polymerization, stopping the reaction after 24 hours, precipitating in methanol, filtering and washing, and drying in vacuum at 60 ℃ to obtain the triblock copolymer PDLAn-b-PDMSm-b-PDLAn。
Referring to the attached figure 2, the prepared triblock copolymer PDLA can be obtained by calculating the integral areas of different hydrogen in a nuclear magnetic hydrogen spectrogramn-b-PDMSm-b-PDLAnThe molar ratio of the segments of (a). Triblock copolymer PDLA obtained in this examplen-b-PDMSm-b-PDLAnM.n of (1) is about 1.6:1: 1.6. The number average molecular weight of PDMS in this example is 2500, so the triblock copolymer can be expressed as PDLA49-b-PDMS31-b-PDLA49。
See FIG. 3 for a triblock copolymer PDLA prepared as described above49-b-PDMS31-b-PDLA49Shows a number average molecular weight Mn of 22200 and a polydispersity index PDI (M)w/Mn) 1.31, the ring-opening polymerization process of D-lactide can be controlled by a single peak with symmetrical peak shape and PDI close to 1, the molecular weight distribution is narrow, and no trace amount of water-initiated homopolymerization byproducts are observed.
This example uses PLLA and the triblock copolymer PDLA synthesized in this example by melt blending49-b-PDMS31-b-PDLA49Preparing polylactic acid stereocomplex. The method comprises the following specific steps: taking 100 parts by mass of PLLA (NatureWorks, Ingeo)TM3052D) And 4 parts by mass of a triblock copolymer PDLA49-b-PDMS31-b-PDLA49The above PLLA and PDLA49-b-PDMS31-b-PDLA49Pre-drying the polylactic acid in an oven at 80 ℃ for 24 hours respectively to remove absorbed water in the polylactic acid, and preventing the degradation of the polylactic acid caused by high-temperature mixing; then melt blending is carried out in a micro double-screw mixing roll at the temperature of 190 ℃ to obtain the polylactic acid stereocomplex.
See FIG. 4. from the thermogram, it can be seen that it is different from pure PDLA49-b-PDMS31-b-PDLA49And pure PLLA, with 4 wt% PDLA added49-b-PDMS31-b-PDLA49After the toughening chain segment PDMS is dispersed and fixed in the PLLA matrix, the heat resistance of the PLLA matrix is improved.
And transferring the molten and mixed compound into a micro injection molding machine, wherein the temperature of an injection barrel is 200 ℃, the temperature of a mold is 60 ℃, and a plurality of sample strips for tensile testing are obtained. The mechanical properties of the prepared polylactic acid stereocomplex and pure PLLA are tested and compared, and tests show that the elongation at break of the polylactic acid stereocomplex added with 4 wt% of triblock copolymer is improved to about 192% from about 5% of the pure PLLA, and the tensile strength is only slightly reduced to about 55MPa from about 63MPa of the pure PLLA, so that the toughness of the polylactic acid stereocomplex is obviously enhanced.
Analysis of the fracture cross-sectional morphology of tensile test samples, see fig. 5, where a and B are Scanning Electron Microscope (SEM) photographs of the fracture cross-sections of pure PLLA and stereocomposite tensile samples containing 4 wt% triblock copolymer, respectively, it is evident that the cross-section of PLLA of fig. 5A is relatively smooth, while the cross-section of the stereocomposite of fig. 5B is much rougher, since these plastic deformations absorb a lot of energy during the fracture process, thus greatly increasing the toughness.
The polylactic acid stereocomplex prepared by the embodiment can be used for preparing plastic products, such as biomedical materials, packaging materials, 3D printing materials and the like.
Example 3:
in this example, 2g of PDMS having aminopropyl groups at both ends, which is purchased from Sigma, was added to 120ml of anhydrous toluene, and the number average molecular weight of the PDMS in this example was 2500; adding 0.4ml stannous octoate and 4g D-lactide monomer under the protection of nitrogen gas
Purity of 99.5 percent), then heating to 120 ℃ for ring-opening polymerization, stopping the reaction after 24 hours, precipitating in methanol, filtering and washing, and drying in vacuum at 60 ℃ to obtain the triblock copolymer PDLAn-b-PDMSm-b-PDLAn。
This example shows the PDLA triblock copolymer prepared in this example from nuclear magnetic hydrogen spectroscopyn-b-PDMSm-b-PDLAnIn the formula (I), n: m: n is about 1.05:1:1.05, GPC results show that the number average molecular weight Mn is 15900 and the PDI is 1.29, and the ring-opening polymerization process of the D-lactide is controllable and the molecular weight distribution is narrow. The triblock copolymer obtained in this example can be represented by PDLA32-b-PDMS31-b-PDLA32。
Example 4:
2g of PDMS having aminopropyl groups at both ends, purchased from Sigma, having a number average molecular weight of 2500Da, was added to 120ml of anhydrous toluene; adding 0.4ml stannous octoate and 2g D-lactide under the protection of nitrogenMonomer (A), (B)
Purity of 99.5 percent), then heating to 120 ℃ for ring-opening polymerization, stopping the reaction after 24 hours, precipitating in methanol, filtering and washing, and drying in vacuum at 60 ℃ to obtain the triblock copolymer PDLAn-b-PDMSm-b-PDLAn。
This example shows PDLA, a triblock copolymer prepared in this example, analyzed from nuclear magnetic hydrogen spectroscopyn-b-PDMSm-b-PDLAnIn the formula (I), n: m: n is about 0.44:1:0.44, GPC results show that the number average molecular weight Mn is 8900, PDI is 1.40, and the ring-opening polymerization process of D-lactide is controllable and the molecular weight distribution is narrow. The triblock copolymer obtained in this example can be expressed as PDLA14-b-PDMS31-b-PDLA14。
Example 5:
this example utilized PLLA and the triblock copolymer PDLA synthesized in example 2 using a melt blending method49-b-PDMS31-b-PDLA49Preparing a polylactic acid stereocomplex, which comprises the following steps: taking 100 parts by mass of PLLA (NatureWorks, Ingeo)TM3052D) And 2 parts by mass of a triblock copolymer PDLA49-b-PDMS31-b-PDLA49The above PLLA and PDLA49-b-PDMS31-b-PDLA49Pre-drying the polylactic acid in an oven at 80 ℃ for 24 hours respectively to remove absorbed water in the polylactic acid, and preventing the degradation of the polylactic acid caused by high-temperature mixing; then melt blending is carried out in a micro double-screw mixing roll at the temperature of 190 ℃ to obtain the polylactic acid stereocomplex.
And transferring the molten compound into a micro injection molding machine, wherein the temperature of an injection barrel is 200 ℃, the temperature of a mold is 60 ℃, and a plurality of sample strips for tensile testing are obtained. The mechanical properties of the prepared polylactic acid stereocomplex and pure PLLA are tested and compared, and tests show that the elongation at break of the polylactic acid stereocomplex added with 2 parts by mass of triblock copolymer is improved to about 89% from about 5% of the pure PLLA, and the tensile strength is only slightly reduced to about 57MPa from about 63MPa of the pure PLLA, so that the toughness of the polylactic acid stereocomplex is obviously enhanced.
The polylactic acid stereocomplex prepared by the embodiment can be used for preparing plastic products, such as biomedical materials, packaging materials, 3D printing materials and the like.
Example 6:
this example utilized PLLA and the triblock copolymer PDLA synthesized in example 2 using a melt blending method49-b-PDMS31-b-PDLA49Preparing a polylactic acid stereocomplex, which comprises the following steps: taking 100 parts by mass of PLLA (NatureWorks, Ingeo)TM3052D) And 1 part by mass of a triblock copolymer PDLA49-b-PDMS31-b-PDLA49The above PLLA and PDLA49-b-PDMS31-b-PDLA49Pre-drying the polylactic acid in an oven at 80 ℃ for 24 hours respectively to remove absorbed water in the polylactic acid, and preventing the degradation of the polylactic acid caused by high-temperature mixing; then melt blending is carried out in a micro double-screw mixing roll at the temperature of 190 ℃ to obtain the polylactic acid stereocomplex.
And transferring the molten compound into a micro injection molding machine, wherein the temperature of an injection barrel is 200 ℃, the temperature of a mold is 60 ℃, and a plurality of sample strips for tensile testing are obtained. The mechanical properties of the prepared polylactic acid stereocomplex and pure PLLA are tested and compared, and tests show that the elongation at break of the polylactic acid stereocomplex added with 1 part by mass of triblock copolymer is improved to about 35% from about 5% of the pure PLLA, and the tensile strength is only slightly reduced to about 56MPa from about 63MPa of the pure PLLA, so that the toughness of the polylactic acid stereocomplex is obviously enhanced.
The polylactic acid stereocomplex prepared by the embodiment can be used for preparing plastic products, such as biomedical materials, packaging materials, 3D printing materials and the like.
The above is an embodiment of the present invention. The embodiments and specific parameters in the embodiments are only for the purpose of clearly illustrating the verification process of the invention and are not intended to limit the scope of the invention, which is defined by the claims, and all equivalent structural changes made by using the contents of the specification and the drawings of the present invention should be covered by the scope of the present invention.
Claims (5)
1. A preparation method of polylactic acid stereocomplex is characterized by comprising the following steps:
s1: synthesis of triblock copolymer PDLAn-b-PDMSm-b-PDLAn
Adding 2g of PDMS with aminopropyl groups at two ends into 120ml of anhydrous toluene, adding 0.4ml of stannous octoate and 2-6 g of dextrorotatory lactide monomer under the protection of nitrogen, heating to 120 ℃ for ring-opening polymerization, stopping the reaction after 24h, precipitating in methanol, filtering, washing and drying in vacuum at 60 ℃ to obtain the triblock copolymer PDLAn-b-PDMSm-b-PDLAn；
S2: preparation of polylactic acid stereocomplex
Using a melt blending method with PLLA and the triblock copolymer PDLA synthesized in step S1n-b-PDMSm-b-PDLAnPreparing polylactic acid stereocomplex.
2. The method of claim 1, wherein the number average molecular weight of the PDMS having aminopropyl groups at both ends in the step S1 is 2500.
3. The method for preparing a polylactic acid stereocomplex according to claim 1, wherein the melt blending method comprises the following steps: taking 100 parts by mass of PLLA and 1-4 parts by mass of the PDLA prepared in the step S1n-b-PDMSm-b-PDLAnThe above PLLA and PDLAn-b-PDMSm-b-PDLAnPre-drying the polylactic acid in an oven at 80 ℃ for 24 hours respectively to remove the water absorbed by the polylactic acid and prevent the degradation of the polylactic acid during high-temperature mixing to cause the reduction of mechanical properties; then melt blending is carried out in a micro double-screw mixing roll at the temperature of 190 ℃ to obtain the polylactic acid stereocomplex.
4. A stereocomplex polylactic acid prepared by the method according to any one of claims 1 to 3.
5. Use of stereocomplex polylactic acid according to claim 4 for the preparation of plastic articles.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114181501A (en) * | 2021-11-08 | 2022-03-15 | 广东众塑降解材料有限公司 | Fully-degradable transparent seafood packaging film material and preparation method thereof |
| CN115354446A (en) * | 2022-08-19 | 2022-11-18 | 吉祥三宝高科纺织有限公司 | Polylactic acid thermal insulating flocculus with high fluffiness and high resilience and preparation method thereof |
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