CN113234308B - Method for improving compatibility of biodegradable blend by using low molecular weight functional copolymer and blend prepared by method - Google Patents
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Abstract
The invention discloses a method for improving the compatibility of biodegradable polymers by using a low-molecular-weight functional copolymer and a prepared blend. The method comprises the following steps: s1, preparing a low-molecular-weight functional copolymer; s2, uniformly mixing the low-molecular-weight functional copolymer with the biodegradable material, and then blending, extruding, cooling and granulating the mixture by a double-screw extruder; the biodegradable polymer comprises a biodegradable material with a reinforcing effect and a biodegradable material with a toughening effect. The functional copolymer with low molecular weight is prepared by the microchannel reactor, and has the characteristics of high reaction efficiency, adjustable components, high yield, large-scale production and environmental protection. In addition, the low molecular weight functional copolymer can effectively enhance the compatibility between biodegradable polymers, such as PLA and PBAT, PLA and PBST, and PLA and PBS, etc.
Description
Technical Field
The invention relates to the technical field of plastic modification, in particular to a method for improving the compatibility of a biodegradable blend by using a low-molecular-weight functional copolymer and a prepared blend, and particularly relates to a blend prepared by toughening and modifying a high-strength high-modulus biodegradable material (such as PLA) and a biodegradable material with excellent ductility (such as PBAT, PBST and PBS).
Background
The biodegradable polymer can be completely degraded by microorganisms after being discarded, and the use of the material is expected to relieve the white pollution problem faced by human beings. However, the currently marketed biodegradable polymers have the following disadvantages: polylactic acid has excellent mechanical strength and modulus, but poor toughness. PBAT, PBST, PBS and the like, while having excellent ductility, have low strength and modulus, limiting their use. Therefore, in practical applications, it is often necessary to blend PLA with PBAT, PBST, PBS and the like,
at present, the method for toughening and modifying polylactic acid is widely reported. For example, core-shell tougheners such as Acrylate Copolymer (ACR), acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer and the like are used for toughening polylactic acid and achieve certain effects, but the tougheners all belong to non-biodegradable polymers, so the toughening research of the all-bio-based polylactic acid material is an important direction for future research. The PBAT, the PBST and the PBS have biodegradable characteristics and are industrially produced, so the polymers are regarded as the PLA toughening agent with the most practical application prospect, but the key point for preparing the biodegradable blend with excellent performance is how to improve the interfacial compatibility of the polymers.
Patent document CN109486138A describes a PHA-modified PLA/PBAT biodegradable resin, which can increase the compatibility of PLA and PBAT by adding a certain amount of PHA during the blending and granulating process of PLA and PBAT. Patent document CN102504506A describes a method of compatibilizing a PLA/PBAT alloy using an oligomer having at least 2 isocyanate (-NCO) functional groups in the molecular chain as a compatibilizing agent. Patent document CN111378259A describes that a compound of formula (I) having a specific structure is used as a compatibilizer, which has a structure containing highly reactive groups such as epoxy groups, double bond groups, and hydroxyl groups, and is capable of reacting with carboxyl groups in the molecules of PLA and PBAT to perform a reactive compatibilization function. However, these methods still have some disadvantages, such as the addition amount of the compatibilizer is large, and the PHA needs at least 20 parts to achieve the compatibilization effect; and secondly, the isocyanate micromolecule chemical is used as a compatilizer, the isocyanate group has high reactivity, is sensitive to humidity and has poor stability, and in addition, the small molecular compound which is not completely reacted is easy to migrate to the surface and has biotoxicity.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for improving the compatibility of a biodegradable blend by using a low-molecular-weight functional copolymer and the prepared blend. In the invention, the functional copolymer with low molecular weight is prepared by adopting the microchannel reactor for the first time, and the method has the characteristics of high reaction efficiency, high yield, large-scale production and environmental protection, and the prepared functional copolymer with low molecular weight has adjustable molecular weight and controllable composition. PMMA, PLA, PBAT, PBST and PBS belong to lipid polymers, and have certain interfacial compatibility with each other, and the introduction of the PMMA part is beneficial to the dispersibility of the functional copolymer in the blend of PLA, PBAT, PBST and PBS, and enhances the interfacial property of the biodegradable material blend to a certain extent. Epoxy groups and maleic anhydride in the functional copolymer form a biodegradable material blend capable of being chemically compatibilized. The styrene is introduced mainly to enhance the reactivity of maleic anhydride.
The purpose of the invention is realized by the following technical scheme:
the invention provides a method for improving the compatibility of a biodegradable polymer by using a low-molecular-weight functional copolymer, which comprises the following steps:
s1, preparing a low molecular weight functional copolymer;
s2, uniformly mixing the low-molecular-weight functional copolymer with the biodegradable polymer, and then blending, extruding, cooling and granulating the mixture by a double-screw extruder;
the biodegradable polymer comprises a biodegradable material with a reinforcing effect and a biodegradable material with a toughening effect; the biodegradable material with the reinforcing effect is PLA, and the biodegradable material with the toughening effect is selected from PBAT, PBST and PBS.
Preferably, the low molecular weight functional copolymer is prepared by a microchannel reactor, and the molecular weight is 2000-20000 g/mol.
Preferably, the specific preparation steps of the low molecular weight functional copolymer include: dissolving a polymerization monomer in an organic solvent, and adding an initiator to carry out copolymerization reaction to obtain the polymer;
the polymerized monomers include at least two of Methyl Methacrylate (MMA), Glycidyl Methacrylate (GMA), styrene (St), and Maleic Anhydride (MA).
Preferably, the organic solvent is a polar solvent; the polar solvent is selected from N, N-dimethylformamide, toluene, dimethyl carbonate, dioxane, dimethyl sulfoxide and N-methylpyrrolidone; the total mass fraction of the polymerized monomers in the organic solvent is 20-90%;
the initiator is selected from one or more of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, dicumyl peroxide, benzoyl peroxide tert-butyl peroxide and methyl ethyl ketone peroxide, and the using amount of the initiator is 1-10 wt% of the total mass of the polymerization monomers;
the temperature of the copolymerization reaction is 100-150 ℃, depending on the type of the initiator selected.
Preferably, the polymerized monomers are methyl methacrylate and glycidyl methacrylate, and the molar ratio of the methyl methacrylate to the glycidyl methacrylate is 7: 3-3: 7.
Preferably, the polymerized monomers are methyl methacrylate, glycidyl methacrylate and maleic anhydride, the glycidyl methacrylate and the maleic anhydride are functional monomers, the molar ratio of the methyl methacrylate to the functional monomers is 7: 3-3: 7, and the molar ratio of the glycidyl methacrylate to the maleic anhydride is 20: 1-1: 20.
Preferably, the polymerized monomers are methyl methacrylate, glycidyl methacrylate, maleic anhydride and styrene, and the glycidyl methacrylate and the maleic anhydride are functional monomers; the molar ratio of methyl methacrylate to the functional monomer is 7: 3-3: 7, the molar ratio of glycidyl methacrylate to maleic anhydride is 20: 1-1: 20, and the molar ratio of styrene to maleic anhydride is equal.
Preferably, in step S2, the amount of the low molecular weight functional copolymer is 0.1 to 5% of the total mass of the biodegradable polymer;
the mass ratio of the biodegradable material with the reinforcing effect to the biodegradable material with the toughening effect is 1: 9-9: 1.
Preferably, in step S2, the temperature of the feeding section of the twin-screw extruder is 120 to 150 ℃, the temperature of the melting and plasticizing section is 190 to 220 ℃, and the temperature of the die orifice is 180 to 210 ℃.
The invention also provides a blend of biodegradable materials, which comprises a low-molecular-weight functional copolymer and a biodegradable polymer, wherein the content of the low-molecular-weight functional copolymer is 0.1-5% of the total mass of the biodegradable polymer; the biodegradable polymer comprises a biodegradable material with a toughening effect and a biodegradable material with a reinforcing effect, wherein the mass ratio of the biodegradable polymer to the biodegradable material is 1: 9-9: 1. Preferably, the low molecular weight functional copolymer is prepared by a microchannel reactor, and the specific preparation steps comprise:
dissolving a polymerization monomer in an organic solvent, and adding an initiator to carry out copolymerization reaction to obtain the polymer;
the polymerized monomer comprises at least two of methyl methacrylate, glycidyl methacrylate, styrene and maleic anhydride.
The blend of biodegradable materials prepared by the present invention can be used for injection molding or stretch film depending on the components.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention adopts the microchannel reactor to prepare the functional copolymer with low molecular weight, has the advantages of high reaction efficiency, low cost, high yield, environmental protection and the like, and realizes the controllable preparation of the molecular weight, the composition and the structure of the copolymer by selecting proper comonomer and process conditions.
2) The invention selects monomers and other reagent raw materials, has low cost and is expected to be used for industrial production.
3) Compared with the epoxy group-containing polymer compatilizer selected at present, the functional oligomer with low molecular weight prepared by the invention has the advantages that the introduction of the methyl methacrylate part is beneficial to the dispersibility of the functional oligomer in the PLA/PBAT blend and plays a role in physical compatibility, the PLA/PBAT blend can be compatibilized due to the composition of glycidyl methacrylate and maleic anhydride, but compared with the composition of glycidyl methacrylate, the reaction activity can be remarkably improved due to the introduction of maleic anhydride, and the polymerization activity of maleic anhydride is enhanced due to the introduction of styrene; from a molecular weight perspective, low molecular weight copolymers not only prevent crosslinking, but also facilitate rapid dispersion thereof in the blend.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a nuclear magnetic spectrum of a low molecular weight functional oligomer obtained in example 4;
FIG. 2 is a gel permeation chromatogram of a low molecular weight functional oligomer prepared in example 4;
FIG. 3 is an IR spectrum of a low molecular weight functional oligomer obtained in examples 8 to 12.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
This example relates to the preparation of a low molecular weight functional oligomer, comprising the following steps: MMA and GMA in equal molar ratio are dissolved in toluene, the total mass fraction of the MMA and the GMA is 50 wt%, and then azodiisobutyronitrile initiator accounting for 5 wt% of the total mass of the MMA and the GMA is added, and the reaction temperature is 130 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 7240 g/mol. The results of nuclear magnetic spectrum and gel permeation chromatography of the obtained low molecular weight functional copolymer are substantially in accordance with example 4.
Example 2
This example relates to the preparation of a low molecular weight functional oligomer, comprising the following steps: MMA and GMA in equal molar ratio are dissolved in toluene, the total mass fraction of the MMA and the GMA is 30 wt%, and then azodiisobutyronitrile initiator accounting for 5 wt% of the total mass of the MMA and the GMA is added, and the reaction temperature is 130 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 5840 g/mol. The results of nuclear magnetic spectrum and gel permeation chromatography of the obtained low molecular weight functional copolymer are substantially consistent with those of example 4.
Example 3
This example relates to the preparation of a low molecular weight functional copolymer, comprising the following steps: MMA and GMA in equal molar ratio are dissolved in toluene, the total mass fraction of the MMA and the GMA is 30 wt%, and then azodiisobutyronitrile initiator accounting for 10 wt% of the total mass of the MMA and the GMA is added, and the reaction temperature is 130 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 5380 g/mol. The results of nuclear magnetic spectrum and gel permeation chromatography of the obtained low molecular weight functional copolymer are substantially in accordance with example 4.
Example 4
This example relates to the preparation of a low molecular weight functional copolymer, comprising the following steps: MMA and GMA in equal molar ratio are dissolved in toluene, the total mass fraction of the MMA and the GMA is 30 wt%, and then azodiisobutyronitrile initiator accounting for 10 wt% of the total mass of the MMA and the GMA is added, and the reaction temperature is 140 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 4880 g/mol. The nuclear magnetic spectrum of the low molecular weight functional copolymer is shown in FIG. 1, and the gel permeation chromatogram is shown in FIG. 2.
Example 5
This example relates to the preparation of a low molecular weight functional copolymer, comprising the following steps: MMA and GMA in equal molar ratio are dissolved in toluene, the total mass fraction of the MMA and GMA is 30 wt%, and then benzoyl peroxide initiator accounting for 10 wt% of the total mass of the MMA and GMA is added, and the reaction temperature is 140 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 6780 g/mol. The results of nuclear magnetic spectrum and gel permeation chromatography of the obtained low molecular weight functional copolymer are substantially in accordance with example 4.
Example 6
This example relates to the preparation of a low molecular weight functional copolymer, comprising the following steps: MMA and GMA in a molar ratio of 3:7 are dissolved in toluene, the total mass fraction of MMA and GMA is 30 wt%, then 10 wt% of the total mass of MMA and GMA of benzoyl peroxide initiator is added, and the reaction temperature is 140 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 6360 g/mol. The results of nuclear magnetic spectrum and gel permeation chromatography of the obtained low molecular weight functional copolymer are substantially in accordance with example 4.
Example 7
This example relates to the preparation of a low molecular weight functional copolymer, comprising the following steps: MMA and GMA in a molar ratio of 8:2 are dissolved in toluene, the total mass fraction of MMA and GMA is 30 wt%, and then benzoyl peroxide initiator is added in an amount of 10 wt% of the total mass of MMA and GMA, the reaction temperature is 140 ℃. The molecular weight of the resulting low molecular weight functional copolymer is about 6170 g/mol. The results of nuclear magnetic spectrum and gel permeation chromatography of the obtained low molecular weight functional copolymer are substantially in accordance with example 4.
Example 8
This example relates to the preparation of a low molecular weight functional copolymer, comprising the following steps: MMA, GMA and MA in a molar ratio of 5:4:1 are dissolved in dimethyl carbonate, the total mass fraction of the MMA, GMA and MA is 30 wt%, then azodiisobutyronitrile initiator with 5 wt% of the total mass of the monomers is added, and the reaction temperature is 130 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 7270 g/mol. The IR spectrum of the resulting low molecular weight functional copolymer is shown in FIG. 3.
Example 9
This example relates to the preparation of a low molecular weight functional copolymer, comprising the following steps: MMA, GMA and MA in a molar ratio of 5:3:2 are dissolved in dimethyl carbonate, the total mass fraction of the MMA, GMA and MA is 30 wt%, then azodiisobutyronitrile initiator accounting for 5 wt% of the total mass of the monomers is added, and the reaction temperature is 130 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 6930 g/mol. The IR spectrum of the resulting low molecular weight functional copolymer is shown in FIG. 3.
Example 10
This example relates to the preparation of a low molecular weight functional copolymer, comprising the following steps: MMA, GMA and MA in a molar ratio of 5:2.5:2.5 are dissolved in toluene, the total mass fraction of MMA, GMA and MA is 30 wt%, and then azobisisobutyronitrile initiator in an amount of 5 wt% of the total mass of the monomers is added, the reaction temperature is 130 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 6740 g/mol. The IR spectrum of the resulting low molecular weight functional copolymer is shown in FIG. 3.
Example 11
This example relates to the preparation of a low molecular weight functional copolymer, comprising the following steps: MMA, GMA, MA and St are dissolved in toluene in a molar ratio of 5:4:1:1, the total mass fraction of MMA, GMA, MA and St is 30 wt%, and then azobisisobutyronitrile initiator is added in an amount of 5 wt% of the total mass of the monomers, the reaction temperature being 130 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 7930 g/mol. The IR spectrum of the resulting low molecular weight functional copolymer is shown in FIG. 3.
Example 12
This example relates to the preparation of a low molecular weight functional copolymer, comprising the following steps: MMA, GMA, MA and St in a molar ratio of 5:3:2:2 are dissolved in toluene, the total mass fraction of MMA, GMA, MA and St is 30 wt%, and then azobisisobutyronitrile initiator in an amount of 5 wt% of the total mass of the monomers is added, the reaction temperature being 130 ℃. The molecular weight of the resulting low molecular weight functional copolymer was about 7570 g/mol. The IR spectrum of the resulting low molecular weight functional copolymer is shown in FIG. 3.
Example 13
The embodiment relates to a preparation method of a low-molecular-weight functional copolymer compatibilized PBAT and PLA, which comprises the following steps: firstly, the materials are dried in vacuum, the ratio of PBAT to PLA is 3:7, a low molecular weight functional copolymer (prepared in example 4 and with the molecular weight of about 4880g/mol) which is 0.5 wt% of the total mass of PBAT and PLA is added, after uniform mixing, the mixture is extruded by a double-screw extruder, granulated and cooled, and then the plastic particles are prepared into tensile sample strips, bending sample strips and impact sample strips according to the national standard for mechanical property testing. The temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
Example 14
The embodiment relates to a preparation method of a low-molecular-weight functional copolymer compatibilized PBAT and PLA, which comprises the following steps: firstly, the materials are dried in vacuum, the proportion of PBAT to PLA is 3:7, a low molecular weight functional copolymer (prepared in example 4 and the molecular weight is about 4880g/mol) which is 1 wt% of the total mass of PBAT and PLA is added, after uniform mixing, the mixture is extruded by a double-screw extruder, granulated and cooled, and then the plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property testing. The temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
Example 15
The embodiment relates to a preparation method of a low-molecular-weight functional copolymer compatibilized PBAT and PLA, which comprises the following steps of firstly, drying materials in vacuum, wherein the proportion of PBAT to PLA is 3:7, adding a low-molecular-weight functional copolymer (prepared in example 4, the molecular weight is about 4880g/mol) accounting for 2 wt% of the total mass of PBAT and PLA, uniformly mixing, extruding by a double-screw extruder, granulating, cooling, and preparing the plastic particles into tensile sample strips and impact sample strips according to national standards for mechanical property testing. The temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
Example 16
The embodiment relates to a preparation method of a low-molecular-weight functional copolymer compatibilized PBAT and PLA, which comprises the following steps of firstly, drying materials in vacuum, wherein the proportion of PBAT to PLA is 3:7, adding a low-molecular-weight functional copolymer (prepared in example 4, the molecular weight is about 4880g/mol) which is 3 wt% of the total mass of PBAT and PLA, uniformly mixing, extruding by a double-screw extruder, granulating, cooling, and preparing the plastic particles into tensile sample strips and impact sample strips according to national standards for mechanical property testing. The temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
Example 17
The embodiment relates to a preparation method of a low-molecular-weight functional copolymer compatibilized PBAT and PLA, which comprises the following steps of firstly, drying materials in vacuum, wherein the ratio of PBAT to PLA is 4:6, adding a low-molecular-weight functional copolymer (prepared in example 4, the molecular weight is about 4880g/mol) accounting for 2 wt% of the total mass of PBAT and PLA, uniformly mixing, extruding by a double-screw extruder, granulating, cooling, and preparing the plastic particles into tensile sample strips and impact sample strips according to national standards for mechanical property testing. The temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
Example 18
This example relates to a method for preparing low molecular weight functional copolymer compatibilized PBAT and PLA, which is the same as example 16 except that: the mass of the low molecular weight functional copolymer added was 5 wt% of the total mass of PBAT and PLA. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
Example 19
This example relates to a method for preparing low molecular weight functional copolymer compatibilized PBAT and PLA, which is the same as example 16 except that: the mass of the low molecular weight functional copolymer added is 10 wt% of the total mass of PBAT and PLA. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
Example 20
This example relates to a method for preparing low molecular weight functional copolymer compatibilized PBAT and PLA, which is the same as example 14 except that: the PBAT/PLA ratio was 1: 9. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
Example 21
This example relates to a method for preparing low molecular weight functional copolymer compatibilized PBAT and PLA, which is the same as example 14 except that: the low molecular weight functional copolymer added was prepared for example 1 and had a molecular weight of 7240 g/mol. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
Example 22
This example relates to a method for preparing low molecular weight functional copolymer compatibilized PBAT and PLA, which is the same as example 14 except that: the low molecular weight functional copolymer added was prepared for example 2 and had a molecular weight of 5840 g/mol. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
Example 23
This example relates to a method for preparing low molecular weight functional copolymer compatibilized PBAT and PLA, which is the same as example 14 except that: the low molecular weight functional copolymer added was prepared for example 3 and had a molecular weight of 5380 g/mol. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
Example 24
This example relates to a method for preparing low molecular weight functional copolymer compatibilized PBAT and PLA, which is the same as example 14 except that: the low molecular weight functional copolymer added was prepared for example 5 and had a molecular weight of 6780 g/mol. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
Example 25
This example relates to a method for preparing low molecular weight functional copolymer compatibilized PBAT and PLA, which is the same as example 41 except that: the low molecular weight functional copolymer added was prepared for example 6 and had a molecular weight of 6360 g/mol. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
Example 26
This example relates to a method for preparing low molecular weight functional copolymer compatibilized PBAT and PLA, which is the same as example 14 except that: the low molecular weight functional copolymer added was prepared for example 7 and had a molecular weight of 6170 g/mol. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
Example 27
The embodiment relates to a preparation method of a low-molecular-weight functional copolymer compatibilized PBAT and PLA, which comprises the following steps: firstly, the materials are dried in vacuum, the ratio of PBAT to PLA is 3:7, a low molecular weight functional copolymer (prepared in example 8 and with the molecular weight of about 7270g/mol) which is 0.5 wt% of the total mass of PBAT and PLA is added, after uniform mixing, the mixture is extruded by a double-screw extruder, granulated and cooled, and then the plastic particles are prepared into tensile sample strips, bending sample strips and impact sample strips according to the national standard for mechanical property testing. The temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
Example 28
The embodiment relates to a preparation method of a low-molecular-weight functional copolymer compatibilized PBAT and PLA, which comprises the following steps: firstly, the materials are dried in vacuum, the proportion of PBAT and PLA is 3:7, a low molecular weight functional copolymer (prepared in example 9 and with the molecular weight of about 6930g/mol) which is 0.5 wt% of the total mass of PBAT and PLA is added, after uniform mixing, the mixture is extruded by a double-screw extruder, granulated and cooled, and then the plastic particles are prepared into tensile sample strips, bending sample strips and impact sample strips according to the national standard for mechanical property testing. The temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
Example 29
The embodiment relates to a preparation method of a low-molecular-weight functional copolymer compatibilized PBAT and PLA, which comprises the following steps: firstly, the materials are dried in vacuum, the ratio of PBAT to PLA is 3:7, a low molecular weight functional copolymer (prepared in example 10 and with the molecular weight of about 6740g/mol) which is 0.5 wt% of the total mass of PBAT and PLA is added, after uniform mixing, the mixture is extruded by a double-screw extruder, granulated and cooled, and then the plastic particles are prepared into tensile sample strips, bending sample strips and impact sample strips according to the national standard for mechanical property testing. The temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
Example 30
The embodiment relates to a preparation method of a low-molecular-weight functional copolymer compatibilized PBAT and PLA, which comprises the following steps: firstly, the materials are dried in vacuum, the ratio of PBAT to PLA is 3:7, a low molecular weight functional copolymer (prepared in example 10 and the molecular weight is about 7930g/mol) which is 0.5 wt% of the total mass of PBAT and PLA is added, after uniform mixing, the mixture is extruded by a double-screw extruder, granulated and cooled, and then the plastic particles are prepared into tensile sample strips, bending sample strips and impact sample strips according to the national standard for mechanical property testing. The temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
Example 31
The embodiment relates to a preparation method of a low-molecular-weight functional copolymer compatibilized PBAT and PLA, which comprises the following steps: firstly, materials are dried in vacuum, the ratio of PBAT to PLA is 3:7, a low molecular weight functional copolymer (prepared in example 11, the molecular weight is about 7570g/mol) which is 0.5 wt% of the total mass of PBAT and PLA is added, after uniform mixing, the mixture is extruded by a double-screw extruder, granulated and cooled, and then the plastic particles are prepared into tensile sample strips, bending sample strips and impact sample strips according to the national standard for mechanical property testing. The temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
Comparative example 1
This comparative example relates to a method of preparing a low molecular weight functional copolymer compatibilized PBAT and PLA, the specific method of preparation being the same as example 12, except that: the PBAT/PLA ratio was 7: 3.
Comparative example 2
The present comparative example relates to a method for preparing PMMA-compatibilized PBAT and PLA, the specific preparation method is the same as example 9, except that: PMMA was used instead of PMMA-PGMA. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
Comparative example 3
The comparative example relates to a preparation method of PGMA compatibilized PBAT and PLA, the specific preparation method is the same as that in example 9, and the difference is only that: PGMA is used instead of PMMA-PGMA. The prepared plastic particles are prepared into tensile sample strips and impact sample strips according to the national standard for mechanical property test.
TABLE 1 comparison of the mechanical properties of PBAT/PLA blends after addition of different amounts of PMMA-PGMA
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (6)
1. A method for preparing a low molecular weight functional copolymer for improving the compatibility of a biodegradable polymer, comprising the steps of:
s1, preparing a low-molecular-weight functional copolymer;
s2, uniformly mixing the low-molecular-weight functional copolymer with the biodegradable polymer, and then blending, extruding, cooling and granulating the mixture by a double-screw extruder;
the biodegradable polymer comprises a biodegradable material with a reinforcing effect and a biodegradable material with a toughening effect; the biodegradable material with the reinforcing effect is PLA, and the biodegradable material with the toughening effect is selected from PBAT, PBST and PBS;
the low-molecular-weight functional copolymer is prepared by a microchannel reactor, and the molecular weight of the low-molecular-weight functional copolymer is 2000-20000 g/mol;
the specific preparation steps of the low molecular weight functional copolymer comprise: dissolving a polymerization monomer in an organic solvent, and adding an initiator to carry out copolymerization reaction to obtain the polymer;
the polymerized monomer comprises a functional monomer, methyl methacrylate and/or styrene, and the functional monomer comprises glycidyl methacrylate and/or maleic anhydride; the molar ratio of the methyl methacrylate to the functional monomer is 7: 3-3: 7;
in step S2, the amount of the low molecular weight functional copolymer is 0.1-5% of the total mass of the biodegradable polymer.
2. The method for preparing a low molecular weight functional copolymer for improving compatibility of biodegradable polymers according to claim 1, wherein the organic solvent is a polar solvent; the polar solvent is selected from N, N-dimethylformamide, toluene, dimethyl carbonate, dioxane, dimethyl sulfoxide and N-methylpyrrolidone; the total mass fraction of the polymerized monomers in the organic solvent is 20-90%;
the initiator is selected from one or more of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, dicumyl peroxide, benzoyl peroxide tert-butyl peroxide and methyl ethyl ketone peroxide, and the using amount of the initiator is 1-10 wt% of the total mass of the polymerization monomers;
the temperature of the copolymerization reaction is 100-150 ℃.
3. The method for preparing the low-molecular-weight functional copolymer capable of improving the compatibility of the biodegradable polymer according to claim 1, wherein the polymerization monomers are methyl methacrylate, glycidyl methacrylate and maleic anhydride, the glycidyl methacrylate and the maleic anhydride are functional monomers, the molar ratio of the methyl methacrylate to the functional monomers is 7: 3-3: 7, and the molar ratio of the glycidyl methacrylate to the maleic anhydride is 20: 1-1: 20.
4. The method for preparing a low molecular weight functional copolymer for improving compatibility of biodegradable polymer according to claim 1, wherein the polymeric monomer is methyl methacrylate, glycidyl methacrylate, maleic anhydride and styrene, and glycidyl methacrylate and maleic anhydride are functional monomers; the molar ratio of methyl methacrylate to the functional monomer is 7: 3-3: 7, the molar ratio of glycidyl methacrylate to maleic anhydride is 20: 1-1: 20, and the molar ratio of styrene to maleic anhydride is equal.
5. The method for preparing the low molecular weight functional copolymer capable of improving the compatibility of the biodegradable polymer according to claim 1, wherein in the step S2, the mass ratio of the biodegradable material with the reinforcing effect to the biodegradable material with the toughening effect is 1: 9-9: 1;
in the step S2, the temperature of the feeding section of the double-screw extruder is 120-150 ℃, the temperature of the melting and plasticizing section is 190-220 ℃, and the temperature of the die orifice is 180-210 ℃.
6. A blend of biodegradable materials, which is characterized by comprising the low-molecular-weight functional copolymer prepared by the method of claim 1 and a biodegradable polymer, wherein the content of the low-molecular-weight functional copolymer is 0.1-5% of the total mass of the biodegradable polymer; the biodegradable polymer comprises a biodegradable material with a toughening effect and a biodegradable material with a reinforcing effect, wherein the mass ratio of the biodegradable polymer to the biodegradable material is 1: 9-9: 1.
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