CN117801483A - Bio-based tough polylactic acid/polyamide 11 material and preparation method thereof - Google Patents
Bio-based tough polylactic acid/polyamide 11 material and preparation method thereof Download PDFInfo
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- CN117801483A CN117801483A CN202311852678.8A CN202311852678A CN117801483A CN 117801483 A CN117801483 A CN 117801483A CN 202311852678 A CN202311852678 A CN 202311852678A CN 117801483 A CN117801483 A CN 117801483A
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- polylactic acid
- polyamide
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- soybean oil
- epoxidized soybean
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 72
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 72
- 229920000571 Nylon 11 Polymers 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003549 soybean oil Substances 0.000 claims abstract description 13
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 13
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 10
- 238000011161 development Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a bio-based tough polylactic acid/polyamide 11 material and a preparation method thereof, wherein 60-80% of polylactic acid, 10-39% of polyamide 11 and 1-10% of epoxidized soybean oil are taken by weight, the polylactic acid, the polyamide 11 and the epoxidized soybean oil are uniformly mixed and added into melt blending equipment to prepare the bio-based tough polylactic acid/polyamide 11 material, the epoxidized soybean oil and the polylactic acid and the polyamide 11 form a moderate cross-linked network between molecular chains in a blending system, the interfacial compatibility of the polylactic acid and the polyamide 11 is improved, and meanwhile, the main materials of the polylactic acid, the polyamide 11 and the epoxidized soybean oil are all bio-based materials, so that the bio-based tough polylactic acid/polyamide 11 material accords with the development concept of green environmental protection. The prepared composite material overcomes the defect of brittleness of polylactic acid, has excellent tensile strength, ductility and impact resistance, can be directly used in the fields of films, packaging materials, plates and the like, has simple production process and low cost, and has good application prospect.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a bio-based tough polylactic acid/polyamide 11 material and a preparation method thereof.
Background
The plastic product is convenient for human life, and simultaneously, a large amount of waste plastics cannot be treated to cause white pollution, and the conventional plastics are prepared from petroleum-based polymers and are non-renewable resources. Therefore, development and application of bio-based degradable plastic products have been a hot topic in recent years. Polylactic acid is taken as a bio-based polymer and has the characteristic of biodegradability, and is expected to replace petroleum-based plastics by human beings, however, the polylactic acid has poor toughness and insufficient impact resistance, and has brittleness under the general condition, so that the application of the polylactic acid is restricted.
To improve the toughness of polylactic acid, it is common to blend an elastomer with polylactic acid to modify the polylactic acid. On one hand, the toughness of the elastomer can make up for the defect of insufficient toughness of the polylactic acid, and on the other hand, the high strength of the polylactic acid can improve the defect of low strength of the elastomer, and the advantages of the two materials are complementary to obtain the high-performance bio-based composite material with both strength and toughness. At present, the mixing of polylactic acid with petroleum-based elastomer is the simplest and most effective method for toughening polylactic acid, such as polyethylene, polyurethane, polyethylene-polyglycidyl methacrylate, and (acrylonitrile-butadiene-styrene) copolymer, etc., however, the addition of petroleum-based elastomer with polylactic acid as a dispersed phase seriously affects the sustainability and biodegradability of polylactic acid.
The preparation of a fully bio-based polylactic acid ductile material is of great importance. Polyamide 11 is also a bio-based material extracted from castor oil, and has the advantages of better toughness, excellent impact strength and the like. The polyamide 11 is used as a second component to be added into polylactic acid for modification, so that a composite material with two main components being biological base materials can be obtained, and the development concept of green and environment protection is met. However, due to the interfacial effect of the polymer, the two phases are separated, and the performance of the composite material obtained by direct melt blending cannot be obviously improved, and the compatibility between the components is improved by adding a third component elastomer polyethylene-glycidyl methacrylate grafted polystyrene-acrylonitrile into polylactic acid and nylon 11 in the patent CN102391628A, so that the impact strength and toughness of the composite material are improved, but the tensile strength and modulus of the composite material are greatly reduced, and the elastomer is a petroleum-based material, so that the biodegradability of the polylactic acid material is damaged.
Disclosure of Invention
The scheme provides a bio-based tough polylactic acid/polyamide 11 material and a preparation method thereof, and provides a full bio-based tough polylactic acid/polyamide 11 material with tensile strength and toughness.
In order to achieve the above purpose, the scheme provides a preparation method of a bio-based tough polylactic acid/polyamide 11 material, which comprises the following steps:
taking 60-80% of polylactic acid, 10-39% of polyamide 11 and 1-10% of epoxidized soybean oil;
uniformly mixing polylactic acid, polyamide 11 and epoxidized soybean oil, adding the mixture into a melt blending device, melt blending for 5-10min at the temperature of between 180 and 230 ℃ at the speed of 60-80r/min, and then discharging, cooling, granulating and drying to obtain the bio-based tough polylactic acid/polyamide 11 material.
In some embodiments, 0.1 to 0.3 weight percent of an initiator is added, the initiator being dicumyl peroxide.
In some embodiments, the epoxidized soybean oil has an epoxy value greater than 6. The epoxy groups on the molecular chain of the epoxidized soybean oil react with the polylactic acid and the terminal groups of the polyamide 11 to form a moderately crosslinked network.
In some embodiments, the bio-based tough polylactic acid/polyamide 11 material is prepared by melt blending at 180-230 ℃ for 5-10min at 60-80r/min with a melt blending device, and then discharging, cooling, granulating and drying
In some embodiments, the melt blending device is any one of an internal mixer, a single screw extruder, or a twin screw extruder.
In a second aspect, the present invention provides a bio-based tough polylactic acid/polyamide 11 material, which is prepared according to the preparation method of the bio-based tough polylactic acid/polyamide 11 material.
In some embodiments, the biobased tough polylactic acid/polyamide 11 material of the present solution has an elongation at break of 146-402%.
Compared with the prior art, the scheme has the following characteristics and beneficial effects:
(1) The polylactic acid, the polyamide 11 and the epoxidized soybean oil are blended, the prepared composite material is completely of a biological base source, the utilization of non-renewable resources can be reduced, the environment is protected, the sustainable development concept is compounded, the prepared composite material is a full-biological base biodegradable material, and the development concept of environment protection is met.
(2) The epoxy group on the molecular chain of the epoxidized soybean oil can react with the molecular chain end of the polylactic acid and the polyamide 11 to form a moderate crosslinking network, so that the polylactic acid molecules and the polyamide 11 molecules form connection, the compatibility between two phases is enhanced, the interfacial compatibility of the polylactic acid and the polyamide 11 is improved, the interfacial stress transmission is promoted, the moderate crosslinking network is also favorable for the improvement of mechanical properties, and the polylactic acid material with excellent comprehensive properties is obtained.
(3) The materials used in the invention are all industrial raw materials, the equipment used in the invention is mainly melt blending equipment, the process equipment is simple, the production cost is low, and the method is suitable for large-scale industrial production.
(4) The prepared composite material overcomes the defect of brittleness of polylactic acid, has excellent tensile strength, ductility and impact resistance, can be directly used in the fields of films, packaging materials, plates and the like, has simple production process and low cost, and has good application prospect.
Drawings
FIG. 1 is a schematic illustration of the variation of tensile stress of different embodiments;
FIG. 2 shows the fracture surface micro morphology of the bio-based tough polylactic acid/polyamide 11 material of various embodiments under a scanning electron microscope.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
It will be understood that the terms "a" and "an" should be interpreted as referring to "at least one" or "one or more," i.e., in one embodiment, the number of elements may be one, while in another embodiment, the number of elements may be plural, and the term "a" should not be interpreted as limiting the number.
The invention is further described below with reference to examples. Main raw material information: PLLA (4032D), nature works LLC, USA, weight average molecular weight 1.7X10 5 g/mol；PA11,BECV0P40 TL, arkema, france, melt index 3.72g/10min (235 ℃,2.16 kg); ESO, shanghai aladin, epoxy number greater than 6. Before use, PLA and PA11 pellets were placed in a vacuum oven at 60 ℃ for 24 hours. The composition ratios of the specific examples and comparative examples are shown in Table 1.
Example 1
70wt% PLA, 29wt% PA11 and 1wt% ESO were added to an internal mixer, and 0.2wt% dicumyl peroxide (DCP) was added as an initiator, and blended at 220℃and 60rmp for 8 minutes to obtain a blend.
Example 2
67wt% PLA, 30wt% PA11 and 3wt% ESO were added to an internal mixer, and 0.2wt% dicumyl peroxide (DCP) was added as an initiator, and blended at 220℃and 60rmp for 8 minutes to obtain a blend.
Example 3
60wt% PLA, 35wt% PA11 and 5wt% ESO were added to an internal mixer, and 0.2wt% dicumyl peroxide (DCP) was added as an initiator, and blended at 220℃and 60rmp for 8 minutes to obtain a blend.
Example 4
66wt% PLA, 27wt% PA11 and 7wt% ESO were added to an internal mixer, and 0.2wt% dicumyl peroxide (DCP) was added as an initiator, and blended at 220℃and 60rmp for 8 minutes to obtain a blend.
Example 5
60wt% PLA, 30wt% PA11 and 10wt% ESO were added to an internal mixer, and 0.2wt% dicumyl peroxide (DCP) was added as an initiator, and blended at 220℃and 60rmp for 8 minutes to obtain a blend.
Example 6
80wt% PLA, 17wt% PA11 and 3wt% ESO were added to an internal mixer, and 0.2wt% dicumyl peroxide (DCP) was added as an initiator, and blended at 220℃and 60rmp for 8 minutes to obtain a blend.
Comparative example 1
PLA was added to an internal mixer and blended for 8min at 220℃at 60rmp to give a blend.
Comparative example 2
70wt% PLA, 30wt% PA11 were added to an internal mixer, and 0.2wt% dicumyl peroxide (DCP) was added as an initiator, and blended at 220℃and 60rmp for 8 minutes to obtain a blend.
The mechanical property verification method of the polylactic acid-based biodegradable material comprises the following steps: the prepared polylactic acid-based biodegradable material is respectively injection molded into standard tensile bars with the length of 30.0x5.0x2.0 mm (length, width and thickness) and standard notch impact test bars with the length of 80.0x10.0x4.0 mm in an injection molding machine at the temperature of 200 ℃, and the mechanical properties of the polylactic acid-based biodegradable material are systematically analyzed. The test results are shown in Table 2 and FIG. 1, wherein the tensile strength and elongation at break index are tested according to GB/T1040.3-2018 and the notched impact strength is tested according to GB/T16420-1997. The scanning electron microscope test method comprises the following steps: and (3) carrying out metal spraying treatment on the tensile fracture surface of the standard spline, and then observing the microscopic morphology of the fracture surface under a scanning electron microscope. The partial results are shown in FIG. 2.
The proportions of the components of the different examples and comparative examples are shown in Table 1 below:
TABLE 1 component proportions of the different examples and comparative examples
TABLE 2 mechanical property data for the different examples and comparative examples
From the comparison of the mechanical properties of the examples with the comparative examples, it can be concluded that: after the ESO is introduced into the PLA/PA11 blend, the elongation at break of the composite material is improved. When the addition amount of ESO reaches 7%, the elongation at break of the material reaches to the maximum 402%, 67 times of pure PLA, and the tensile strength reaches to the maximum 56MPa. While the impact strength of the material was 17.8kJ/m 2 Is 3.6 times that of pure PLA. As the epoxy group on the ESO molecular chain reacts with the tail ends of the PLA and PA11 molecular chains, cross-linking occurs between the PLA and the PA11 molecular chains, the compatibility between the two phases is improved, and the mechanical property of the material is greatly improved. When the ESO is added in excess (10%), a large number of crosslinking points appear in the system, so that the toughness of the material is lowered.
As can be seen from SEM results of tensile fracture surfaces of some examples and comparative examples, a large amount of PA11 microspheres exist on a cross section of the material without ESO, while less fibrous structure is drawn out, which shows poor compatibility of PLA with PA 11. As the addition and content of ESO are increased, PA11 microspheres at the fracture surface disappear, and the fibrous structure generated by ductile tearing existing on the fracture surface gradually increases, when the addition of ESO reaches 7%, the fracture surface has the thinnest fiber diameter and the maximum quantity due to ductile tearing, so that the best mechanical property is shown, and when the addition of ESO reaches 10%, more nodules exist among the fracture surface fibers, presumably because the excessive ESO causes a great amount of crosslinking reaction of the system.
The present invention is not limited to the above-described preferred embodiments, and any person who can obtain other various products under the teaching of the present invention, however, any change in shape or structure of the product is within the scope of the present invention, and all the products having the same or similar technical solutions as the present application are included.
Claims (7)
1. The preparation method of the bio-based tough polylactic acid/polyamide 11 material is characterized by comprising the following steps:
taking 60-80% of polylactic acid, 10-39% of polyamide 11 and 1-10% of epoxidized soybean oil;
uniformly mixing polylactic acid, polyamide 11 and epoxidized soybean oil, adding the mixture into a melt blending device, melt blending for 5-10min at the temperature of between 180 and 230 ℃ at the speed of 60-80r/min, and then discharging, cooling, granulating and drying to obtain the bio-based tough polylactic acid/polyamide 11 material.
2. The method for preparing the bio-based tough polylactic acid/polyamide 11 material according to claim 1, wherein 0.1-0.3% by weight of an initiator is added, and the initiator is dicumyl peroxide.
3. The method for preparing the bio-based tough polylactic acid/polyamide 11 material according to claim 1, wherein the epoxy value of the epoxidized soybean oil is more than 6.
4. The method for preparing the bio-based tough polylactic acid/polyamide 11 material according to claim 1, wherein the melt blending equipment performs melt blending at 60-80r/min and 180-230 ℃ for 5-10min.
5. The method for preparing the bio-based tough polylactic acid/polyamide 11 material according to claim 1, wherein the melt blending device is any one of an internal mixer, a single screw extruder or a twin screw extruder.
6. A bio-based tough polylactic acid/polyamide 11 material, characterized in that it is prepared by the method for preparing a bio-based tough polylactic acid/polyamide 11 material according to any one of claims 1 to 5.
7. The bio-based tough polylactic acid/polyamide 11 material according to claim 6, wherein the elongation at break is 146-402%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311852678.8A CN117801483A (en) | 2023-12-29 | 2023-12-29 | Bio-based tough polylactic acid/polyamide 11 material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311852678.8A CN117801483A (en) | 2023-12-29 | 2023-12-29 | Bio-based tough polylactic acid/polyamide 11 material and preparation method thereof |
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| CN202311852678.8A Pending CN117801483A (en) | 2023-12-29 | 2023-12-29 | Bio-based tough polylactic acid/polyamide 11 material and preparation method thereof |
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