CN114350130A - High-toughness polylactic acid composite material and preparation method thereof - Google Patents
High-toughness polylactic acid composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114350130A CN114350130A CN202210094648.4A CN202210094648A CN114350130A CN 114350130 A CN114350130 A CN 114350130A CN 202210094648 A CN202210094648 A CN 202210094648A CN 114350130 A CN114350130 A CN 114350130A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- composite material
- acid composite
- antioxidant
- polyethylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 128
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 127
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 48
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 48
- 239000002135 nanosheet Substances 0.000 claims abstract description 34
- 239000012948 isocyanate Substances 0.000 claims abstract description 29
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 29
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000001746 injection moulding Methods 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 32
- 239000013638 trimer Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 16
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 16
- 238000004108 freeze drying Methods 0.000 claims description 16
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 16
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940022769 d- lactic acid Drugs 0.000 claims description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 abstract description 9
- 229920002635 polyurethane Polymers 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000003993 interaction Effects 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000010008 shearing Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 description 31
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 13
- 238000007599 discharging Methods 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 12
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 4
- 229940120638 avastin Drugs 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 229920013724 bio-based polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The invention provides a high-toughness polylactic acid composite material and a preparation method thereof, wherein the composite material comprises raw materials such as polylactic acid, polyethylene glycol, an isocyanate cross-linking agent, MXene nano-sheets, an antioxidant and the like; the composite material has the characteristics of high mechanical strength, excellent impact property and the like; according to the preparation method of the composite material, the isocyanate crosslinking agent, the polyethylene glycol, the polylactic acid and the MXene nanosheets are dynamically vulcanized in situ under the high-speed shearing action of an internal mixer or a double-screw extruder to generate the crosslinked polyurethane, the polylactic acid-g-polyurethane copolymer and the grafting modified MXene nanosheets, so that the crosslinked polyurethane, the MXene nanosheets and a polylactic acid matrix have strong interface interaction; the preparation method of the polylactic acid composite material is simple in process, and the preparation route meets the development trend and requirements of green, low-carbon and environmental protection.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a high-toughness polylactic acid composite material and a preparation method thereof.
Background
In recent years, with the depletion of petroleum resources and the enhancement of environmental awareness, the development and development of environment-friendly bio-based polymer materials have received extensive attention from academia and industry. Polylactic acid (PLA) is expected to replace traditional petroleum-based polymer materials in various fields due to the characteristics of excellent biocompatibility and biodegradability, higher mechanical strength and modulus, easy processing and forming and the like, is one of the most active bio-based polymer materials researched and developed in recent years, and has wide application prospect. However, the low normal temperature notch impact strength (2.0-3.0 kJ/m2) and elongation at break (2-10%) severely limit the large-scale application of PLA, and cover the prospect of replacing petroleum-based polymer materials with a layer of shadow. Therefore, in order to further widen the application field, improving the toughness is one of the important research points of PLA modification.
Aiming at the brittleness defect of PLA, various toughening modification methods such as plasticizing, copolymerization, blending, stereo compounding and the like have been developed, but the blending toughening modification still attracts attention because the method is simple and efficient, and is easy to realize industrial preparation. Compared with the common blending toughening modification means, in order to improve the interaction of phase interfaces and realize the maximum toughening effect, the dynamic vulcanization technology based on reactive blending is widely applied. However, when the brittle material is subjected to toughening modification by using an elastomer, the strength and modulus are inevitably lost. The rigid nano material can improve the interfacial interaction of the blend, reduce the size of a dispersed phase and improve the performance of the blend. However, it is still difficult to achieve uniform dispersion of the nanomaterial in the polymer matrix and strong interfacial interaction during melt processing.
Disclosure of Invention
In view of this, the invention provides a high-toughness polylactic acid composite material and a preparation method thereof, so as to solve or at least partially solve the technical problems in the prior art.
In a first aspect, the invention provides a high-toughness polylactic acid composite material, which comprises the following raw materials in parts by weight: 60-90 parts of polylactic acid, 5-20 parts of polyethylene glycol, 5-20 parts of isocyanate crosslinking agent, 0.05-5 parts of MXene nanosheet and 0.3-1.0 part of antioxidant.
Preferably, the polylactic acid composite material with high toughness comprises at least one of poly-L-lactic acid, poly-D-lactic acid and racemic polylactic acid.
Preferably, the polyethylene glycol has an average molecular weight of 400-5000 in the high-toughness polylactic acid composite material.
Preferably, the isocyanate crosslinking agent of the high-toughness polylactic acid composite material comprises at least one of hexamethylene diisocyanate trimer, toluene diisocyanate trimer, isophorone diisocyanate trimer, diphenylmethane diisocyanate trimer and dicyclohexylmethane-4, 4' -diisocyanate trimer.
Preferably, the antioxidant of the high-toughness polylactic acid composite material comprises at least one of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant DLTP.
In a second aspect, the invention also provides a preparation method of the high-toughness polylactic acid composite material, which comprises the following steps:
adding polyethylene glycol and MXene nanosheets into water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
and (2) putting the polylactic acid, the polyethylene glycol/MXene blend and the antioxidant into an internal mixer or a double-screw extruder for melting and plasticizing, then adding an isocyanate crosslinking agent, and carrying out crosslinking reaction to obtain the high-strength and high-toughness polylactic acid composite material.
Preferably, in the preparation method of the high-strength and high-toughness polylactic acid composite material, if an internal mixer is adopted, the temperature of the internal mixer is controlled to be 160-220 ℃, the rotating speed of a rotor is 50-100 rpm, and the crosslinking reaction time is 5-20 min.
Preferably, in the preparation method of the high-toughness polylactic acid composite material, if a double-screw extruder is adopted, the temperature of the double-screw extruder is controlled to be 120-220 ℃, the rotating speed of a rotor is controlled to be 100-250 rpm, and the crosslinking reaction time is 3-5 min.
Preferably, the preparation method of the high-toughness polylactic acid composite material further comprises the step of injecting the material subjected to the crosslinking reaction into an injection molding machine for molding, wherein the injection molding temperature is 180-220 ℃, and the injection molding pressure is 50-60 MPa.
Compared with the prior art, the high-toughness polylactic acid composite material and the preparation method thereof have the following beneficial effects:
1. the high-toughness polylactic acid composite material comprises polylactic acid, polyethylene glycol, an isocyanate cross-linking agent, MXene nanosheets and an antioxidant, has the characteristics of high mechanical strength, excellent impact property and the like, and can be widely applied to the fields of automobile industry, agricultural production, packaging, clothing and the like;
2. according to the preparation method of the high-strength and high-toughness polylactic acid composite material, polylactic acid, a polyethylene glycol/MXene blend and an antioxidant are placed in an internal mixer or a double-screw extruder for melting and plasticizing, then an isocyanate crosslinking agent is added, and the isocyanate crosslinking agent, the polyethylene glycol, the polylactic acid and the MXene nanosheet are dynamically vulcanized in situ under the high-speed shearing action of the internal mixer or the double-screw extruder to generate crosslinked polyurethane, a polylactic acid-g-polyurethane copolymer and a grafting modified MXene nanosheet, so that the crosslinked polyurethane, the MXene nanosheet and a polylactic acid matrix have strong interface interaction, and the performance of the polylactic acid composite material can be randomly regulated and controlled by adjusting the molecular weight and content of the polyethylene glycol and the content of the MXene nanosheet; the preparation method of the polylactic acid composite material is simple in process, and the preparation route meets the development trend and requirements of green, low-carbon and environmental protection.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides a high-toughness polylactic acid composite material, which comprises the following raw materials in parts by weight: 60-90 parts of polylactic acid, 5-20 parts of polyethylene glycol, 5-20 parts of isocyanate crosslinking agent, 0.05-5 parts of MXene nanosheet and 0.3-1.0 part of antioxidant.
The polylactic acid composite material has the characteristics of high mechanical strength, excellent impact property and the like, and can be widely applied to the fields of automobile industry, agricultural production, packaging, clothing and the like.
In some embodiments, the polylactic acid comprises at least one of poly-L-lactic acid, poly-D-lactic acid, and racemic polylactic acid.
In some embodiments, the polyethylene glycol has an average molecular weight of 400 to 5000, preferably an average molecular weight of 800 to 1200, and more preferably 1000.
In some embodiments, the isocyanate crosslinker comprises at least one of hexamethylene diisocyanate trimer (HDIT), toluene diisocyanate trimer (TDIT), isophorone diisocyanate trimer (IPDIT), diphenylmethane diisocyanate trimer (MDIT), and dicyclohexylmethane-4, 4' -diisocyanate trimer (HMDIT).
In some embodiments, the antioxidant comprises at least one of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant DLTP.
In some embodiments, the molar ratio of isocyanate crosslinker to polyethylene glycol is (0.5-1.5): 1.
Specifically, the MXene nanosheets adopted in the application can be purchased in the market, and can also be prepared by the existing conventional method, and the specific preparation method comprises the following steps: selectively and chemically etching Al in MAX phase (Ti3AlC2) powder by using a mixed etchant of hydrochloric acid (HCl) and lithium fluoride (LiF) by using an in-situ HF method, centrifugally washing to obtain stacked brown or black brown MXene (Ti3C2) powder, and preparing the MXene nanosheets which can be stably dispersed in water and efficiently stripped by combining the means of hand shaking, water bath ultrasound, probe type ultrasound, gradient level centrifugal separation, freeze drying and the like.
Based on the same inventive concept, the embodiment of the application also provides a preparation method of the high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding polyethylene glycol and MXene nanosheets into water, performing ultrasonic dispersion, and performing freeze drying to obtain a polyethylene glycol/MXene blend;
and S2, placing the polylactic acid, the polyethylene glycol/MXene blend and the antioxidant into an internal mixer or a double-screw extruder for melting and plasticizing, then adding an isocyanate crosslinking agent, and carrying out crosslinking reaction to obtain the high-strength and high-toughness polylactic acid composite material.
The preparation method of the high-toughness polylactic acid composite material comprises the steps of placing polylactic acid, a polyethylene glycol/MXene blend and an antioxidant into an internal mixer or a twin-screw extruder for melting and plasticizing, then adding an isocyanate crosslinking agent, and dynamically vulcanizing the isocyanate crosslinking agent, the polyethylene glycol, the polylactic acid and the MXene nanosheets in situ under the high-speed shearing action of the internal mixer or the twin-screw extruder to generate crosslinked polyurethane, a polylactic acid-g-polyurethane copolymer and graft-modified MXene nanosheets, so that the crosslinked polyurethane, the MXene and a polylactic acid matrix have strong interface interaction, and the performance of the polylactic acid composite material can be randomly regulated and controlled by adjusting the molecular weight and content of the polyethylene glycol and the content of the MXene nanosheets; the preparation method of the polylactic acid composite material is simple in process, and the preparation route meets the development trend and requirements of green, low-carbon and environmental protection.
Specifically, in the step S1, water is used as a medium for mixing polyethylene glycol and MXene nanosheets, the water is removed by a freeze-drying method after the uniform mixing, the addition amount of the water has no influence on the performance of the prepared polylactic acid composite material, and the specific addition amount of the water can be determined according to actual conditions.
In some embodiments, if an internal mixer is used, the temperature of the internal mixer is controlled to be 160-220 ℃, the rotation speed of the rotor is 50-100 rpm, and the crosslinking reaction time is 5-20 min.
In some embodiments, if a twin-screw extruder is used, the temperature of the twin-screw extruder is controlled to be 120-220 ℃, the rotation speed of the rotor is controlled to be 100-250 rpm, and the crosslinking reaction time is controlled to be 3-5 min.
In some embodiments, the method further comprises injecting the material after the crosslinking reaction into an injection molding machine for molding, wherein the injection molding temperature is 180-220 ℃ and the injection molding pressure is 50-60 MPa.
The following further describes the preparation method of the high toughness polylactic acid composite material of the present application in specific examples, and the polylactic acid used in the following examples and comparative examples is dried at 80 ℃ for 4 hours before use.
Example 1
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 28.94g of polyethylene glycol 1000 (an avadine reagent) and 0.2g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 160g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 11.06g of isocyanate crosslinking agent hexamethylene diisocyanate trimer (HDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Example 2
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 28.94g of polyethylene glycol 1000 (an avadine reagent) and 0.4g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 160g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 11.06g of isocyanate crosslinking agent hexamethylene diisocyanate trimer (HDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Example 3
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 28.94g of polyethylene glycol 1000 (an avadine reagent) and 0.8g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 160g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 11.06g of isocyanate crosslinking agent hexamethylene diisocyanate trimer (HDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Example 4
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 28.94g of polyethylene glycol 1000 (an avastin reagent) and 1.6g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 160g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 11.06g of isocyanate crosslinking agent hexamethylene diisocyanate trimer (HDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Example 5
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 28.94g of polyethylene glycol 1000 (an avadine reagent) and 3g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 160g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 11.06g of isocyanate crosslinking agent hexamethylene diisocyanate trimer (HDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Example 6
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 14.47g of polyethylene glycol 1000 (an avadine reagent) and 0.4g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 180g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 5.53g of isocyanate cross-linking agent hexamethylene diisocyanate trimer (HDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Example 7
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 23.26g of polyethylene glycol 1000 (an avadine reagent) and 0.4g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 160g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 16.74g of isocyanate cross-linking agent isophorone diisocyanate trimer (IPDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Example 8
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 19.52g of polyethylene glycol 1000 (an avadine reagent) and 0.4g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 160g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 20.48g of isocyanate cross-linking agent toluene diisocyanate trimer (TDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Example 9
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 26.23g of polyethylene glycol 1000 (an avadine reagent) and 0.4g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 160g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 13.77g of isocyanate cross-linking agent diphenylmethane diisocyanate trimer (MDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Example 10
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 30.34g of polyethylene glycol 1000 (an avadine reagent) and 0.4g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 160g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 9.66g of isocyanate cross-linking agent hexamethylene diisocyanate trimer (HDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Example 11
The embodiment provides a preparation method of a high-toughness polylactic acid composite material, which comprises the following steps:
s1, adding 27.43g of polyethylene glycol 1000 (an avastin reagent) and 0.4g of MXene nanosheet into 100g of water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
s2, adding 160g of polylactic acid (L-polylactic acid 4032D, PLLA, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding the polyethylene glycol/MXene blend in S1 after 2min, mixing for 5min, adding 12.57g of isocyanate cross-linking agent hexamethylene diisocyanate trimer (HDIT), continuously blending for 13min, and discharging;
s3, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Comparative example 1
The comparative example provides a preparation method of a polylactic acid composite material, comprising the following steps:
s1, adding 200g of polylactic acid (PLLA, L-polylactic acid 4032D, Nature Works company, USA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, mixing for 20min and discharging;
s2, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
Comparative example 2
The comparative example provides a preparation method of a polylactic acid composite material, comprising the following steps:
s1, adding 160g of polylactic acid (the American Nature Works company, L-polylactic acid 4032D, PLLA), 0.4g of antioxidant 1010 and 0.2g of antioxidant 168 into a Haake torque rheometer (one type of internal mixer) with the temperature of 180 ℃ and the rotor speed of 60r/min, adding 28.94g of polyethylene glycol 1000 (an avastin reagent) after 2min, mixing for 5min, adding 11.06g of isocyanate crosslinking agent hexamethylene diisocyanate trimer (HDIT), continuously blending for 13min, and discharging;
s2, crushing the discharged product by using a crusher, and injecting the crushed product into a single-screw injection molding machine for injection molding to obtain the polylactic acid composite material, wherein the injection molding temperature is 200 ℃ and the injection molding pressure is 55 MPa.
The polylactic acid composite materials prepared in examples 1 to 11 and comparative examples 1 to 2 were tested for tensile strength, elongation at break, and impact strength, and the results are shown in table 1 below. Wherein, the tensile strength and the elongation at break are tested according to GB/T1040-2006, and the impact strength is tested according to GB/T1843-2008.
TABLE 1 Properties of the polylactic acid composites obtained in the different examples
| Examples | Tensile strength | Elongation at break | Impact strength |
| Example 1 | 38.72MPa | 198.32％ | 31.95kJ/m2 |
| Example 2 | 42.44MPa | 172.12％ | 25.91kJ/m2 |
| Example 3 | 41.38MPa | 149.33％ | 19.43kJ/m2 |
| Example 4 | 40.47MPa | 135.58％ | 17.21kJ/m2 |
| Example 5 | 38.89MPa | 72.62％ | 15.60kJ/m2 |
| Example 6 | 51.85MPa | 28.19％ | 19.04kJ/m2 |
| Example 7 | 35.77MPa | 161.37％ | 21.83kJ/m2 |
| Example 8 | 34.51MPa | 130.78％ | 17.82kJ/m2 |
| Example 9 | 40.39MPa | 84.94％ | 15.65kJ/m2 |
| Example 10 | 39.25MPa | 215.2％ | 14.64kJ/m2 |
| Example 11 | 44.27MPa | 205.46％ | 27.48kJ/m2 |
| Comparative example 1 | 61.24MPa | 5.61％ | 2.31kJ/m2 |
| Comparative example 2 | 25.79MPa | 283.82％ | 73.62kJ/m2 |
As can be seen from table 1, the polylactic acid composite material of comparative example 1 is high in tensile strength, but not high in toughness (elongation at break and impact strength); therefore, the polylactic acid material needs to be toughened and modified, but the general modification method tends to reduce the tensile strength of the polylactic acid material while improving the toughness of the polylactic acid material, such as shown in comparative example 2 of the application. According to the preparation method of the polylactic acid composite material, a small amount of MXene nanosheets are introduced through special process steps, the dispersing effect of the MXene nanosheets is improved, and the polylactic acid composite material with moderate strength and toughness, namely the polylactic acid composite material with high strength and high toughness, is obtained. In the polylactic acid composite materials prepared in the embodiments 1 to 11 of the present application, the embodiments 6 and 11 are preferred embodiments in terms of the final comprehensive properties.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The high-toughness polylactic acid composite material is characterized by comprising the following raw materials in parts by weight: 60-90 parts of polylactic acid, 5-20 parts of polyethylene glycol, 5-20 parts of isocyanate crosslinking agent, 0.05-5 parts of MXene nanosheet and 0.3-1.0 part of antioxidant.
2. The high toughness polylactic acid composite material according to claim 1, wherein the polylactic acid comprises at least one of poly-L-lactic acid, poly-D-lactic acid and racemic polylactic acid.
3. The high-toughness polylactic acid composite material as claimed in claim 1, wherein the average molecular weight of the polyethylene glycol is 400-5000.
4. The high toughness polylactic acid composite material according to claim 1, wherein the isocyanate crosslinking agent comprises at least one of hexamethylene diisocyanate trimer, toluene diisocyanate trimer, isophorone diisocyanate trimer, diphenylmethane diisocyanate trimer, and dicyclohexylmethane-4, 4' -diisocyanate trimer.
5. The high-toughness polylactic acid composite material as claimed in claim 1, wherein the antioxidant comprises at least one of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant DLTP.
6. A preparation method of the high-toughness polylactic acid composite material as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
adding polyethylene glycol and MXene nanosheets into water, ultrasonically dispersing, and freeze-drying to obtain a polyethylene glycol/MXene blend;
and (2) putting the polylactic acid, the polyethylene glycol/MXene blend and the antioxidant into an internal mixer or a double-screw extruder for melting and plasticizing, then adding an isocyanate crosslinking agent, and carrying out crosslinking reaction to obtain the high-strength and high-toughness polylactic acid composite material.
7. The preparation method of the high-toughness polylactic acid composite material as claimed in claim 6, wherein if an internal mixer is adopted, the temperature of the internal mixer is controlled to be 160-220 ℃, the rotating speed of a rotor is 50-100 rpm, and the crosslinking reaction time is 5-20 min.
8. The preparation method of the high-toughness polylactic acid composite material as claimed in claim 6, wherein if a double-screw extruder is adopted, the temperature of the double-screw extruder is controlled to be 120-220 ℃, the rotating speed of a rotor is controlled to be 100-250 rpm, and the crosslinking reaction time is 3-5 min.
9. The preparation method of the high-strength and high-toughness polylactic acid composite material as claimed in claim 6, further comprising the step of injecting the material after the crosslinking reaction into an injection molding machine for molding, wherein the injection molding temperature is 180-220 ℃ and the injection molding pressure is 50-60 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210094648.4A CN114350130A (en) | 2022-01-26 | 2022-01-26 | High-toughness polylactic acid composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210094648.4A CN114350130A (en) | 2022-01-26 | 2022-01-26 | High-toughness polylactic acid composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114350130A true CN114350130A (en) | 2022-04-15 |
Family
ID=81093782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210094648.4A Pending CN114350130A (en) | 2022-01-26 | 2022-01-26 | High-toughness polylactic acid composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114350130A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853978A (en) * | 2022-05-23 | 2022-08-05 | 中国科学院长春应用化学研究所 | High-gas-barrier weather-resistant polyurethane film and preparation method thereof |
| CN115195325A (en) * | 2022-07-13 | 2022-10-18 | 常州工学院 | Animal-imitated writing brush containing MXene and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435984A (en) * | 2013-07-22 | 2013-12-11 | 北京化工大学 | Method for toughening polydactyl acid through crosslinking sliding graft polymer |
| CN103450649A (en) * | 2013-09-13 | 2013-12-18 | 四川大学 | High-toughness polylactic acid/crosslinked polyurethane compound and preparation method thereof |
| CN109608841A (en) * | 2018-12-12 | 2019-04-12 | 广安长明高端产业技术研究院 | A kind of preparation method and product of MXene enhancing polylactic acid 3D printing material |
| CN111978694A (en) * | 2020-08-14 | 2020-11-24 | 华南理工大学 | Polylactic acid composite material with tensile resistance and impact resistance and preparation method thereof |
| CN113023809A (en) * | 2021-05-07 | 2021-06-25 | 南京林业大学 | Preparation method of membrane material for solar interface evaporation seawater desalination |
-
2022
- 2022-01-26 CN CN202210094648.4A patent/CN114350130A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435984A (en) * | 2013-07-22 | 2013-12-11 | 北京化工大学 | Method for toughening polydactyl acid through crosslinking sliding graft polymer |
| CN103450649A (en) * | 2013-09-13 | 2013-12-18 | 四川大学 | High-toughness polylactic acid/crosslinked polyurethane compound and preparation method thereof |
| CN109608841A (en) * | 2018-12-12 | 2019-04-12 | 广安长明高端产业技术研究院 | A kind of preparation method and product of MXene enhancing polylactic acid 3D printing material |
| CN111978694A (en) * | 2020-08-14 | 2020-11-24 | 华南理工大学 | Polylactic acid composite material with tensile resistance and impact resistance and preparation method thereof |
| CN113023809A (en) * | 2021-05-07 | 2021-06-25 | 南京林业大学 | Preparation method of membrane material for solar interface evaporation seawater desalination |
Non-Patent Citations (1)
| Title |
|---|
| XINXIN SHENG ET AL: ""Properties of two-dimensional Ti 3 C 2 MXene/thermoplastic polyurethane nanocomposites with effective reinforcement via melt blending"", 《COMPOSITES SCIENCE AND TECHNOLOGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853978A (en) * | 2022-05-23 | 2022-08-05 | 中国科学院长春应用化学研究所 | High-gas-barrier weather-resistant polyurethane film and preparation method thereof |
| CN115195325A (en) * | 2022-07-13 | 2022-10-18 | 常州工学院 | Animal-imitated writing brush containing MXene and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114350130A (en) | High-toughness polylactic acid composite material and preparation method thereof | |
| Jonoobi et al. | Mechanical properties of cellulose nanofiber (CNF) reinforced polylactic acid (PLA) prepared by twin screw extrusion | |
| Nie et al. | Bio-based epoxidized natural rubber/chitin nanocrystals composites: Self-healing and enhanced mechanical properties | |
| Li et al. | Cotton cellulose nanofiber-reinforced high density polyethylene composites prepared with two different pretreatment methods | |
| CN103642184B (en) | Dynamic vulcanization polylactic acid plastic/rubber thermoplastic elastomer and preparation method thereof | |
| Liu et al. | Bamboo fiber and its reinforced composites: structure and properties | |
| Liu et al. | Regulating tannic acid-crosslinked epoxidized soybean oil oligomers for strengthening and toughening bamboo fibers-reinforced poly (lactic acid) biocomposites | |
| EP3998311A1 (en) | Biodegradable product and preparation method therefor | |
| Nunes | Rubber nanocomposites with nanocellulose | |
| CN111410828B (en) | Preparation method of plant wood powder/montmorillonite filled high-performance fully biodegradable polylactic acid composite material | |
| CN101875765A (en) | Plasticized polylactic acid/inorganic nano composite material and preparation method thereof | |
| CN114213817B (en) | Preparation method of PBAT/PLA/CaCO3 full-biodegradable composite material | |
| Ghari et al. | Morphology development and mechanical properties of PLA/differently plasticized starch (TPS) binary blends in comparison with PLA/dynamically crosslinked “TPS+ EVA” ternary blends | |
| Wang et al. | Modified alkaline lignin for ductile polylactide composites | |
| Mohamad et al. | Properties enhancement of polylactic acid biocomposite | |
| Jia et al. | Superior toughened biodegradable poly (L-lactic acid)-based blends with enhanced melt strength and excellent low-temperature toughness via in situ reaction compatibilization | |
| CN103571165B (en) | Lactic acid composite material and preparation method thereof | |
| CN107400344B (en) | Ultra-toughness PLA/NBR biology base thermoplastic sulfurized rubber with shape memory function and preparation method thereof | |
| Al-Malki et al. | Study the effect of recycled tire rubber on the mechanical and rheological properties of TPV (HDPE/Recycled tire rubber) | |
| Kaesaman et al. | Influence of vulcanization system on curing, mechanical, dynamic and morphological properties of maleated natural rubber and its thermoplastic vulcanizate with thermoplastic copolyester elastomer | |
| CN106854347A (en) | A kind of polymeric lactic acid compound film material and preparation method thereof | |
| CN103102561B (en) | A kind of LDPE/EPMD/POM composite foam material and preparation method thereof | |
| Subyakto et al. | Injection molded of bio-micro-composites from natural fibers and polylactic acid | |
| CN108017889B (en) | A kind of polylactic acid/methyl methacrylate rubber composite material and preparation method of strong and unyielding equilibrium | |
| CN107722579A (en) | A kind of Novel sliding ring material/PLA thermoplastic elastomer (TPE) and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220415 |
|
| RJ01 | Rejection of invention patent application after publication |