CN114907677A - Scratch-resistant polylactic acid material with balanced rigidity and toughness and preparation method thereof - Google Patents
Scratch-resistant polylactic acid material with balanced rigidity and toughness and preparation method thereof Download PDFInfo
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- CN114907677A CN114907677A CN202111179620.2A CN202111179620A CN114907677A CN 114907677 A CN114907677 A CN 114907677A CN 202111179620 A CN202111179620 A CN 202111179620A CN 114907677 A CN114907677 A CN 114907677A
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- polylactic acid
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 150
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 149
- 239000000463 material Substances 0.000 title claims abstract description 79
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 35
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 34
- 229920001971 elastomer Polymers 0.000 claims abstract description 32
- 239000005060 rubber Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 34
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 26
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 23
- 244000043261 Hevea brasiliensis Species 0.000 claims description 20
- 229920000459 Nitrile rubber Polymers 0.000 claims description 20
- 229920003052 natural elastomer Polymers 0.000 claims description 20
- 229920001194 natural rubber Polymers 0.000 claims description 20
- 238000004132 cross linking Methods 0.000 claims description 19
- -1 acyloxy aluminate Chemical class 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 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 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 229910052755 nonmetal Inorganic materials 0.000 claims description 8
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 241000208689 Eucommia ulmoides Species 0.000 claims description 6
- 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 6
- 238000000034 method Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 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 4
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 3
- 229940022769 d- lactic acid Drugs 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000012763 reinforcing filler Substances 0.000 abstract description 2
- 239000011499 joint compound Substances 0.000 description 94
- 230000000052 comparative effect Effects 0.000 description 20
- 238000001035 drying Methods 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 241000208688 Eucommia Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- UJKMGUWJWAGVTA-UHFFFAOYSA-N propan-2-ylperoxybenzene Chemical compound CC(C)OOC1=CC=CC=C1 UJKMGUWJWAGVTA-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 102220040412 rs587778307 Human genes 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of high polymer materials, and provides a scratch-resistant polylactic acid material with balanced rigidity and toughness and a preparation method thereof. The preparation raw materials of the polylactic acid material provided by the invention comprise 10-40 parts of rubber, 60-90 parts of polylactic acid, 0.2-1 part of antioxidant, 0.5-2 parts of cross-linking agent and 10-50 parts of modified red mud. According to the invention, the polylactic acid material is toughened by using rubber with a continuous phase structure, and the modified red mud is introduced to be used as a functional reinforcing filler, so that the polylactic acid material is effectively reinforced, and the rigidity and toughness of the polylactic acid material are balanced, thereby the polylactic acid material has excellent scratch resistance. The preparation method provided by the invention has simple steps and easy operation, and can be used for forming products with any shapes according to the use working conditions.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a scratch-resistant polylactic acid material with balanced rigidity and toughness and a preparation method thereof.
Background
In the face of increasingly intensified environmental problems such as energy crisis, white pollution, black pollution and the like, green products and advanced manufacturing technologies thereof become new hotspots of international and domestic market competition, and green raw materials and green processes become effective ways for solving the problems of petroleum resource shortage, environmental deterioration and the like.
Polylactic acid is a typical bio-based renewable degradable polymer, has great potential in replacing traditional petroleum polymers due to good processing performance and higher mechanical strength, and is known as a bio-based polymer material with the best development prospect. However, the polylactic acid has obvious defects such as poor toughness and scratch resistance, which causes scratches to be easily generated during the production, transportation and use processes, affects the appearance and limits the application of the polylactic acid in the fields of automobiles, household appliances, packaging, daily necessities and the like. Therefore, the toughening and scratch-resistant modification of polylactic acid is very important.
Patent CN109912950A discloses a scratch-resistant PLA/PP composite material, wherein polylactic acid and polypropylene are blended, and a styrene-acrylonitrile grafted glycidyl methacrylate and/or polyvinyl alcohol grafted polylactic acid and a scratch-resistant modifier are added to prepare the PLA/PP composite material with excellent scratch resistance. However, the scratch-resistant agent used in the invention is an organosilicon/ketone polymer, an acrylic copolymer or PTFE micropowder, and the dosage is large, and the scratch-resistant agent not only has high cost, but also has poor compatibility with a PLA/PP matrix, so that the toughness of the finally obtained composite material is poor, and the application and popularization of the composite material are severely limited.
Disclosure of Invention
In view of this, the invention provides a scratch-resistant polylactic acid material with balanced rigidity and toughness and a preparation method thereof. The polylactic acid material provided by the invention has the advantages of balanced rigidity and toughness, excellent impact resistance, high mechanical strength and excellent scratch resistance.
In order to achieve the above object, the present invention provides the following technical solutions:
the scratch-resistant polylactic acid material with balanced rigidity and toughness comprises the following preparation raw materials in parts by weight: 10-40 parts of rubber, 60-90 parts of polylactic acid, 0.2-1 part of antioxidant,
0.5-2 parts of a cross-linking agent and 10-50 parts of modified red mud;
the modified red mud is obtained by carrying out organic modification on dealkalized red mud.
Preferably, the rubber comprises one or more of eucommia rubber, natural rubber and nitrile rubber.
Preferably, the polylactic acid includes one or more of poly-L-lactic acid, poly-D-lactic acid and racemic polylactic acid.
Preferably, the antioxidant comprises one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626 and antioxidant DLTDP.
Preferably, the cross-linking agent comprises one or more of isophenylene peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, and 2, 4-dichloroperoxybenzoyl.
Preferably, the modified red mud comprises metal oxide and/or non-metal oxide; the particle size distribution of the metal oxide and the nonmetal oxide is independently 20 nm-10 μm.
Preferably, the organic matter adopted for the organic modification of the dealkalized red mud comprises isopropoxy distearoyl acyloxy aluminate and isopropoxy tri (ethylenediamine N-ethoxy) titanate.
The invention also provides a preparation method of the scratch-resistant polylactic acid material with balanced rigidity and toughness, which comprises the following steps:
mixing the modified red mud and rubber to obtain master batch;
plasticizing and mixing the master batch, polylactic acid and an antioxidant to obtain a plasticized mixture;
and mixing the plasticized mixture and a crosslinking agent for dynamic crosslinking to obtain the scratch-resistant polylactic acid material with balanced rigidity and toughness.
Preferably, the mixing temperature is 30-90 ℃, and the mixing time is 10-20 min; the temperature of the plasticizing mixing is 130-160 ℃, and the rotating speed is 50-90 r/min.
Preferably, the dynamic crosslinking time is 5-10 min, the temperature is 130-160 ℃, and the rotating speed is 50-90 r/min.
The invention provides a scratch-resistant polylactic acid material with balanced rigidity and toughness, which comprises the following preparation raw materials in parts by weight: 10-40 parts of rubber, 60-90 parts of polylactic acid, 0.2-1 part of antioxidant, 0.5-2 parts of cross-linking agent and 10-50 parts of modified red mud; the modified red mud is obtained by organically modifying dealkalized red mud. The polylactic acid material provided by the invention has a bicontinuous phase structure of polylactic acid phase and rubber phase, the unique phase structure increases the contact area of the two phases, is beneficial to interface compatibilization, and can more effectively realize energy transfer and dissipation when being impacted by the outside, thereby obtaining higher toughness; the modified red mud is added into the polylactic acid material, and the modified red mud mainly comprises multi-component and multi-scale micro-nano metal oxide or nonmetal oxide, has a reinforcing effect on the polylactic acid material, and particularly enhances the interaction with a polylactic acid matrix after organic modification, so that the rigidity of the polylactic acid material is improved.
According to the invention, the polylactic acid material is toughened by using rubber with a continuous phase structure, and the modified red mud is introduced to be used as a functional reinforcing filler, so that the polylactic acid material is effectively reinforced, and the rigidity and toughness of the polylactic acid material are balanced, thereby the polylactic acid material has excellent scratch resistance.
In addition, the red mud is strong alkaline solid waste residue generated in the alumina industry, and the main component of the red mud is Al 2 O 3 、Fe 2 O 3 、TiO 2 、SiO 2 The stacking of the red mud not only occupies land but also pollutes the environment, the existing recycling ways of the red mud mainly comprise the recovery of heavy metals, the application of the red mud in building materials, the application of the red mud as environment-friendly adsorption materials, the application of the red mud in the flame retardant field and the like, but most of the red mud are remained in the fields of heavy metal recovery, environmental protection and the likeIn the laboratory stage, the industrial application value is low, and the red mud is modified and used in the polylactic acid material, so that a new digestion way can be provided for the red mud while the performance of the polylactic acid material is improved, the comprehensive utilization of the red mud is realized, and the industrial application value of the red mud is improved.
The invention also provides a preparation method of the scratch-resistant polylactic acid material with balanced rigidity and toughness. The preparation method provided by the invention has simple steps and easy operation, and can be used for forming products with any shapes according to the use working conditions.
Detailed Description
The invention provides a scratch-resistant polylactic acid material with balanced rigidity and toughness, which comprises the following preparation raw materials in parts by weight: 10-40 parts of rubber, 60-90 parts of polylactic acid, 0.2-1 part of antioxidant, 0.5-2 parts of cross-linking agent and 10-50 parts of modified red mud;
the modified red mud is obtained by carrying out organic modification on dealkalized red mud.
The scratch-resistant polylactic acid material with balanced rigidity and toughness comprises, by mass, 10-40 parts of rubber, and preferably 15-30 parts of raw materials. In the present invention, the rubber preferably includes one or more of eucommia ulmoides rubber (EUG), Natural Rubber (NR), and nitrile rubber (NBR). In a specific embodiment of the present invention, the weight average molecular weight of the eucommia ulmoides rubber is preferably 300000, and the dispersibility index (PDI) is preferably 3.4; the natural rubber is preferably domestic standard rubber No. 2; the nitrile rubber is preferably a type 1043N nitrile rubber manufactured by Taiwan south emperor chemical industries, Inc.
The scratch-resistant polylactic acid material with balanced rigidity and toughness comprises, by mass, 60-90 parts of polylactic acid (PLA), and preferably 65-85 parts of PLA. In the present invention, the polylactic acid preferably includes one or more of poly-L-lactic acid, poly-D-lactic acid and racemic polylactic acid. In a specific embodiment of the present invention, the polylactic acid used is PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA.
The preparation raw material of the scratch-resistant polylactic acid material with balanced rigidity and toughness comprises 0.2-1 part of antioxidant, preferably 0.3-0.8 part by weight of rubber. In the present invention, the antioxidant preferably includes one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626 and antioxidant DLTDP.
The preparation raw material of the scratch-resistant polylactic acid material with balanced rigidity and toughness comprises 0.5-2 parts by mass of a cross-linking agent, preferably 0.5-1 part by mass of rubber. In the present invention, the crosslinking agent preferably includes one or more of isopropyl peroxybenzene (DCP), 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane (bis-25), and 2, 4-dichloroperoxybenzoyl (bis-24).
The preparation raw material of the scratch-resistant polylactic acid material with balanced rigidity and toughness comprises, by mass, 10-50 parts of modified red mud, and preferably 20-40 parts of modified red mud. In the invention, the modified red mud is obtained by organically modifying dealkalized red mud, and the organic matters adopted for the organic modification preferably comprise isopropoxy distearoyl acyloxy aluminate (ACA-K30) and isopropoxy tri (ethylenediamine N-ethoxy) titanate (ACA-K44); the modified red mud preferably comprises metal oxide and/or nonmetal oxide, and in the specific embodiment of the invention, the modified red mud comprises Fe 2 O 3 、Al 2 O 3 、SiO 2 、TiO 2 、Na 2 O and CaO 2 In which Fe 2 O 3 Is preferably 48.78%, Al 2 O 3 Is preferably 20 to 25%, more preferably 21.63%, SiO 2 The mass fraction of (b) is preferably 10 to 15%, more preferably 11.30%, TiO 2 The mass fraction (b) of (c) is preferably 5 to 6%, more preferably 5.69%, and Na 2 The mass fraction of O is preferably 8 to 10%, more preferably 8.74%, CaO 2 The mass fraction of (b) is preferably 2 to 3%, more preferably 2.32%; the particle size distribution of the metal oxide and the non-metal oxide is independently preferably 20nm to 10 μm, more preferably 50nm to 8 μm. The modified red mud used in the invention contains multi-component and multi-scale micro-nano metal oxide and non-metal oxide, has an enhanced effect on polylactic acid materials, and particularly has an interaction with a polylactic acid matrix after organic modificationThe rigidity of the polylactic acid material is enhanced and improved.
In the present invention, the preparation method of the modified red mud preferably comprises the following steps:
mixing the dealkalized red mud, isopropoxy distearoyl acyloxy aluminate and isopropoxy tri (ethylenediamine N-ethoxy) titanate for grafting reaction to obtain the modified red mud.
In the invention, the preparation method of the dealkalized red mud preferably comprises the following steps: mixing red mud, water and acid for neutralization reaction, carrying out first standing on the obtained reaction liquid, then sequentially stirring and carrying out second standing, taking supernate, and filtering the supernate to obtain dealkalized red mud. The invention has no special requirements on the source of the red mud, and the red mud which is familiar to the technical personnel in the field can be adopted; the red mud is preferably subjected to superfine grinding and drying before use; the acid preferably comprises one or more of oxalic acid, citric acid, acetic acid, sulfuric acid, nitric acid and hydrochloric acid, and more preferably oxalic acid; the water is preferably deionized water; the preferable dosage ratio of the red mud, water and acid is 80-200 g: 300-800 mL: 25-50 g, more preferably 100-180 g: 400-600 mL: 30-45 g; the temperature of the neutralization reaction is preferably 60-100 ℃, more preferably 70-90 ℃, and the time of the neutralization reaction is preferably 0.5-3 h, more preferably 1-2.5 h; the neutralization reaction is preferably carried out in a water bath and under stirring conditions; the invention neutralizes the strong alkaline component in the red mud by acid through neutralization reaction; the first standing time is not specially required, and the method is carried out after the reaction liquid is cooled to the room temperature; after the first standing, stirring until solid products in the reaction liquid are uniformly dispersed, and then carrying out second standing; the second standing time is preferably 1-10 min, and more preferably 3-5 min; after the second standing, the obtained supernatant is specifically a suspension, the hydroxyl content of the surface of the red mud is increased after dealkalization, the hydrophilicity is improved, the part with small particle size is dispersed in water to form the suspension (namely the supernatant), the lower layer mainly comprises red mud particles with extremely large size mainly comprising ferric sulfide, the hardness is extremely high, and the red mud particles cannot be pretreated by superfine grinding; in the embodiment of the invention, the lower layer precipitate is preferably repeatedly settled until the upper layer does not form suspension any more, so as to improve the yield of the dealkalized red mud. The red mud has high content of sodium oxide and strong alkalinity, and if the red mud is not subjected to dealkalization treatment, the red mud can be used as a filler, so that the material is easy to absorb water, and the service performance of the material is reduced.
After the dealkalized red mud is obtained, the dealkalized red mud, the isopropoxy distearoyl acyloxy aluminate and the isopropoxy tri (ethylenediamine N-ethoxy) titanate are mixed for grafting reaction to obtain the modified red mud. In the invention, the mass ratio of the dealkalized red mud, the isopropoxy distearoyl acyloxy aluminate ester and the isopropoxy tri (ethylenediamine N-ethoxy) titanate is preferably 50-200: 1-4: 0.1-1, and more preferably 100-150: 2-3: 0.3-0.8; the isopropoxy distearoyl acyloxy aluminate is preferably used in the form of isopropoxy distearoyl acyloxy aluminate solution, the solvent of the isopropoxy distearoyl acyloxy aluminate solution is preferably isopropanol, and the mass ratio of the isopropoxy distearoyl acyloxy aluminate to the isopropanol in the isopropoxy distearoyl acyloxy aluminate solution is preferably 1: 1-6, and more preferably 1: 2-5; the isopropoxytris (ethylenediamine-N-ethoxy) titanate is preferably used in the form of a solution of isopropoxytris (ethylenediamine-N-ethoxy) titanate; the solvent of the isopropoxy tri (ethylenediamine N-ethoxy) titanate solution is preferably isopropanol, and the mass ratio of the isopropoxy tri (ethylenediamine N-ethoxy) titanate to the isopropanol in the isopropoxy tri (ethylenediamine N-ethoxy) titanate solution is preferably 1: 1-6, and more preferably 1: 2-5.
In the invention, the temperature of the grafting reaction is preferably 100-150 ℃, more preferably 120-130 ℃, and the time of the grafting reaction is preferably 1-3 h, more preferably 1.5-2.5 h. In the grafting reaction process, the isopropoxy tri (ethylenediamine N-ethoxy) titanate in the isopropoxy tri (ethylenediamine N-ethoxy) titanate solution is coupled with the red mud and grafted on the surface of the red mud.
In the specific embodiment of the invention, preferably, dealkalized red mud is subjected to nano-crushing and then added into a superfine crusher, then an isopropoxy distearoyl acyloxy aluminate solution and an isopropoxy tri (ethylenediamine N-ethoxy) titanate solution are added into the superfine crusher, stirred and mixed for 3-15 min, and then the mixture is placed into an oven to react at the temperature of a grafting reaction; in the present invention, the rotation speed of the stirring and mixing is preferably 25000 rpm.
After grafting modification, an amino active group and an aliphatic long chain are grafted on the surface of the red mud, the amino active group can react with carboxyl of a polylactic acid matrix and an epoxy group in a rubber component, so that the interface effect of the polylactic acid matrix and the matrix is greatly improved, and the aliphatic long chain not only can improve the compatibility of the red mud and the matrix, but also can participate in dynamic crosslinking of the rubber component to form a covalent bond effect.
The invention also provides a preparation method of the scratch-resistant polylactic acid material with balanced rigidity and toughness, which comprises the following steps:
mixing the modified red mud and rubber to obtain master batch;
plasticizing and mixing the master batch, polylactic acid and an antioxidant to obtain a plasticized mixture;
and mixing the plasticized mixture and a crosslinking agent for dynamic crosslinking to obtain the scratch-resistant polylactic acid material with balanced rigidity and toughness.
The invention mixes the modified red mud and rubber to obtain the master batch. In the present invention, the mixing is preferably carried out in an open mill; the mixing temperature is preferably 30-90 ℃, more preferably 40-80 ℃, and the mixing time is preferably 10-20 min, more preferably 13-15 min.
The masterbatch, the polylactic acid and the antioxidant are plasticized and mixed to obtain a plasticized mixture. According to the invention, preferably, the polylactic acid is dried, and then plasticized and mixed, wherein the drying temperature is preferably 70 ℃, and the drying time is preferably 24 h; the plasticizing mixing is preferably carried out in an internal mixer, the temperature of the plasticizing mixing is preferably 130-160 ℃, more preferably 140-150 ℃, and the rotating speed of the plasticizing mixing is preferably 50-90 r/min, more preferably 60-80 r/min. In the specific embodiment of the invention, the polylactic acid and the antioxidant are preferably plasticized and mixed in an internal mixer for 5-10 min, and then the masterbatch is added for plasticizing and mixing for 5-10 min.
After the plasticized mixture is obtained, the plasticized mixture and the cross-linking agent are preferably mixed for dynamic cross-linking, so that the scratch-resistant polylactic acid material with balanced rigidity and toughness is obtained. In the invention, the time of dynamic crosslinking is preferably 5-10 min, the temperature is preferably 130-160 ℃, the more preferably 140-150 ℃, and the rotating speed is preferably 50-90 r/min, the more preferably 60-80 r/min; the dynamic crosslinking is preferably carried out in an internal mixer; in the embodiment of the invention, the cross-linking agent is preferably added directly to the internal mixer for dynamic cross-linking without taking out the plasticized mixture after the plasticized mixture is obtained.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Preparing modified red mud:
weighing 150g of superfine crushed and dried red mud, adding the red mud into a single-neck flask containing 600ml of deionized water and 30g of oxalic acid, heating the mixture in a water bath at the temperature of 80 ℃, reacting the mixture for 2 hours under the condition of continuous stirring, and fully neutralizing strong alkaline components in the red mud; and then standing the reaction solution, cooling to room temperature, stirring again, standing for 3min again after the red mud is uniformly dispersed, and taking supernatant and carrying out suction filtration to obtain the dealkalized red mud.
Taking 100g dealkalized red mud, carrying out nano-crushing, adding the dealkalized red mud into a superfine crusher, then adding 0.75g isopropoxy distearoyl acyloxy aluminate solution (ACA-K30: isopropanol is 1:5) and 0.35g isopropoxy tri (ethylenediamine N-ethoxy) titanate solution (ACA-K44: isopropanol is 1:5), mixing for 15min under the stirring action of the superfine crusher at high speed (25000rpm), placing the uniformly mixed product in an oven at 120 ℃ for reacting for 2h, and completing the surface grafting reaction of the red mud to obtain the modified red mud.
Through detection, the modified red mud contains Fe 2 O 3 48.78％，Al 2 O 3 21.63％，SiO 2 11.30％，TiO 2 5.69％，Na 2 O 8.74％，CaO 2 2.32 percent; the particle size distribution of each oxide is 20nm to 10 μm.
The modified red mud is applied to the preparation of the polylactic acid materials in the subsequent examples and comparative examples.
Example 1
In this example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA; the adopted Natural Rubber (NR) is a domestic 2# standard rubber.
The polylactic acid material comprises the following raw materials in parts by weight: 90 parts of PLA, 10 parts of NR, 10100.5 parts of antioxidant, 250.3 parts of bis-modified red mud and 15 parts of modified red mud.
The preparation steps are as follows: mixing Natural Rubber (NR) and modified red mud for 10min at 40 ℃ to obtain master batch; drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; an internal mixer is adopted, the rotating speed is set to be 80r/min, the dried polylactic acid, the masterbatch and the antioxidant 1010 are added into the internal mixer, and the mixture is uniformly plasticized at the temperature of 150 ℃ to obtain a mixture; and adding the bis-25 into the mixture, setting the rotating speed of an internal mixer to be 80r/min, and carrying out dynamic crosslinking for 10min to obtain the scratch-resistant polylactic acid material with balanced rigidity and toughness.
Example 2
In this example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA; the adopted Natural Rubber (NR) is a domestic 2# standard rubber.
The polylactic acid material comprises the following raw materials in parts by weight: 60 parts of PLA, 40 parts of NR, 10100.8 parts of antioxidant, 0.8 part of DCP and 45 parts of modified red mud.
The preparation steps are as follows: mixing Natural Rubber (NR) and modified red mud for 10min at 40 ℃ to obtain master batch; drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; an internal mixer is adopted, the rotating speed is set to be 80r/min, the dried polylactic acid, the master batch and the antioxidant 1010 are added into the internal mixer, and the mixture is uniformly plasticized at the temperature of 150 ℃ to obtain a mixture; adding the DCP into the mixture, setting the rotating speed of an internal mixer to be 80r/min, and carrying out dynamic crosslinking for 10min to obtain the scratch-resistant polylactic acid material with balanced rigidity and toughness.
Example 3
In this example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA; the average molecular weight of the eucommia ulmoides rubber (EUG) used was 300000, and the PDI was 3.4.
The polylactic acid material comprises the following raw materials in parts by weight: 80 parts of PLA, 20 parts of EUG, 1681.0 parts of antioxidant, 240.5 parts of bis-modified red mud and 30 parts of modified red mud.
The preparation steps are as follows: mixing EUG and modified red mud at 80 ℃ for 15min to obtain master batch; drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; an internal mixer is adopted, the rotating speed is set to be 70r/min, the dried polylactic acid, the masterbatch and the antioxidant 168 are added into the internal mixer, and the mixture is uniformly plasticized at the temperature of 160 ℃ to obtain a mixture; and adding the bis-24 into the mixture, setting the rotating speed of an internal mixer to be 70r/min, and carrying out dynamic crosslinking for 8min to obtain the scratch-resistant polylactic acid material with balanced rigidity and toughness.
Example 4
In this example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA; the average molecular weight of the eucommia ulmoides rubber adopted is 300000, and the PDI is 3.4.
The polylactic acid material comprises the following raw materials in parts by weight: 70 parts of PLA, 30 parts of EUG, 17060.8 parts of antioxidant, 0.5 part of DCP and 25 parts of modified red mud.
The preparation steps are as follows: mixing EUG and modified red mud at 80 ℃ for 15min to obtain master batch; drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; an internal mixer is adopted, the rotating speed is set to be 70r/min, the dried polylactic acid, the masterbatch and the antioxidant 1076 are added into the internal mixer, and the mixture is uniformly plasticized at the temperature of 160 ℃ to obtain a mixture; adding the DCP into the mixture, setting the rotating speed of an internal mixer to be 70r/min, and carrying out dynamic crosslinking for 8min to obtain the scratch-resistant polylactic acid material with balanced rigidity and toughness.
Example 5
In this example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA; the nitrile rubber (NBR) is 1043N type NBR produced by Taiwan south emperor chemical industry Co.
The polylactic acid material comprises the following raw materials in parts by weight: 80 parts of PLA, 20 parts of NBR, 1681.0 parts of antioxidant, 240.4 parts of bis-modified red mud and 20 parts of modified red mud.
The preparation steps are as follows: mixing NBR and modified red mud at 60 ℃ for 10min to obtain master batch; drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; an internal mixer is adopted, the rotating speed is set to be 70r/min, the dried polylactic acid, the masterbatch and the antioxidant 168 are added into the internal mixer, and the mixture is uniformly plasticized at the temperature of 170 ℃ to obtain a mixture; and adding the bis-24 into the mixture, setting the rotating speed of an internal mixer to be 60r/min, and carrying out dynamic crosslinking for 15min to obtain the scratch-resistant polylactic acid material with balanced rigidity and toughness.
Example 6
In this example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA; the nitrile rubber (NBR) used was 1043N type NBR manufactured by Taiwan south emperor chemical industry Co.
The polylactic acid material comprises the following raw materials in parts by weight: 70 parts of PLA, 30 parts of NBR, 0.8 part of antioxidant DLTDP, 50 parts of double-250.8 parts of modified red mud.
The preparation steps are as follows: mixing NBR and modified red mud for 10min at 60 ℃ to obtain master batch; drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; an internal mixer is adopted, the rotating speed is set to be 70r/min, the dried polylactic acid, the masterbatch and the antioxidant DLTDP are added into the internal mixer, and the mixture is uniformly plasticized at the temperature of 170 ℃ to obtain a mixture; and adding the bis-24 into the mixture, setting the rotating speed of an internal mixer to be 60r/min, and carrying out dynamic crosslinking for 15min to obtain the scratch-resistant polylactic acid material with balanced rigidity and toughness.
Comparative example 1
The polylactic acid used in this comparative example was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA; the adopted polypropylene is T30S type homopolymerized PP produced by Chinese petrochemical company;
the dosage of each raw material is as follows according to the mass portion: 70 parts of PLA, 20 parts of PP, 15 parts of scratch-resistant modifier (PVA-g-PLLA, 12 ten thousand of number average molecular weight and 10 percent of grafting ratio), 10100.4 parts of antioxidant, 3 parts of scratch-resistant agent (AST-50 silicone master batch) and 1.5 parts of zinc stearate.
The preparation steps are as follows: and (2) adopting an internal mixer, setting the rotating speed to be 80r/min, adding the dried polylactic acid, polypropylene and antioxidant 1010 into the internal mixer, plasticizing uniformly at 170 ℃, adding a scratch-resistant modifier (PVA-g-PLLA), a scratch-resistant agent (AST-50 silicone master batch) and zinc stearate, and continuously mixing uniformly.
Comparative example 2
In this comparative example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA;
the polylactic acid material comprises the following raw materials in parts by weight: 100 parts of PLA and 10100.5 parts of antioxidant.
The preparation steps are as follows: drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; and (2) adopting an internal mixer, setting the rotating speed to be 80r/min, adding the dried polylactic acid and the antioxidant 1010 into the internal mixer, and plasticizing uniformly at 150 ℃ to obtain the polylactic acid material.
Comparative example 3
In this comparative example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA;
the polylactic acid material comprises the following raw materials in parts by weight: 100 parts of PLA, 10100.5 parts of antioxidant and 30 parts of modified red mud.
The preparation steps are as follows: drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; and (2) adopting an internal mixer, setting the rotating speed to be 80r/min, adding the dried polylactic acid and the antioxidant 1010 into the internal mixer, plasticizing uniformly at 150 ℃, then adding the red mud, and mixing uniformly to obtain the polylactic acid material.
Comparative example 4
In this comparative example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA; the adopted natural rubber is domestic 2# standard rubber;
the polylactic acid material comprises the following raw materials in parts by weight: 90 parts of PLA, 10 parts of NR, 10100.5 parts of antioxidant and 250.3 parts of bis-antioxidant.
The preparation steps are as follows: drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; adopting an internal mixer, setting the rotating speed to be 80r/min, adding the dried polylactic acid, the dried natural rubber and the antioxidant 1010 into the internal mixer, and plasticizing uniformly at 150 ℃ to obtain a mixture; and adding the bis-25 into the mixture, setting the rotating speed of an internal mixer to be 80r/min, and carrying out dynamic crosslinking for 10min to obtain the polylactic acid material.
Comparative example 5
In this comparative example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA; the average molecular weight of the adopted eucommia ulmoides rubber is 300000, and the PDI is 3.4;
the polylactic acid material comprises the following raw materials in parts by weight: 80 parts of PLA, 20 parts of EUG, 1681.0 parts of antioxidant and 240.5 parts of bis-methyl methacrylate.
The preparation steps are as follows: drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; adopting an internal mixer, setting the rotating speed at 70r/min, adding the dried polylactic acid, the dried natural rubber and the antioxidant 168 into the internal mixer, and plasticizing uniformly at 160 ℃ to obtain a mixture; and adding the bis-24 into the mixture, setting the rotating speed of an internal mixer to be 70r/min, and carrying out dynamic crosslinking for 8min to obtain the polylactic acid material.
Comparative example 6
In this comparative example, the polylactic acid used was PLA (poly-L-lactic acid) type 2003D produced by Nature Works, USA; the nitrile-butadiene rubber (NBR) is 1043N type NBR produced by Taiwan south emperor chemical industry Co., Ltd;
the polylactic acid material comprises the following raw materials in parts by mass: 70 parts of PLA, 30 parts of NBR, 0.8 part of antioxidant DLTDP and 250.8 parts of bis-O-methyl methacrylate.
The preparation steps are as follows: drying the polylactic acid for 24 hours at the temperature of 70 ℃ to obtain dried polylactic acid; adopting an internal mixer, setting the rotating speed at 70r/min, adding the dried polylactic acid, the dried natural rubber and the antioxidant DLTDP into the internal mixer, and plasticizing uniformly at 170 ℃ to obtain a mixture; and adding the bis-25 into the mixture, setting the rotating speed of an internal mixer to be 60r/min, and carrying out dynamic crosslinking for 15min to obtain the polylactic acid material.
Performance test
Carrying out hot press molding on the polylactic acid materials prepared in the examples 1-6 and the comparative examples 1-6 for 3min by using a flat vulcanizing machine (the hot press temperature of the examples 1-2, 5-6 and the comparative examples 1-4 and 6 is 170 ℃, the hot press temperature of the examples 3-4 and the comparative example 5 is 180 ℃), and then carrying out cold press for 15min to prepare test pieces with the thicknesses of 2mm and 4mm, wherein the test piece with the thickness of 4mm is used for testing the impact performance, and the test piece with the thickness of 2mm is used for testing the tensile performance and the scratch resistance; the pressure in the hot-press forming and cold-pressing processes is 15 MPa; the performance test is carried out according to a type 2 tensile test sample specified in GB/T528-92, an A-type notch impact test sample specified in GB/T1843-2008 and a popular-3952 scratch resistance test standard, and the results are shown in Table 1.
TABLE 1 comprehensive Property test results of polylactic acid materials obtained in examples 1 to 6 and comparative examples 1 to 6
According to the data in the table 1, the polylactic acid material provided by the invention has excellent comprehensive performance, higher tensile strength, elongation at break and impact strength, balanced rigidity and toughness and good scratch resistance. In the comparative example 1, the scratch-resistant modifier and the scratch-resistant agent are adopted, and although the obtained polylactic acid material has higher tensile strength, the elongation at break and impact strength are very low, and the toughness is poorer; in the comparison documents 2-3, rubber is not used, and the toughness and the scratch resistance of the obtained polylactic acid material are poor; in comparative examples 4 to 6, the modified red mud is not used, although the elongation at break and the impact strength are higher, the tensile strength is lower, which shows that the rigidity is poorer, and the effect of rigidity and toughness balance cannot be realized, and in examples 1, 3 and 6, compared with comparative examples 4 to 6, the modified red mud is added, the tensile strength, the elongation at break and the impact strength are higher, which accords with the characteristics of hard and tough materials, and shows that the material of the invention has rigidity and toughness balance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The scratch-resistant polylactic acid material with balanced rigidity and toughness is characterized by comprising the following preparation raw materials in parts by mass: 10-40 parts of rubber, 60-90 parts of polylactic acid, 0.2-1 part of antioxidant, 0.5-2 parts of cross-linking agent and 10-50 parts of modified red mud;
the modified red mud is obtained by organically modifying dealkalized red mud.
2. The stiffness-toughness balanced scratch-resistant polylactic acid material according to claim 1, wherein the rubber comprises one or more of eucommia ulmoides rubber, natural rubber and nitrile rubber.
3. The scratch resistant polylactic acid material with balanced rigidity and toughness as claimed in claim 1, wherein the polylactic acid comprises one or more of poly-L-lactic acid, poly-D-lactic acid and racemic polylactic acid.
4. The stiffness-toughness balanced scratch-resistant polylactic acid material according to claim 1, wherein the antioxidant comprises one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626 and antioxidant DLTDP.
5. The stiffness-toughness balanced scratch-resistant polylactic acid material according to claim 1, wherein the crosslinking agent comprises one or more of isophenylene peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, and 2, 4-dichloroperoxybenzoyl.
6. The rigidity-toughness balanced scratch-resistant polylactic acid material according to claim 1, wherein components of the modified red mud comprise metal oxides and/or non-metal oxides; the particle size distribution of the metal oxide and the nonmetal oxide is independently 20 nm-10 μm.
7. The scratch-resistant polylactic acid material with balanced rigidity and toughness as claimed in claim 1, wherein the organic substances adopted for the organic modification of the dealkalized red mud comprise isopropoxy distearoyl acyloxy aluminate and isopropoxy tri (ethylenediamine N-ethoxy) titanate.
8. The preparation method of the scratch-resistant polylactic acid material with balanced rigidity and toughness as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
mixing the modified red mud and rubber to obtain master batch;
plasticizing and mixing the master batch, polylactic acid and an antioxidant to obtain a plasticized mixture;
and mixing the plasticized mixture and a crosslinking agent for dynamic crosslinking to obtain the scratch-resistant polylactic acid material with balanced rigidity and toughness.
9. The method according to claim 8, wherein the mixing temperature is 30 to 90 ℃ and the mixing time is 10 to 20 min; the temperature of the plasticizing mixing is 130-160 ℃, and the rotating speed is 50-90 r/min.
10. The preparation method according to claim 8 or 9, wherein the dynamic crosslinking time is 5-10 min, the temperature is 130-160 ℃, and the rotation speed is 50-90 r/min.
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Application publication date: 20220816 |