CN114456119A - Hydrogenated cardanol-heterocyclic Schiff base compound, preparation method and application thereof, polylactic acid composite material and preparation method thereof - Google Patents
Hydrogenated cardanol-heterocyclic Schiff base compound, preparation method and application thereof, polylactic acid composite material and preparation method thereof Download PDFInfo
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- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
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- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
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- C07D277/62—Benzothiazoles
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Abstract
The invention provides a hydrogenated cardanol-heterocyclic Schiff base compound, a preparation method and application thereof, a polylactic acid composite material and a preparation method thereof, and relates to the technical field of antioxidants. According to the invention, cardanol with oxidation resistance is used as a mother ring, a heterocyclic ring with photostability and metal ion passivation performance is used as another structural unit, and a Schiff base functional group with metal ion complexing characteristic is used as a bridging structure of the mother ring and the heterocyclic ring, so that the hydrogenated cardanol-heterocyclic Schiff base compound provided by the invention has excellent oxidation resistance, photostability and metal ion passivation performance. In addition, the hydrogenated cardanol-heterocyclic schiff base compound provided by the invention has the advantages that two structures of phenol and a heterocycle are connected into a macromolecule through a chemical bond, the molecular weight is obviously increased compared with cardanol, and meanwhile, the volatility of the whole molecule of the hydrogenated cardanol-heterocyclic schiff base compound is reduced, so that the hydrogenated cardanol-heterocyclic schiff base compound is endowed with excellent thermal stability.
Description
Technical Field
The invention relates to the technical field of antioxidants, and particularly relates to a hydrogenated cardanol-heterocyclic Schiff base compound, a preparation method and application thereof, a polylactic acid composite material and a preparation method thereof.
Background
Cardanol is a main component extracted from agricultural waste cashew shells, has wide sources and natural antioxidant characteristics, meets the definition of green chemistry and the requirement of national sustainable development strategy, and is widely applied to the industries of high polymer materials, foods, lubricants, fibers and rubbers as a substitute of alkylphenol of petrochemical sources. Because cardanol is in a meta-alkylphenol structure, the antioxidant activity of cardanol is much lower than that of 2, 6-di-tert-butyl-p-cresol (BHT) which is used in the largest commercial amount, and the antioxidant activity of cardanol as an antioxidant in the aspect of materials needs to be improved.
The antioxidant activity of the cardanol can be improved by introducing other structures into the cardanol structure. For example, chinese patent CN201811433025 discloses cardanol-arylamine schiff base derivatives having a structure shown in formula (I), wherein R is selected from one of structures shown in formulae (II) to (V), and R is selected from1Selected from H or a structure of formula (VI):
however, the oxidation induction period of the cardanol-arylamine schiff base derivative is maximum 44.6min, and the oxidation resistance is poor.
Disclosure of Invention
In view of the above, the invention aims to provide a hydrogenated cardanol-heterocyclic schiff base compound, a preparation method and an application thereof, a polylactic acid composite material and a preparation method thereof. The hydrogenated cardanol-heterocyclic Schiff base compound provided by the invention has excellent oxidation resistance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a hydrogenated cardanol-heterocyclic schiff base compound, which has a structure shown in a formula I:
in the formula I, R has a heterocyclic structure and comprises any one of the following structures:
in the R, R1、R2And R3Independently comprise H, C1～C12Alkyl or halo.
The invention provides a preparation method of the hydrogenated cardanol-heterocyclic Schiff base compound in the technical scheme, which comprises the following steps:
mixing cardanol, aldehyde, metal halide salt, an addition reaction catalyst and a solvent, and carrying out an addition reaction to obtain cardanol formaldehyde;
mixing the cardanol formaldehyde and R-NH2Mixing with a solvent, and carrying out Schiff base reaction to obtain the hydrogenated cardanol-heterocyclic Schiff base compound;
R-NH2r in (a) is the same as R in the formula I.
Preferably, the aldehyde comprises one or more of aliphatic aldehyde, alicyclic aldehyde, aromatic aldehyde and terpene aldehyde;
the mol ratio of cardanol to aldehyde is 1: 1-10; the aldehyde is calculated by the amount of formaldehyde;
the metal halide salt comprises magnesium chloride and/or aluminum chloride;
the addition reaction catalyst comprises one or more of organic amine, hydroxide, boric acid compounds, benzenesulfonic acid compounds and palladium carbon;
the mol ratio of the cardanol to the metal halide salt to the addition reaction catalyst is 1: 1-15: 1 to 15.
Preferably, the cardanol formaldehyde and R-NH are2In a molar ratio of 1: 0.3 to 3.
Preferably, the temperature of the addition reaction and the Schiff base reaction is independently 20-120 ℃, and the time is independently 0.5-48 h.
The invention provides application of the hydrogenated cardanol-heterocyclic Schiff base compound in the technical scheme as an antioxidant.
The invention also provides an antioxidant polymer composite material, which comprises a high molecular polymer and the antioxidant of claim 1; the high molecular polymer comprises one or more of general high molecular resin, engineering plastics and special plastics.
Preferably, the general polymer resin comprises one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate and polyethylene-vinyl acetate;
the engineering plastic comprises one or more of poly (acrylonitrile-butadiene-styrene), polycarbonate, polyformaldehyde, polyamide, polyethylene terephthalate, polybutylene terephthalate and polyphenyl ether;
the special plastic comprises one or more of polyarylate, polyphenyl ester, polysulfone, polyarylsulfone, polyethersulfone, polyimide, polyetherimide, polyamideimide, polyphenylene sulfide, polyether ether ketone, polyether ketone, liquid crystal polymer, thermoplastic fluoroplastic, reinforced plastic and foamed plastic;
preferably, the mass fraction of the hydrogenated cardanol-heterocyclic schiff base compound in the antioxidant polymer composite material is 0.05-5%.
Preferably, the composite material further comprises an auxiliary agent, wherein the auxiliary agent comprises one or more of an inorganic filler, a processing modifier, a compatilizer, a light stabilizer, a dispersing agent, a dye, a plasticizer and a toughening agent.
The invention provides a hydrogenated cardanol-heterocyclic Schiff base compound which has a structure shown in a formula I, wherein R has a heterocyclic structure. According to the invention, cardanol is used as a mother ring, a phenolic hydroxyl structure on the cardanol has natural oxidation resistance, a heterocyclic ring (benzoxazole, benzothiazole, benzimidazole and benzimidazolone) with light stability and metal ion passivation performance is used as another structural unit, and a Schiff base functional group with a certain metal ion complexing characteristic is used as a bridging structure of the mother ring and the heterocyclic ring, so that the hydrogenated cardanol-heterocyclic Schiff base compound provided by the invention has excellent oxidation resistance, light stability and metal ion passivation performance. In addition, the hydrogenated cardanol-heterocyclic schiff base compound provided by the invention has the advantages that two structures of phenol and a heterocycle are connected into a macromolecule through a chemical bond, the molecular weight is obviously increased compared with cardanol, and meanwhile, the volatility of the whole molecule of the hydrogenated cardanol-heterocyclic schiff base compound is reduced, so that the hydrogenated cardanol-heterocyclic schiff base compound is endowed with excellent thermal stability. The hydrogenated cardanol-heterocyclic Schiff base compound provided by the invention has a good application prospect in oxidation resistance of plastics, rubber, coatings and fibers.
The invention provides a preparation method of the hydrogenated cardanol-heterocyclic Schiff base compound in the technical scheme. The preparation method provided by the invention takes cardanol derivative hydrogenated cardanol derived from natural biomass as one of raw materials, and the raw materials are low in price and wide in source, have the advantages of reproducibility and low toxicity, and are green and environment-friendly; short reaction route, simple process, high product yield and suitability for industrialized production.
The invention provides a polylactic acid composite material, which comprises polylactic acid and a hydrogenated cardanol-heterocyclic Schiff base compound. The invention takes the hydrogenated cardanol-heterocyclic Schiff base compound as an antioxidant, and obviously improves the oxidation resistance, light stability, metal ion passivation and heat stability of the polylactic acid.
The invention provides a preparation method of the polylactic acid composite material. The preparation method provided by the invention is simple to operate and is green and environment-friendly.
Drawings
Fig. 1 is a hydrogen spectrum of cardanol formaldehyde prepared in example 1;
fig. 2 is a hydrogen spectrum of the hydrogenated cardanol-heterocyclic schiff base compound prepared in example 1;
fig. 3 is a hydrogen spectrum of the hydrogenated cardanol-heterocyclic schiff base compound prepared in example 2;
fig. 4 is a hydrogen spectrum of the hydrogenated cardanol-heterocyclic schiff base compound prepared in example 3;
fig. 5 is an infrared spectrum of the hydrogenated cardanol-heterocyclic schiff base compound prepared in example 4;
FIG. 6 is a graph showing the results of thermal stability tests of the hydrogenated cardanol-heterocyclic Schiff base compounds, the commercial antioxidants BHT, the commercial antioxidants 4010NA and m-pentadecylphenol prepared in examples 1 to 4;
FIG. 7 is a graph showing the effect of xenon lamp aging on the tensile strength of the antioxidant polylactic acid composite materials prepared in examples 5 to 8 and comparative examples 2 to 3;
FIG. 8 shows the results of the thermo-oxidative aging performance test of the antioxidant polylactic acid composite materials prepared in examples 5 to 8 and comparative examples 2 to 3 and the pure polylactic acid prepared in comparative example 1;
FIG. 9 is a graph showing the tensile property test results of the antioxidant polylactic acid composite materials prepared in examples 5 to 8 and comparative examples 2 to 3 and the pure polylactic acid prepared in comparative example 1.
Detailed Description
The invention provides a hydrogenated cardanol-heterocyclic schiff base compound, which has a structure shown in a formula I:
in the formula I, R has a heterocyclic structure and comprises any one of the following structures:
in the R, R1、R2And R3Independently comprise H, C1～C10Alkyl or halo. In the present invention, said C1～C12Alkyl preferably includes independently hydrogen, C1-C12Alkyl, tertiary C4-C12Alkyl radical, C5-C8Cycloalkyl radical, C1-C12Alkyl or by S-C1-C12Alkyl, O-C1-C12Alkyl, CO-O-C1-C12Alkyl and/or O-CO-C12Alkyl substituted C1-C12An alkyl group; . In the present invention, the halo group preferably includes Cl or Br.
In the present invention, the R preferably has any one of the structures shown below:
the invention provides a preparation method of a hydrogenated cardanol-heterocyclic Schiff base compound, which comprises the following steps:
mixing cardanol, aldehyde, metal halide salt, an addition reaction catalyst and a solvent, and carrying out an addition reaction to obtain cardanol formaldehyde;
mixing the cardanol formaldehyde and R-NH2Mixing with a solvent, and carrying out Schiff base reaction to obtain the hydrogenated cardanol-heterocyclic Schiff base compound;
R-NH2r in (a) is the same as R in the formula I.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
Mixing cardanol, aldehyde, metal halide salt, an addition reaction catalyst and a solvent, and carrying out an addition reaction to obtain cardanol formaldehyde.
In the present invention, the aldehyde preferably includes one or more of aliphatic aldehyde, alicyclic aldehyde, aromatic aldehyde and terpene aldehyde; the aliphatic aldehyde preferably comprises one or more of formaldehyde, formaldehyde solution, trioxymethylene, acetaldehyde, octanal, nonanal, decanal, undecanal, lauraldehyde (dodecanal), tridecanal, myristylaldehyde (tetradecanal), methylhexylacetaldehyde, methyloctylacetaldehyde, methylnonylacetaldehyde, trimethylhexanal and tetramethylhexanal; the alicyclic aldehyde preferably comprises one or more of ligustral, elargualdehyde, isocyclocitral, citral, methyl citral, and lyral; the aromatic aldehyde preferably comprises one or more of benzaldehyde, phenylacetaldehyde, phenylpropyl aldehyde, cinnamic aldehyde, lilial, vanillin and ethyl vanillin; the terpene aldehyde preferably comprises one or more of trans-2-hexenal, 2-nonenal, trans-4-decenal, undecenal, nonadienal, citral, citronellal, hydroxycitronellal, perillaldehyde and trimethylheptenal. In the present invention, the molar ratio of cardanol to aldehyde is preferably 1: 1-10, more preferably 1: 2-8, and more preferably 1: 5-6; the aldehyde is calculated as formaldehyde.
In the present invention, the metal halide salt preferably includes magnesium chloride and/or aluminum chloride; the metal halide salt is preferably used in the form of an anhydrous metal halide salt.
In the invention, the addition reaction catalyst preferably comprises one or more of organic amine, hydroxide, boric acid compounds, benzenesulfonic acid compounds and palladium carbon; the organic amine preferably comprises triethylamine and/or tributylamine, the tributylamine preferably comprises tri-n-butylamine; the hydroxide preferably comprises sodium hydroxide and/or potassium hydroxide; the boric compounds preferably comprise fluoroboric acid and/or boric acid; the benzenesulfonic acid compound preferably comprises one or more of m-nitrobenzenesulfonic acid, p-hydroxybenzenesulfonic acid, m-hydroxybenzenesulfonic acid, p-nitrobenzenesulfonic acid and m-nitrobenzenesulfonic acid; the mass fraction of carbon in the palladium-carbon is preferably 0.5-10%, more preferably 2-8%, and further preferably 4-5%.
In the present invention, the molar ratio of the cardanol, the metal halide salt, and the addition reaction catalyst is preferably 1: 1-15: 1-15, more preferably 1: 3-12: 3 to 12, and more preferably 1: 5-10: 5 to 10.
In the invention, the solvent preferably comprises one or more of nitrile solvents, furan solvents, chlorohydrocarbon solvents, alcohol solvents and ketone solvents, and more preferably comprises one or more of acetonitrile, tetrahydrofuran, chloroform, ethanol, methanol and acetone; the solvent is preferably a dry solvent. In the present invention, the ratio of the mass of cardanol to the volume of the solvent is preferably 1 g: 4-100 mL, more preferably 1 g: 20-50 mL. The mixing method of the invention is not particularly limited, and the raw materials can be uniformly mixed.
In the invention, the temperature of the addition reaction is preferably 20-120 ℃, more preferably 30-100 ℃, and further preferably 50-80 ℃; the time of the addition reaction is preferably 0.5-48 h, more preferably 5-40 h, and further preferably 10-20 h; the addition reaction is preferably carried out under a protective atmosphere, which preferably comprises nitrogen, argon or helium. In the present invention, the reaction occurring during the addition reaction is represented by formula (1):
after the addition reaction, the present invention preferably further comprises a post-treatment, which preferably comprises: and (3) adding an organic solvent into the reaction liquid of the addition reaction after the first concentration for purification, adjusting the pH value to be neutral, and sequentially carrying out water washing, drying by a drying agent, second concentration and column chromatography purification on the obtained organic phase to obtain the cardanol formaldehyde. The present invention is not particularly limited to the first concentration and the second concentration, and a concentration method known to those skilled in the art may be adopted, specifically, reduced pressure distillation; in the examples of the present invention, it is preferable to concentrate to remove the solvent. In the present invention, the organic solvent for purification preferably includes one or more of a nitrile solvent, a furan solvent, a chlorinated hydrocarbon solvent, an alcohol solvent, and a ketone solvent, more preferably includes one or more of acetonitrile, tetrahydrofuran, chloroform, ethanol, methanol, and acetone, and the ratio of the mass of cardanol to the volume of the organic solvent for purification is preferably 1 g: 4-100 mL, more preferably 1 g: 20-50 mL. In the invention, the acid used for adjusting the pH value preferably comprises one or more of hydrochloric acid, acetic acid, sulfuric acid and nitric acid, the acid is preferably used in the form of an acid aqueous solution, and the concentration of the acid aqueous solution is preferably 0.1-37 wt%, more preferably 5-30 wt%, and further preferably 10-20 wt%. In the invention, the washing times are preferably 2-3 times; the ratio of the mass of cardanol to the volume of water for single water washing is preferably 1 g: 4-100 mL, more preferably 1 g: 15-50 mL. In the present invention, the desiccant for drying preferably includes anhydrous magnesium sulfate and/or anhydrous sodium sulfate. In the present invention, the eluent used for the column chromatography purification is preferably a mixed solvent of small polarity and large polarity; the small-polarity-large-polarity mixed solvent preferably contains hexane and/or petroleum ether as the small-polarity solvent, and preferably contains one or more of ethyl acetate, chloroform, dichloromethane, acetone, tetrahydrofuran, methanol and ethanol as the large-polarity solvent; the volume ratio of the small-polarity solvent to the large-polarity solvent in the small-polarity-large-polarity mixed solvent is preferably 100-00.01: 1, more preferably 20 to 0.2: 1.
after the cardanol formaldehyde is obtained, the cardanol formaldehyde and R-NH are mixed2Mixing with a solvent, and carrying out Schiff base reaction to obtain the hydrogenated cardanol-heterocyclic Schiff base compound;
R-NH2r in (a) includes any one of the following structures:
in the present invention, the R-NH group2Preferably 2-aminobenzoxazole, 2-aminobenzothiazole, 2-aminobenzimidazole or 5-amino-2-benzimidazolone. In the invention, the cardanol formaldehyde and R-NH2Is preferably 1: 0.3 to 3, more preferably 1: 0.5 to 2.5, and more preferably 1: 1～2。
In the invention, the solvent preferably comprises one or more of nitrile solvents, furan solvents, chlorohydrocarbon solvents, alcohol solvents and ketone solvents, and more preferably comprises one or more of acetonitrile, tetrahydrofuran, chloroform, ethanol, methanol and acetone; the solvent is preferably a dry solvent. In the present invention, the ratio of the mass of cardanol formaldehyde to the volume of the solvent is preferably 1 g: 4-100 mL, more preferably 1 g: 40-80 mL. The mixing method of the invention is not particularly limited, and the raw materials can be uniformly mixed.
In the invention, the temperature of the Schiff base reaction is preferably 20-120 ℃, more preferably 30-100 ℃, and further preferably 50-80 ℃; the time of the Schiff base reaction is preferably 0.5-48 h, more preferably 5-40 h, and further preferably 10-20 h. In the invention, the reaction generated in the Schiff base reaction process is shown as a formula (2):
after the schiff base has reacted, the present invention preferably further comprises a post-treatment, which preferably comprises: and (3) carrying out solid-liquid separation on the reaction liquid of the Schiff base reaction, washing the obtained solid product with an organic solvent, and drying to obtain the hydrogenated cardanol-heterocyclic Schiff base compound. The solid-liquid separation method is not particularly limited, and a solid-liquid separation method known to those skilled in the art, such as filtration, may be employed. In the present invention, the washing organic solvent is preferably a small-large polar solvent; the small polar solvent in the small polar-large polar solvent preferably comprises hexane and/or petroleum ether, and the large polar solvent preferably comprises one or more of methanol, ethyl acetate, chloroform, dichloromethane, acetone, tetrahydrofuran, ethanol, diethyl ether and butanol; the volume ratio of the small polar solvent to the large polar solvent in the small polar-large polar solvent is preferably 100-0.01: 1, more preferably 20 to 0.2: 1; the number of washing with the organic solvent is preferably 1 to 5. In the invention, the drying temperature is preferably 20-100 ℃, more preferably 35-80 ℃, the drying time is not particularly limited, and the drying is carried out until the weight is constant.
The invention provides application of the hydrogenated cardanol-heterocyclic Schiff base compound as an antioxidant. In the present invention, the hydrogenated cardanol-heterocyclic schiff base compound is preferably used as an antioxidant for plastics, rubber, paint, fiber or lubricating oil.
The invention provides an antioxidant polymer composite material, which comprises a polymer and the antioxidant. In the invention, the high molecular polymer preferably comprises one or more of general high molecular resin, engineering plastics and special plastics.
In the present invention, the general polymer resin preferably includes one or more of Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), Polystyrene (PS), polymethyl methacrylate (PMMA), and polyethylene-vinyl acetate (EVA). In the present invention, the engineering plastic preferably includes one or more of poly (acrylonitrile-butadiene-styrene) (ABS), Polycarbonate (PC), Polyoxymethylene (POM), Polyamide (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyphenylene oxide (PPO). In the present invention, the specialty plastic preferably includes one or more of polyarylate, polyphenyl ester, polysulfone, polyarylsulfone, polyethersulfone, polyimide, polyetherimide, polyamideimide, polyphenylene sulfide, polyether ether ketone, polyether ketone, liquid crystal polymer, thermoplastic fluoroplastic, reinforced plastic and foam plastic. In the present invention, the antioxidant polymer composite preferably comprises an antioxidant polylactic acid composite.
In the invention, the mass fraction of the hydrogenated cardanol-heterocyclic schiff base compound in the antioxidant polymer composite material is preferably 0.05-5%, more preferably 0.1-3%, and even more preferably 1-2%.
In the invention, the antioxidant polymer composite material preferably further comprises an auxiliary agent, wherein the auxiliary agent preferably comprises one or more of an inorganic filler, a processing modifier, a compatilizer, a light stabilizer, a dispersing agent, a dye, a plasticizer and a toughening agent.
In the present invention, the inorganic filler preferably includes one or more of calcium carbonate, talc, kaolin, wollastonite, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, silica, alumina trihydrate, magnesium hydroxide, mica, clay, natural phyllosilicate, and synthetic phyllosilicate; the content of the inorganic filler in the antioxidant polymer composite material is preferably 0-80%, more preferably 10-60%, and further preferably 30-50%.
In the present invention, the processing modifier preferably includes one or more of Chlorinated Polyethylene (CPE), methyl methacrylate-butadiene-styrene copolymer (NIBS), acrylonitrile-butadiene-styrene copolymer (ABS), ethylene-vinyl acetate copolymer (EVA), acrylate material (ACR), acrylonitrile-butadiene random copolymer (NBR), and rigid particles. In the invention, the acrylic ester material preferably comprises one or more of ACR-201, ACR-301, ACR-401, ACR-901 and ACR-MBS. In the invention, the rigid particles preferably comprise one or more of calcium carbonate, talcum powder, carbon black, barium sulfate, graphite, molybdenum disulfide, mica, aluminum powder, boron nitride powder, boron carbide, glass beads, glass fiber, kaolin, silicon dioxide, magnesium hydroxide, titanium dioxide, diatomite and carbon fiber. In the invention, the content of the processing modifier in the antioxidant polymer composite material is preferably 0-15%, more preferably 1-12%, and even more preferably 5-10%.
In the invention, the compatilizer preferably comprises one or more of PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH and PP-g-MAH. In the invention, the content of the processing modifier in the antioxidant polymer composite material is preferably 0-10%, more preferably 1-8%, and even more preferably 2-5%.
In the present invention, the light stabilizer preferably includes one or more of an o-hydroxybenzophenone-based light stabilizer, a benzotriazole-based light stabilizer, a salicylate-based light stabilizer, a triazine-based light stabilizer, an organic nickel chelate, and a hindered amine light stabilizer. In the invention, the o-hydroxybenzophenone light stabilizer preferably comprises one or more of Mark LA51, Seesorb 1000, Cyasorb UV-9, Cyasorb UV-24, Cyasorb UV-531 and Eastman DOBP. In the present invention, the benzotriazole-based light stabilizer preferably includes Tinuvin p, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 350, Tinuvin 360, Tinuvin 171, Tinuvin 213, Tinuvin 234, Tinuvin 571, and Tinuvin 840. In the present invention, the triazine light stabilizer preferably includes Tinuvin 1557 and/or Cyasorb UV-1164. In the present invention, the organic nickel chelate compound preferably includes one or more of Irgastab 2002, UV-ChekAM101 and SanduvorNPU. In the present invention, the hindered amine light stabilizer preferably comprises a HALS. In the invention, the content of the light stabilizer in the antioxidant polymer composite material is preferably 0-5%, more preferably 1-4%, and even more preferably 2-3%.
In the present invention, the dispersant preferably includes one or more of a fatty acid dispersant (stearic acid, calcium stearate, magnesium stearate), a fatty amide dispersant (ethylene bis stearamide (EBS), oleamide), an ester dispersant (glyceryl monostearate (GMS), glyceryl tristearate (HTG)), a paraffin dispersant (liquid paraffin, microcrystalline paraffin), a metallic soap dispersant (cadmium stearate (CdSt), magnesium stearate (MgSt), copper stearate (CuSt)), and a low molecular wax dispersant (polyethylene wax, polyethylene homopolymer, polyethylene oxide homopolymer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, low molecular ionomer). In the present invention, the fatty acid-based dispersing agent preferably includes one or more of stearic acid, calcium stearate, and magnesium stearate. In the present invention, the aliphatic amide-based dispersant preferably includes Ethylene Bis Stearamide (EBS) and/or oleic acid amide. In the present invention, the ester dispersant preferably includes Glycerol Monostearate (GMS) and/or glycerol tristearate (HTG). In the present invention, the paraffin-based dispersant preferably includes liquid paraffin and/or microcrystalline paraffin. In the present invention, the metal soap dispersant preferably includes one or more of cadmium stearate (CdSt), magnesium stearate (MgSt), and copper stearate (CuSt). In the present invention, the low molecular wax dispersant preferably includes one or more of polyethylene wax, polyethylene homopolymer, polyethylene oxide homopolymer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and low molecular ionomer. In the present invention, the low molecular ionomer preferably includes one or more of a-C295A, AClyn201, 201A, and 285. In the invention, the content of the dispersant in the antioxidant polymer composite material is preferably 0-15%, more preferably 1-12%, and even more preferably 5-10%.
In the present invention, the dye preferably includes an inorganic dye and/or an organic dye, and more preferably includes one or more of carbon black, titanium oxide, phthalocyanine blue, and phthalocyanine green. In the invention, the content of the dye in the antioxidant polymer composite material is preferably 0-2%, more preferably 0.5-1.5%, and even more preferably 1-1.5%.
In the present invention, the plasticizer preferably includes one or more of phthalate, fatty acid ester, polyol ester and epoxy hydrocarbon plasticizer. In the present invention, the phthalate preferably includes one or more of dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), dioctyl phthalate (DOP), Butyl Benzyl Phthalate (BBP), di (2-ethyl) hexyl phthalate (DEHP) and diisononyl phthalate (DINP). In the present invention, the fatty acid ester preferably includes one or more of fatty acid methyl ester, fatty acid ethyl ester and fatty acid butyl ester. In the present invention, the polyol ester preferably includes one or more of dipentaerythritol ester, glycol benzoate ester, and triacetin. In the present invention, the epoxidized hydrocarbon preferably includes epoxidized soybean oil. In the invention, the content of the processing modifier in the antioxidant polymer composite material is preferably 0-30%, more preferably 5-25%, and even more preferably 10-20%.
In the present invention, the toughening agent preferably comprises a phthalate and/or a polyol ester. In the present invention, the optional kinds of the phthalate ester and the polyol ester are preferably the same as those of the aforementioned phthalate ester and polyol ester, and will not be described herein again. In the invention, the content of the plasticizer in the antioxidant polymer composite material is preferably 0-50%, more preferably 5-45%, and even more preferably 10-30%.
The preparation method of the antioxidant polymer composite material is not particularly limited, and the antioxidant polymer composite material is prepared by a preparation method of the antioxidant polymer composite material known by the technical personnel in the field, specifically, the antioxidant polymer composite material is prepared by a solution blending method and a melt blending method. The preparation conditions of the solution blending method and the melt blending method are not particularly limited in the present invention, and the preparation conditions well known to those skilled in the art may be adopted.
The form of the antioxidant polymer composite material is not particularly limited, and may be a form known to those skilled in the art, such as a film or a particle.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Synthesis of hydrogenated cardanol-heterocyclic schiff base compound with structure shown in formula I, wherein
(1) Adding 5.02 cardanol, 3.45g trioxymethylene, 2.34g anhydrous magnesium chloride, 6.64g triethylamine and 100mL acetonitrile into a 250mL three-mouth reaction bottle in sequence, mixing, carrying out addition reaction for 2h at 80 ℃ in a nitrogen atmosphere, distilling under reduced pressure to remove the solvent, adding 50mL trichloromethane for purification, neutralizing with 5 wt% hydrochloric acid aqueous solution to be neutral, standing for phase separation, washing the obtained organic phase with water for 2 times (80 mL of single water), and carrying out anhydrous MgSO (MgSO) in sequence4Drying, removing solvent under reduced pressure, and purifying by column chromatography with n-hexane as eluent to obtain cardanol formaldehyde (2-hydroxy-4-pentadecylbenzeneFormaldehyde, white solid, 3.95 g).
(2) Adding 1.663g cardanol formaldehyde, 0.74g 2-aminobenzoxazole and 80mL anhydrous methanol into a 200mL single-mouth reaction bottle in sequence, mixing, reacting for 6h under the condition of stirring at 80 ℃, filtering, washing the obtained solid product methanol for 6 times to obtain a hydrogenated cardanol-heterocyclic Schiff base compound (abbreviated as AO1, 1.953g)
The hydrogen spectrum of cardanol formaldehyde prepared in this example is shown in fig. 1, and the hydrogen spectrum of AO1 is shown in fig. 2. As can be seen from fig. 1 to 3, the cardanol formaldehyde and the hydrogenated cardanol-heterocyclic schiff base compound having the structure shown in the present invention are prepared.
Example 2
Synthesis of hydrogenated cardanol-heterocyclic schiff base compound with structure shown in formula I, wherein
A hydrogenated cardanol-heterocyclic schiff base compound was prepared according to the method of example 1, differing from example 1 in that 0.74g of 2-aminobenzoxazole was replaced with 0.7512g of 2-aminobenzothiazole in step (2) to give a hydrogenated cardanol-heterocyclic schiff base compound (abbreviated as AO2, 2.012 g).
The hydrogen spectrum of AO2 prepared in this example is shown in FIG. 3. As can be seen from fig. 3, the hydrogenated cardanol-heterocyclic schiff base compound having the structure shown in the figure is prepared by the present invention.
Example 3
Synthesis of hydrogenated cardanol-heterocyclic schiff base compound with structure shown in formula I, wherein
A hydrogenated cardanol-heterocyclic schiff base compound was prepared according to the method of example 1, differing from example 1 in that 0.74g of 2-aminobenzoxazole was replaced with 0.666g of 2-aminobenzimidazole in step (2) to give a hydrogenated cardanol-heterocyclic schiff base compound (abbreviated as AO3, 2.1031 g).
The hydrogen spectrum of AO3 prepared in this example is shown in FIG. 4. As can be seen from fig. 4, the hydrogenated cardanol-heterocyclic schiff base compound having the structure shown in the figure is prepared by the present invention.
Example 4
Synthesis of hydrogenated cardanol-heterocyclic schiff base compound with structure shown in formula I, wherein
A hydrogenated cardanol-heterocyclic schiff base compound was prepared according to the method of example 1, except that 0.74g of 2-aminobenzoxazole was replaced with 0.7457g of 5-amino-2-benzimidazolone in step (2) to give a hydrogenated cardanol-heterocyclic schiff base compound (abbreviated as AO4, 2.3 g).
The IR spectrum of AO4 prepared in this example is shown in FIG. 5. As can be seen from FIG. 5, the length of the probe is 1704cm-1C ═ O stretching vibration absorption peak of benzimidazolone structure; at 3450cm-1A phenolic hydroxyl absorption peak exists; at 1637cm-1The existence of a-C ═ N-stretching vibration absorption peak indicates that the hydrogenated cardanol-heterocyclic schiff base compound with the structure shown in the invention is prepared.
Test example 1
Thermal stability
The thermal stability test results of the hydrogenated cardanol-heterocyclic schiff base compounds prepared in examples 1 to 4, the commercial antioxidant BHT (2, 6-di-tert-butyl-4-methylphenol), the commercial antioxidant 4010NA, and m-pentadecylphenol are shown in fig. 6. As can be seen from FIG. 6, the thermal stability of the hydrogenated cardanol-heterocyclic Schiff base compound prepared by the invention is far higher than the initial decomposition temperature (T) of the commercial antioxidant BHT, the commercial antioxidant 4010NA and m-pentadecylphenol, especially AO45%) highest decomposition temperature (T) than commercial antioxidant 4010NA5%) about 130 ℃ higher than the decomposition temperature (T) of the commercial antioxidant BHT5%) is about 240 ℃.
Example 5
Putting 5g of polylactic acid (PLA) into 100g of trichloromethane, and magnetically stirring for 5 hours at room temperature to fully dissolve the PLA to obtain a transparent and uniform PLA solution.
Placing AO1 prepared in example 1 in 10g of PLA solution, magnetically stirring for 1h at room temperature to obtain a PLA antioxidant composite solution, spreading the PLA antioxidant composite solution in a glass dish, placing the glass dish on a horizontal and dry workbench to naturally cast the PLA antioxidant composite solution into a film, drying at room temperature, and then placing in a vacuum oven at 55 ℃ for drying for 8h to obtain an antioxidant polylactic acid composite (abbreviated as PLA/AO 1); wherein, the mass percentage concentration of AO1 in the PLA antioxidant composite material solution is 0.1%.
Example 6
An antioxidant polylactic acid composite material (abbreviated as PLA/AO2) was prepared according to the method of example 5, except that AO1 was replaced with AO2 prepared in example 2.
Example 7
An antioxidant polylactic acid composite material (abbreviated as PLA/AO3) was prepared according to the method of example 5, except that AO1 was replaced with AO3 prepared in example 3.
Example 8
An antioxidant polylactic acid composite material (abbreviated as PLA/AO4) was prepared according to the method of example 5, except that AO1 was replaced with AO4 prepared in example 4.
Comparative example 1
The only difference from example 5 is that no AO1 was added, resulting in a pure polylactic acid film.
Comparative example 2
An antioxidant polylactic acid composite material (abbreviated as PLA/BHT) was prepared according to the method of example 5, except that AO1 was replaced with a commercial antioxidant BHT, to obtain an antioxidant polylactic acid composite material (abbreviated as PLA/BHT).
Comparative example 3
An antioxidant polylactic acid composite material was prepared according to the method of example 5, except that AO1 was replaced with a commercial antioxidant 1010 to obtain an antioxidant polylactic acid composite material (abbreviated as PLA/1010).
Test example 2
Antioxidant property
Respectively testing the Oxidation Induction Time (OIT) of the antioxidant polylactic acid composite material prepared in the embodiments 5-8 and the pure polylactic acid prepared in the comparative example 1 by using a differential scanning calorimeter, wherein the specific testing method comprises the following steps: GB/T19466.6-2009. The test results are shown in table 1:
TABLE 1 Oxidation Induction Time (OIT) of Oxidation resistant polylactic acid composites and pure polylactic acid
As can be seen from table 1, after the hydrogenated cardanol-heterocyclic schiff base compound prepared according to the present invention is added to polylactic acid, the oxidation induction time of the composite material is far superior to that of pure polylactic acid, which indicates that the hydrogenated cardanol-heterocyclic schiff base compound provided by the present invention has excellent oxidation resistance.
Test example 3
Xenon lamp aging Performance of the antioxidant polylactic acid composite materials prepared in examples 5 to 8 and comparative examples 2 to 3 and the pure polylactic acid prepared in comparative example 1
The light source accelerated ageing test in the laboratory is an ageing test method commonly used in plastic ageing tests, is suitable for plastics which are often exposed to sunlight or sunlight penetrating through window glass for a long time and are used indoors and outdoors, and the xenon lamp ageing test box is used for carrying out tests to comprehensively consider the influences of light, oxygen, heat, humidity and rainfall on the appearance and the performance of the plastics. Xenon arc lamps have spectral power distributions most similar to sunlight and are therefore widely used in aging tests for plastics.
The test method comprises the following steps: GB/T16422.2-2014, the specific test parameter setting is shown in Table 2, the sampling is carried out when the irradiation is carried out for 0h, 12h, 24h, 36h and 48h respectively, and 48h is a period and is circulated; the test specimens were subjected to tensile strength testing at a tensile rate of 5mm/min at room temperature in accordance with GB/T1040.3-2006. FIG. 7 is a graph showing the effect of xenon lamp aging on the tensile strength of the antioxidant polylactic acid composite materials prepared in examples 5 to 8 and comparative examples 2 to 3.
Table 2 xenon lamp aging test exposure conditions
As can be seen from FIG. 7, the photo-aging properties were improved with the addition of the antioxidant. Compared with commercial 1010 and BHT antioxidants, after aging for 48 hours, after AO 1-AO 4 in the invention examples are added into PLA, the tensile strength of the aged PLA xenon lamp is higher than that of the commercial antioxidants, which shows that the antioxidant has good light aging resistance
Test example 4
Thermo-oxidative aging Properties of the antioxidant polylactic acid composite materials prepared in examples 5 to 8 and comparative examples 2 to 3 and the pure polylactic acid prepared in comparative example 1
The accelerated thermal oxidation aging test method comprises the following steps: GB/T3512-2001, the aging temperature is 100 ℃, and the aging time is variable.
FIG. 8 shows the results of the thermal oxidative aging box test. As can be seen from FIG. 8, the thermal-oxidative aging performance was improved with the addition of the antioxidant, wherein the performance was best AO2 with minimal decrease in tensile strength; AO1 and AO4 were comparable to commercial 1010 and BHT antioxidant performance.
Test example 5
Mechanical properties of the antioxidant polylactic acid composite materials prepared in examples 5 to 8 and comparative examples 2 to 3 and the pure polylactic acid prepared in comparative example 1
The tensile property test method comprises the following steps: GB/T1040.3-2006, the antioxidant polylactic acid composite materials prepared in examples 5-8 and comparative examples 2-3 and the pure polylactic acid dumbbell-shaped standard sample prepared in comparative example 1 were tested at room temperature at a tensile rate of 5 mm/min.
FIG. 9 is a graph showing the tensile property test results of the antioxidant polylactic acid composite materials prepared in examples 5 to 8 and comparative examples 2 to 3 and the pure polylactic acid prepared in comparative example 1. As can be seen from fig. 9, after the antioxidant is added, except that BHT and AO2 can slightly reduce the tensile strength of the antioxidant polylactic acid composite material, the tensile strength of the antioxidant polylactic acid composite material can be increased or maintained unchanged, which indicates that the hydrogenated cardanol-heterocyclic schiff base compound prepared by the present invention has little influence on the mechanical properties of the antioxidant polylactic acid composite material.
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. A hydrogenated cardanol-heterocyclic schiff base compound having the structure shown in formula I:
in the formula I, R has a heterocyclic structure and comprises any one of the following structures:
in the R, R1、R2And R3Independently comprise H, C1～C12Alkyl or halo.
2. A method of preparing the hydrogenated cardanol-heterocyclic schiff base compound of claim 1, comprising the steps of:
mixing cardanol, aldehyde, metal halide salt, an addition reaction catalyst and a solvent, and carrying out an addition reaction to obtain cardanol formaldehyde;
mixing the cardanol formaldehyde and R-NH2Mixing with a solvent, and carrying out Schiff base reaction to obtain the hydrogenated cardanol-heterocyclic Schiff base compound;
R-NH2r in (a) is the same as R in the formula I.
3. The preparation method according to claim 2, wherein the aldehyde comprises one or more of aliphatic aldehyde, alicyclic aldehyde, aromatic aldehyde and terpene aldehyde;
the mol ratio of cardanol to aldehyde is 1: 1-10; the aldehyde is calculated by the amount of formaldehyde;
the metal halide salt comprises magnesium chloride and/or aluminum chloride;
the addition reaction catalyst comprises one or more of organic amine, hydroxide, boric acid compounds, benzenesulfonic acid compounds and palladium carbon;
the mol ratio of the cardanol to the metal halide salt to the addition reaction catalyst is 1: 1-15: 1 to 15.
4. The method of claim 2, wherein the cardanol formaldehyde and R-NH are present2In a molar ratio of 1: 0.3 to 3.
5. The method according to any one of claims 2 to 4, wherein the temperature of the addition reaction and the Schiff base reaction is 20 to 120 ℃ independently, and the time is 0.5 to 48 hours independently.
6. Use of the hydrogenated cardanol-heterocyclic schiff base compound of claim 1 as an antioxidant.
7. An antioxidant polymer composite comprising a polymer and the antioxidant of claim 1; the high molecular polymer comprises one or more of general high molecular resin, engineering plastics and special plastics.
8. The antioxidant polymer composite of claim 7, wherein the general polymer resin comprises one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, and polyethylene-vinyl acetate;
the engineering plastic comprises one or more of poly (acrylonitrile-butadiene-styrene), polycarbonate, polyformaldehyde, polyamide, polyethylene terephthalate, polybutylene terephthalate and polyphenyl ether;
the special plastic comprises one or more of polyarylate, polyphenyl ester, polysulfone, polyarylsulfone, polyethersulfone, polyimide, polyetherimide, polyamideimide, polyphenylene sulfide, polyether ether ketone, polyether ketone, liquid crystal polymer, thermoplastic fluoroplastic, reinforced plastic and foam plastic.
9. The antioxidant polymer composite material as claimed in claim 7 or 8, wherein the mass fraction of the hydrogenated cardanol-heterocyclic schiff base compound in the antioxidant polymer composite material is 0.05-5%.
10. The antioxidant polymer composite of claim 7 or 8, further comprising an auxiliary agent, wherein the auxiliary agent comprises one or more of an inorganic filler, a processing modifier, a compatibilizer, a light stabilizer, a dispersant, a dye, a plasticizer, and a toughening agent.
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