CN114456119B - Hydrogenated cardanol-heterocyclic Schiff base compound, preparation method and application thereof, polylactic acid composite material and preparation method - Google Patents
Hydrogenated cardanol-heterocyclic Schiff base compound, preparation method and application thereof, polylactic acid composite material and preparation method Download PDFInfo
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- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- 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
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
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- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
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- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
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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, heterocycle with light stability and metal ion passivation performance is used as another structural unit, and Schiff base functional group with metal ion complexing characteristic is used as a bridging structure of the mother ring and heterocycle, so that the hydrogenated cardanol-heterocycle Schiff base compound provided by the invention has excellent oxidation resistance, light stability and metal ion passivation performance. The hydrogenated cardanol-heterocyclic schiff base compound provided by the invention has a structure in which two structures of phenol and a heterocyclic ring are connected into one macromolecule through a chemical bond, the molecular weight is remarkably increased compared with cardanol, and 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, in particular to a hydrogenated cardanol-heterocyclic Schiff base compound, a preparation method and application thereof, and a polylactic acid composite material and a preparation method thereof.
Background
Cardanol is a main component extracted from agricultural waste cashew nutshells, has wide sources, natural antioxidation property, meets the definition of green chemistry and national sustainable development strategic requirements, and is widely applied to the industries of high polymer materials, foods, lubricants, fibers and rubber as a substitute for alkylphenol from petrochemical sources. Because cardanol is an m-alkylphenol structure, the antioxidant activity of cardanol is much lower than that of 2, 6-di-tert-butyl-p-cresol (BHT) with the largest commercial dosage, and the antioxidant activity of cardanol needs to be improved in order to realize the practical application of cardanol as an antioxidant in materials.
The antioxidant activity of the cardanol structure can be improved by introducing other structures into the cardanol structure. For example, chinese patent CN201811433025 discloses cardanol-aromatic amine Schiff base derivatives having a structure represented by formula (I), wherein R is selected from one of the structures represented by formulas (II) to (V), R 1 Selected from H or a structure represented by formula (VI):
however, the oxidation induction period of the cardanol-like aromatic amine Schiff base derivative is 44.6min at maximum, 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 application thereof, and 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 R, R is 1 、R 2 And R is 3 Independently comprise H, C 1 ～C 12 Alkyl or halo.
The invention provides a preparation method of the hydrogenated cardanol-heterocyclic Schiff base compound, which comprises the following steps:
mixing cardanol, aldehyde, metal halide, an addition reaction catalyst and a solvent, and performing an addition reaction to obtain cardanol formaldehyde;
the cardanol formaldehyde, R-NH 2 Mixing the hydrogenated cardanol-heterocyclic Schiff base compound with a solvent, and carrying out Schiff base reaction to obtain the hydrogenated cardanol-heterocyclic Schiff base compound;
R-NH 2 r in (2) is the same as R in formula I.
Preferably, the aldehyde comprises one or more of aliphatic aldehyde, alicyclic aldehyde, aromatic aldehyde and terpene aldehyde;
the molar ratio of cardanol to aldehyde is 1:1 to 10; the aldehyde is calculated by the 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 molar ratio of the cardanol to the metal halide to the addition reaction catalyst is 1:1 to 15:1 to 15.
Preferably, the cardanol formaldehyde and R-NH 2 The molar ratio of (2) is 1:0.3 to 3.
Preferably, the temperature of the addition reaction and the Schiff base reaction are independently 20-120 ℃ and the time is independently 0.5-48 h.
The invention provides application of the hydrogenated cardanol-heterocyclic Schiff base compound as an antioxidant.
The invention also provides an antioxidant high molecular composite material, which comprises a high molecular polymer and the hydrogenated cardanol-heterocyclic Schiff base compound according to the technical scheme; the high polymer comprises one or more of general high polymer resin, engineering plastic and special plastic.
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, polyoxymethylene, polyamide, polyethylene terephthalate, polybutylene terephthalate and polyphenyl ether;
the special plastic comprises one or more of polyarylate, polyphenyl ester, polysulfone, polyarylsulfone, polyether sulfone, polyimide, polyether imide, polyamide imide, 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 is 0.05-5%.
Preferably, the modified polyurethane foam 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. The invention takes cardanol as a mother ring, the phenolic hydroxyl structure on cardanol has natural oxidation resistance, heterocycle (benzoxazole, benzothiazole, benzimidazole and benzimidazolinone) with light stability and metal ion passivation performance is taken as another structural unit, and Schiff base functional group with certain metal ion complexing property is taken as a bridging structure of the mother ring and heterocycle, so that the hydrogenated cardanol-heterocycle Schiff base compound provided by the invention has excellent oxidation resistance, light stability and metal ion passivation property. The hydrogenated cardanol-heterocyclic schiff base compound provided by the invention has a structure in which two structures of phenol and a heterocyclic ring are connected into one macromolecule through a chemical bond, the molecular weight is remarkably increased compared with cardanol, and 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 good application prospects in antioxidation of plastics, rubber, coatings and fibers.
The invention provides a preparation method of the hydrogenated cardanol-heterocyclic Schiff base compound. According to the preparation method provided by the invention, the cardanol derivative hydrogenated cardanol derived from natural biomass is used as one of the raw materials, the raw materials are low in price and wide in source, and the preparation method has the advantages of reproducibility, low toxicity, environment friendliness and the like; short reaction route, simple process, high product yield and suitability for technological production.
The invention provides a polylactic acid composite material, which comprises polylactic acid and the hydrogenated cardanol-heterocyclic Schiff base compound. According to the invention, the hydrogenated cardanol-heterocyclic Schiff base compound is used as an antioxidant, so that the oxidation resistance, the photostability, the metal ion passivation and the heat stability of the polylactic acid are remarkably improved.
The invention provides a preparation method of the polylactic acid composite material. The preparation method provided by the invention is simple to operate 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 a 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 antioxidant BHT, the commercial antioxidant 4010NA and the m-pentadecyl phenol prepared in examples 1 to 4;
FIG. 7 is a graph showing the effect of xenon lamp aging for various times on the tensile strength of the antioxidant polylactic acid composite prepared in examples 5 to 8 and comparative examples 2 to 3;
FIG. 8 is a thermal oxidative aging test result of the antioxidant polylactic acid composite 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 tensile property test results of the antioxidant polylactic acid composite 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 R, R is 1 、R 2 And R is 3 Independently comprise H, C 1 ～C 10 Alkyl or halo. In the present invention, the C 1 ～C 12 Alkyl preferably includes independently hydrogen, C 1 -C 12 Alkyl, tertiary C 4 -C 12 Alkyl, C 5 -C 8 Cycloalkyl, C 1 -C 12 Alkyl or S-C 1 -C 12 Alkyl, O-C 1 -C 12 Alkyl, CO-O-C 1 -C 12 Alkyl and/or O-CO-C 12 Alkyl substituted C 1 -C 12 An alkyl group. In the present invention, the halogeno group preferably includes Cl or Br.
In the present invention, the R preferably has any one of the following structures:
the invention provides a preparation method of a hydrogenated cardanol-heterocyclic Schiff base compound, which comprises the following steps:
mixing cardanol, aldehyde, metal halide, an addition reaction catalyst and a solvent, and performing an addition reaction to obtain cardanol formaldehyde;
the cardanol formaldehyde, R-NH 2 Mixing the hydrogenated cardanol-heterocyclic Schiff base compound with a solvent, and carrying out Schiff base reaction to obtain the hydrogenated cardanol-heterocyclic Schiff base compound;
R-NH 2 r in (2) is the same as R in formula I.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
Mixing cardanol, aldehyde, metal halide, an addition reaction catalyst and a solvent, and performing 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 fatty aldehyde preferably comprises one or more of formaldehyde, formaldehyde solution, trioxymethylene, acetaldehyde, octanal, nonanal, decanal, undecanal, lauraldehyde (dodecanal), tridecanol, myristyl aldehyde (tetradecanal), methylhexyl acetaldehyde, methyloctyl acetaldehyde, methylnonyl acetaldehyde, trimethylhexanal and tetramethylhexanal; the alicyclic aldehyde preferably comprises one or more of glossy privet aldehyde, argyl aldehyde, isocyclic citral, orange aldehyde, methyl orange aldehyde and neotame aldehyde; the aromatic aldehyde preferably comprises one or more of benzaldehyde, phenylacetaldehyde, phenylpropionaldehyde, cinnamaldehyde, muguet aldehyde, vanillin and ethyl vanillin; the terpene aldehydes preferably include one or more of trans-2-hexenal, 2-nonenal, trans-4-decenal, undecenal, nonenal, citral, citronellal, hydroxycitronellal, perillaldehyde, and trimethylheptenal. In the present invention, the molar ratio of cardanol to aldehyde is preferably 1:1 to 10, more preferably 1:2 to 8, more preferably 1:5 to 6; the aldehyde is based on the amount of 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 present invention, the addition reaction catalyst preferably includes one or more of organic amine, hydroxide, boric acid-based compound, benzenesulfonic acid-based compound and palladium carbon; the organic amine preferably comprises triethylamine and/or tributylamine, and the tributylamine preferably comprises tri-n-butylamine; the hydroxide preferably comprises sodium hydroxide and/or potassium hydroxide; the boric acid compound preferably comprises 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 to 10%, more preferably 2 to 8%, and even more preferably 4 to 5%.
In the present invention, the molar ratio of cardanol, metal halide salt and addition reaction catalyst is preferably 1:1 to 15:1 to 15, more preferably 1:3 to 12:3 to 12, more preferably 1: 5-10: 5 to 10.
In the present invention, the solvent preferably includes one or more of nitrile-based solvents, furan-based solvents, chlorinated hydrocarbon-based solvents, alcohol-based solvents, and ketone-based solvents, more preferably includes 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 1g:4 to 100mL, more preferably 1g: 20-50 mL. The mode of the mixing is not particularly limited in the present invention, and the raw materials may be uniformly mixed.
In the present invention, the temperature of the addition reaction is preferably 20 to 120 ℃, more preferably 30 to 100 ℃, still more preferably 50 to 80 ℃; the time of the addition reaction is preferably 0.5 to 48 hours, more preferably 5 to 40 hours, still more preferably 10 to 20 hours; 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 includes a post-treatment, which preferably includes: and (3) adding an organic solvent for purification after the first concentration of the reaction liquid of the addition reaction, regulating 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 method of the present invention is not particularly limited, and the first concentration and the second concentration may be performed by any concentration method known to those skilled in the art, such as distillation under reduced pressure; in embodiments of the invention, it is preferred to concentrate to remove the solvent. In the present invention, the organic solvent for purification preferably includes one or more of nitrile-based solvent, furan-based solvent, chlorohydrocarbon-based solvent, alcohol-based solvent and ketone-based 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 1g:4 to 100mL, more preferably 1g: 20-50 mL. In the present invention, the acid used for adjusting the pH preferably includes one or more of hydrochloric acid, acetic acid, sulfuric acid and nitric acid, and the acid is preferably used in the form of an aqueous acid solution, and the concentration of the aqueous acid solution is preferably 0.1 to 37wt%, more preferably 5 to 30wt%, still more preferably 10 to 20wt%. In the present invention, the number of times of the water washing is preferably 2 to 3 times; the ratio of the mass of cardanol to the volume of the single water washing water is preferably 1g:4 to 100mL, more preferably 1g: 15-50 mL. In the present invention, the desiccant for drying a desiccant 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 small-polarity-large-polarity mixed solvent; the small polar solvent preferably comprises hexane and/or petroleum ether, and the large polar solvent preferably comprises one or more of ethyl acetate, chloroform, dichloromethane, acetone, tetrahydrofuran, methanol and ethanol; the volume ratio of the small polar solvent to the large polar solvent in the small polar-large polar mixed solvent is preferably 100-00.01: 1, more preferably 20 to 0.2:1.
after obtaining the cardanol formaldehyde, the invention uses the cardanol formaldehyde and R-NH 2 Mixing the hydrogenated cardanol-heterocyclic Schiff base compound with a solvent, and carrying out Schiff base reaction to obtain the hydrogenated cardanol-heterocyclic Schiff base compound;
R-NH 2 r in (2) comprises any one of the following structures:
in the present invention, the R-NH group 2 Preferably comprises 2-aminobenzoxazole, 2-aminobenzothiazole, 2-aminobenzimidazole or 5-amino-2-benzimidazolone. In the invention, the cardanol formaldehyde and R-NH 2 Preferably 1:0.3 to 3, more preferably 1:0.5 to 2.5, more preferably 1:1 to 2.
In the present invention, the solvent preferably includes one or more of nitrile-based solvents, furan-based solvents, chlorinated hydrocarbon-based solvents, alcohol-based solvents, and ketone-based solvents, more preferably includes 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 the cardanol formaldehyde to the volume of the solvent is preferably 1g:4 to 100mL, more preferably 1g: 40-80 mL. The mode of the mixing is not particularly limited in the present invention, and the raw materials may be uniformly mixed.
In the present invention, the temperature of the schiff base reaction is preferably 20 to 120 ℃, more preferably 30 to 100 ℃, further preferably 50 to 80 ℃; the time for the schiff base reaction is preferably 0.5 to 48 hours, more preferably 5 to 40 hours, and still more preferably 10 to 20 hours. In the invention, the reaction occurring in the Schiff base reaction process is shown as a formula (2):
after the schiff base reaction, the invention preferably further comprises a post-treatment, preferably comprising: and (3) carrying out solid-liquid separation on the reaction liquid of the Schiff base reaction, washing an obtained solid product with an organic solvent, and drying to obtain the hydrogenated cardanol-heterocyclic Schiff base compound. The mode of the solid-liquid separation is not particularly limited, and the solid-liquid separation can be carried out by a method known to those skilled in the art, such as filtration. In the present invention, the organic solvent for washing is preferably a small-polar-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, a step of; the number of times of the organic solvent washing is preferably 1 to 5 times. In the present invention, the drying temperature is preferably 20 to 100 ℃, more preferably 35 to 80 ℃, and the drying time is not particularly limited, and the drying time is required to be 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 high molecular composite material, which comprises a high molecular polymer and the hydrogenated cardanol-heterocyclic Schiff base compound. In the present invention, the high molecular polymer preferably includes one or more of general-purpose high molecular resin, engineering plastic and special plastic.
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 special plastic preferably 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. In the present invention, the antioxidant polymer composite preferably includes an antioxidant polylactic acid composite.
In the present invention, the mass fraction of the hydrogenated cardanol-heterocyclic schiff base compound in the antioxidant polymer composite is preferably 0.05 to 5%, more preferably 0.1 to 3%, still more preferably 1 to 2%.
In the invention, the antioxidant polymer composite material preferably further comprises an auxiliary agent, and 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 is preferably 0 to 80%, more preferably 10 to 60%, and even more preferably 30 to 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), acrylic material (ACR), acrylonitrile-butadiene random copolymer (NBR), and rigid particles. In the present invention, the acrylic material preferably includes one or more of ACR-201, ACR-301, ACR-401, ACR-901 and ACR-MBS. In the present invention, the rigid particles preferably include one or more of calcium carbonate, talc, carbon black, barium sulfate, graphite, molybdenum disulfide, mica, aluminum powder, boron nitride powder, boron carbide, glass beads, glass fibers, kaolin, silica, magnesium hydroxide, titanium dioxide, diatomaceous earth, and carbon fibers. In the present invention, the content of the processing modifier in the antioxidant polymer composite is preferably 0 to 15%, more preferably 1 to 12%, and even more preferably 5 to 10%.
In the present invention, the compatibilizing agent preferably comprises one or more of PE-g-ST, PP-g-ST, ABS-g-MAH, PE-g-MAH and PP-g-MAH. In the present invention, the content of the processing modifier in the antioxidant polymer composite is preferably 0 to 10%, more preferably 1 to 8%, and even more preferably 2 to 5%.
In the present invention, the light stabilizer preferably includes one or more of an o-hydroxybenzophenone-type light stabilizer, a benzotriazole-type light stabilizer, a salicylate-type light stabilizer, a triazine-type light stabilizer, an organonickel chelate and a hindered amine light stabilizer. In the present invention, the o-hydroxybenzophenone type light stabilizer preferably includes one or more of MarkLA51, seesorb1000, cyasorbUV-9, cyasorbUV-24, cyasorbUV-531 and EastmanDOBP. In the present invention, the benzotriazole-based light stabilizer preferably includes TinuvinP, tinuvin, tinuvin326, tinuvin327, tinuvin328, tinuvin329, tinuvin350, tinuvin360, tinuvin171, tinuvin213, tinuvin234, tinuvin571 and Tinuvin 840. In the present invention, the triazine-based light stabilizer preferably includes Tinuvin1557 and/or CyasorbUV-1164. In the present invention, the organonickel chelate preferably includes one or more of Irgastab2002, UV-ChekAM101, and SanduvorNPU. In the present invention, the hindered amine light stabilizer preferably comprises HALS. In the present invention, the content of the light stabilizer in the antioxidant polymer composite is preferably 0 to 5%, more preferably 1 to 4%, and even more preferably 2 to 3%.
In the present invention, the dispersant preferably includes one or more of fatty acid-based dispersants (stearic acid, calcium stearate, magnesium stearate), aliphatic amide-based dispersants (ethylene bis stearamide (EBS), oleamide), ester-based dispersants (glyceryl monostearate (GMS), glyceryl tristearate (HTG)), paraffin-based dispersants (liquid paraffin, microcrystalline paraffin), metal soap-based dispersants (cadmium stearate (CdSt), magnesium stearate (MgSt), copper stearate (CuSt)), and low-molecular wax-based dispersants (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 oleamide. In the present invention, the ester dispersant preferably includes Glyceryl Monostearate (GMS) and/or glyceryl 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-based 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-based 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, AClyn, 201A and 285. In the present invention, the content of the dispersant in the antioxidant polymer composite is preferably 0 to 15%, more preferably 1 to 12%, and even more preferably 5 to 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 present invention, the content of the dye in the antioxidant polymer composite is preferably 0 to 2%, more preferably 0.5 to 1.5%, and even more preferably 1 to 1.5%.
In the present invention, the plasticizer preferably includes one or more of phthalate, fatty acid ester, polyol ester, and epoxy hydrocarbon type 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, and triacetin. In the present invention, the epoxyhydrocarbon preferably comprises epoxidized soybean oil. In the present invention, the content of the processing modifier in the antioxidant polymer composite is preferably 0 to 30%, more preferably 5 to 25%, and even more preferably 10 to 20%.
In the present invention, the toughening agent preferably includes phthalate esters and/or polyol esters. In the present invention, the optional types of the phthalate and the polyol ester are preferably the same as those of the phthalate and the polyol ester described above, and are not described herein. In the present invention, the plasticizer content in the antioxidant polymer composite is preferably 0 to 50%, more preferably 5 to 45%, and even more preferably 10 to 30%.
The preparation method of the antioxidant polymer composite material is not particularly limited, and the antioxidant polymer composite material can be prepared by a preparation method of the antioxidant polymer composite material well known to a person skilled in the art, and particularly, 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, and those well known to those skilled in the art may be employed.
The form of the antioxidant polymer composite is not particularly limited, and forms well known to those skilled in the art, such as films or particles, may be adopted.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Synthesis of hydrogenated cardanol-heterocyclic Schiff base Compound having Structure shown in formula I, wherein
(1) Sequentially adding 5.02 cardanol, 3.45g trioxymethylene, 2.34g anhydrous magnesium chloride, 6.64g triethylamine and 100mL acetonitrile into a 250mL three-port reaction bottle, mixing, adding the mixture into the three-port reaction bottle under the condition of 80 ℃ in a nitrogen atmosphere for 2h, distilling the mixture under reduced pressure to remove the solvent, adding 50mL of chloroform for purification, neutralizing the mixture to be neutral by using 5wt% hydrochloric acid aqueous solution, standing the mixture for phase separation, washing the obtained organic phase for 2 times (80 mL of single water) and anhydrous MgSO sequentially 4 The solvent was removed under reduced pressure and purified by column chromatography using n-hexane as an eluent to give cardanol formaldehyde (2-hydroxy-4-pentadecyl benzaldehyde, white solid, 3.95 g).
(2) 1.663g of cardanol formaldehyde, 0.74g of 2-aminobenzoxazole and 80mL of absolute methanol are sequentially added into a 200mL single-port reaction bottle, mixed, schiff base reacted for 6 hours at 80 ℃ under stirring, filtered, and the obtained solid product methanol is washed for 6 times to obtain a hydrogenated cardanol-heterocyclic Schiff base compound (abbreviated as AO1,1.953 g)
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 2, the present invention provides cardanol formaldehyde and hydrogenated cardanol-heterocyclic schiff base compounds of the structure shown.
Example 2
Synthesis of hydrogenated cardanol-heterocyclic Schiff base Compound having Structure shown in formula I, wherein
The hydrogenated cardanol-heterocyclic schiff base compound was prepared as in example 1, except that 0.74g of 2-aminobenzoxazole was replaced with 0.7512g of 2-aminobenzothiazole in step (2), giving 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 with the structure shown in the specification is prepared.
Example 3
Synthesis of hydrogenated cardanol-heterocyclic Schiff base Compound having Structure shown in formula I, wherein
The hydrogenated cardanol-heterocyclic schiff base compound was prepared as in example 1, except that 0.74g of 2-aminobenzoxazole was replaced with 0.666g of 2-aminobenzimidazole in step (2), giving 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 with the structure shown in the specification is prepared.
Example 4
Hydrogenated cardanol having a structure represented by formula I-synthesis of heterocyclic schiff base compounds, wherein
The hydrogenated cardanol-heterocyclic schiff base compound was prepared as in example 1, except that 0.7457g of 2-aminobenzoxazole was replaced with 0.7457g of 5-amino-2-benzimidazolone in step (2), giving a hydrogenated cardanol-heterocyclic schiff base compound (abbreviated as AO4,2.3 g).
The infrared spectrum of AO4 prepared in this example is shown in FIG. 5. As can be seen from FIG. 5, at 1704cm -1 A c=o telescopic vibration absorption peak of the benzimidazolone structure exists; at 3450cm -1 A phenolic hydroxyl absorption peak exists at the position; at 1637cm -1 There is-C=N-stretching vibration absorption peak, which shows that the hydrogenated cardanol-heterocyclic Schiff base compound with the structure shown in the invention is prepared.
Test example 1
Thermal stability
The results of the thermal stability test of the hydrogenated cardanol-heterocyclic schiff base compound prepared in examples 1 to 4, the commercial antioxidant BHT (2, 6-di-t-butyl-4-methylphenol), the commercial antioxidant 4010NA and m-pentadecyl phenol are shown in FIG. 6. As can be seen from FIG. 6, the thermal stability of the hydrogenated cardanol-heterocyclic Schiff base compound of the present invention is far higher than the initial decomposition temperature (T 5 % is highest, and is higher than the decomposition temperature (T) of commercial antioxidant 4010NA 5 % of the total molecular weight of the antioxidant BHT) at about 130℃higher than the decomposition temperature (T) of the commercial antioxidant BHT 5 %) is about 240 ℃.
Example 5
5g of polylactic acid (PLA) is placed in 100g of chloroform, and the mixture is magnetically stirred for 5 hours at room temperature to fully dissolve the polylactic acid (PLA) to obtain transparent and uniform PLA solution.
Placing AO1 prepared in the example 1 in 10g PLA solution, magnetically stirring for 1h at room temperature to obtain PLA antioxidant composite material solution, spreading the PLA antioxidant composite material solution in a glass dish, placing the glass dish on a horizontal and dry workbench to naturally cast the PLA antioxidant composite material 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 material (abbreviated as PLA/AO 1); wherein the mass percentage concentration of AO1 in the PLA antioxidant composite material solution is 0.1 percent.
Example 6
An antioxidant polylactic acid composite was prepared according to the method of example 5, except that AO1 was replaced with AO2 prepared in example 2, to obtain an antioxidant polylactic acid composite (abbreviated as PLA/AO 2).
Example 7
An antioxidant polylactic acid composite was prepared according to the method of example 5, except that AO1 was replaced with AO3 prepared in example 3, resulting in an antioxidant polylactic acid composite (abbreviated as PLA/AO 3).
Example 8
An antioxidant polylactic acid composite was prepared according to the method of example 5, except that AO1 was replaced with AO4 prepared in example 4, resulting in an antioxidant polylactic acid composite (abbreviated as PLA/AO 4).
Comparative example 1
The difference from example 5 is that the pure polylactic acid film was obtained without adding AO 1.
Comparative example 2
An antioxidant polylactic acid composite was prepared according to the method of example 5, except that AO1 was replaced with a commercial antioxidant BHT to give an antioxidant polylactic acid composite (abbreviated as PLA/BHT) as compared with example 5.
Comparative example 3
An antioxidant polylactic acid composite was prepared according to the method of example 5, except that AO1 was replaced with a commercial antioxidant 1010, resulting in an antioxidant polylactic acid composite (abbreviated as PLA/1010).
Test example 2
Oxidation resistance
The Oxidation Induction Time (OIT) of the antioxidant polylactic acid composite materials prepared in examples 5 to 8 and the pure polylactic acid prepared in comparative example 1 were measured by a differential scanning calorimeter, respectively, and the specific measurement method is as follows: GB/T19466.6-2009. The test results are shown in table 1:
TABLE 1 Oxidation Induction Time (OIT) of antioxidant polylactic acid composite and pure polylactic acid
As can be seen from Table 1, after the hydrogenated cardanol-heterocyclic Schiff base compound prepared by the invention is added into polylactic acid, the oxidation induction time of the composite material is far longer than that of pure polylactic acid, which indicates that the hydrogenated cardanol-heterocyclic Schiff base compound provided by the invention has excellent oxidation resistance.
Test example 3
Antioxidant polylactic acid composite materials prepared in examples 5 to 8 and comparative examples 2 to 3 and xenon lamp aging properties of pure polylactic acid prepared in comparative example 1
The laboratory light source accelerated aging test is a common aging test method in plastic aging tests, is suitable for indoor and outdoor plastic which is often exposed to sunlight or sunlight irradiation penetrating window glass for a long time, and comprehensively considers the influence of light, oxygen, heat, humidity and rainfall on the appearance and performance of the plastic by using a xenon lamp aging test box for test. Xenon arc lamps have a spectral energy distribution most similar to that of sunlight and are therefore widely used in ageing tests of plastics.
The testing method comprises the following steps: GB/T16422.2-2014, specific test parameter settings are shown in Table 2, samples are taken when irradiating for 0h, 12h, 24h, 36h and 48h respectively, and 48h is a period and circulates; the bars after testing were tested for tensile strength at a tensile rate of 5mm/min at room temperature according to GB/T1040.3-2006. FIG. 7 is a graph showing the effect of aging of a xenon lamp for various times on the tensile strength of the antioxidant polylactic acid composite 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 performance was improved by adding an antioxidant. Compared with commercial 1010 and BHT antioxidants, after aging for 48 hours, the AO 1-AO 4 in the embodiment of the invention is added into PLA, so that the tensile strength of the PLA xenon lamp after aging is higher than that of the commercial antioxidants, and the PLA xenon lamp has good photo-aging resistance
Test example 4
Antioxidant polylactic acid composite materials prepared in examples 5 to 8 and comparative examples 2 to 3 and pure polylactic acid prepared in comparative example 1 were excellent in thermal oxidative aging properties
Accelerated thermo-oxidative aging test method: GB/T3512-2001, ageing temperature is 100 ℃, and ageing time is variable.
FIG. 8 shows the results of the thermal oxidative aging oven test. As can be seen from FIG. 8, the thermal oxidative aging performance was improved by the addition of the antioxidant, wherein AO2 was the best performance and the decrease in tensile strength was the smallest; AO1 and AO4 are comparable to commercial 1010 and BHT antioxidant performance.
Test example 5
Mechanical Properties of the antioxidant polylactic acid composite 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 testing method comprises the following steps: GB/T1040.3-2006 the antioxidant polylactic acid composites prepared in examples 5 to 8 and comparative examples 2 to 3 and the pure polylactic acid dumbbell-shaped standard sample prepared in comparative example 1 were tested at a tensile rate of 5mm/min at room temperature.
Fig. 9 is a graph showing tensile property test results of the antioxidant polylactic acid composite prepared in examples 5 to 8 and comparative examples 2 to 3 and the pure polylactic acid prepared in comparative example 1. As shown in FIG. 9, after the antioxidant is added, the tensile strength of the antioxidant polylactic acid composite material can be slightly reduced by BHT and AO2, and other hydrogenated cardanol-heterocyclic Schiff base compounds prepared by the method can be increased or kept unchanged, so that the mechanical properties of the antioxidant polylactic acid composite material are not greatly influenced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A hydrogenated cardanol-heterocyclic schiff base compound having a structure represented by formula I:
in the formula I, R has any one of the following structures:
2. the process for producing a hydrogenated cardanol-heterocyclic schiff base compound according to claim 1, comprising the steps of:
mixing cardanol, aldehyde, metal halide, an addition reaction catalyst and a solvent, and performing an addition reaction to obtain cardanol formaldehyde;
the cardanol formaldehyde, R-NH 2 Mixing the hydrogenated cardanol-heterocyclic Schiff base compound with a solvent, and carrying out Schiff base reaction to obtain the hydrogenated cardanol-heterocyclic Schiff base compound;
R-NH 2 r in (2) is the same as R in formula I.
3. The production method according to claim 2, wherein the aldehyde comprises one or more of aliphatic aldehyde, alicyclic aldehyde, aromatic aldehyde and terpene aldehyde;
the molar ratio of cardanol to aldehyde is 1:1 to 10; the aldehyde is calculated by the 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 molar ratio of the cardanol to the metal halide to the addition reaction catalyst is 1:1 to 15:1 to 15.
4. The method of claim 2, wherein the cardanol formaldehyde and R-NH 2 The molar ratio of (2) is 1:0.3 to 3.
5. The process according to any one of claims 2 to 4, wherein the temperature of the addition reaction and the schiff base reaction are independently 20 to 120 ℃ and the time is independently 0.5 to 48 hours.
6. Use of a hydrogenated cardanol-heterocyclic schiff base compound according to claim 1 for the preparation of an antioxidant.
7. An antioxidant high molecular composite material comprising a high molecular polymer and the hydrogenated cardanol-heterocyclic schiff base compound of claim 1; the high molecular polymer is polylactic acid.
8. The antioxidant polymer composite according to claim 7, wherein the mass fraction of the hydrogenated cardanol-heterocyclic schiff base compound in the antioxidant polymer composite is 0.05-5%.
9. 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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