CN108164750B - Hindered amine antioxidant and polyethylene material - Google Patents
Hindered amine antioxidant and polyethylene material Download PDFInfo
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- CN108164750B CN108164750B CN201611114276.8A CN201611114276A CN108164750B CN 108164750 B CN108164750 B CN 108164750B CN 201611114276 A CN201611114276 A CN 201611114276A CN 108164750 B CN108164750 B CN 108164750B
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 98
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 85
- -1 polyethylene Polymers 0.000 title claims abstract description 74
- 150000001412 amines Chemical class 0.000 title claims abstract description 55
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 40
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 6
- 235000013539 calcium stearate Nutrition 0.000 claims description 6
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- 239000011737 fluorine Substances 0.000 claims description 6
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 3
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- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019305 distearyl thiodipropionate Nutrition 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
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- 239000003017 thermal stabilizer Substances 0.000 claims 1
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- 230000003712 anti-aging effect Effects 0.000 abstract description 4
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- XFNJVKMNNVCYEK-UHFFFAOYSA-N 1-naphthaleneacetamide Chemical compound C1=CC=C2C(CC(=O)N)=CC=CC2=C1 XFNJVKMNNVCYEK-UHFFFAOYSA-N 0.000 description 13
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- 239000011259 mixed solution Substances 0.000 description 4
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- NRESDXFFSNBDGP-UHFFFAOYSA-N (4-bromophenyl)hydrazine Chemical compound NNC1=CC=C(Br)C=C1 NRESDXFFSNBDGP-UHFFFAOYSA-N 0.000 description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- ZSBLNRQSHLZWNV-UHFFFAOYSA-N n-(4-bromophenyl)prop-2-enamide Chemical compound BrC1=CC=C(NC(=O)C=C)C=C1 ZSBLNRQSHLZWNV-UHFFFAOYSA-N 0.000 description 3
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- FFJWPGGBISIFHI-UHFFFAOYSA-N 1-methylnaphthalen-2-amine Chemical compound C1=CC=C2C(C)=C(N)C=CC2=C1 FFJWPGGBISIFHI-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a hindered amine antioxidant and a polyethylene material, wherein the hindered amine antioxidant comprises the following structure (I):
wherein R is1Is alkyl, R2And R3Selected from hydrogen or the following general formula (II), and R2And R3At least one of them is selected from the following general formula (II):
wherein R is4Is a chain hydrocarbon group, R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15Independently selected from hydrogen or alkyl. The hindered amine antioxidant has good compatibility with polymers, good migration resistance and solvent extraction resistance, and can be applied to the anti-aging of various high polymer materials; and the hindered amine antioxidant has light color and is not easy to color.
Description
Technical Field
The invention relates to a hindered amine antioxidant and a polyethylene material, belonging to the technical field of organic chemistry.
Background
The antioxidant is an anti-aging agent commonly added in high polymer materials, can prevent the high polymer materials from losing service performance due to the action of heat and oxygen in the processing, storage and use processes, and commonly used antioxidants comprise hindered phenol antioxidants and hindered amine antioxidants, wherein the hindered amine antioxidants can prevent the high polymer materials from being oxidized thermally and also can prevent photooxidation, so the antioxidant is widely applied to the field of the high polymer materials.
At present, most of main antioxidants used in polyethylene materials are hindered phenol antioxidants, while amine antioxidants are generally easy to color and are not generally suitable for plastic products. However, amine antioxidants have more excellent antioxidant performance than hindered phenol antioxidants, and particularly, phenyl-2-naphthylamine antioxidants have more active hydrogen atoms and stronger capability of terminating free radicals due to the existence of electron-donating groups on benzene rings. Phenyl-2-naphthylamine has been widely used as a rubber antioxidant, but its use is limited due to its coloring property and toxicity. And the consumption proportion of the N, N' -di (2-naphthyl) -1, 4-phenylenediamine is continuously increased due to the advantages of excellent thermal aging resistance, natural aging resistance, low pollution and the like, and the phenylenediamine can be applied to engineering plastics such as ABS, polyformaldehyde, polyamide and the like.
In recent years, the market demand of high-end polyethylene materials is increasing, and research and development of high-end polyethylene materials are promoted. The problems of surface speckling and shaft winding are found in the development process of high-end polyethylene materials, which are mainly caused by the fact that hindered phenol antioxidants added in the polyethylene materials have high polarity, are poor in compatibility with the polyethylene materials and are easy to migrate to lose oxidation resistance; on the other hand, hindered phenol antioxidants are easy to hydrolyze, so that the capability of terminating free radicals is reduced, chain free radicals interact to generate crosslinking reaction, and gelation phenomenon occurs, so that the processability of the polyethylene material is reduced. In order to meet the requirement of developing high-end polyethylene materials, it is necessary to develop an antioxidant which has high compatibility and is difficult to hydrolyze.
Disclosure of Invention
The invention mainly aims to provide a hindered amine antioxidant and a polyethylene material, so as to solve the problems of poor compatibility and easy dissolution of the antioxidant in the prior art.
The object of the present invention is achieved by a hindered amine antioxidant comprising the following structure (I):
wherein R is1Is alkyl, R2And R3Selected from hydrogen or the following general formula (II), and R2And R3At least one of them is selected from the following general formula (II):
wherein R is4Is a chain hydrocarbon group, R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15Independently selected from hydrogen or alkyl.
The hindered amine antioxidant of the present invention, wherein R is1Is preferably an even number greater than 8.
The hindered amine antioxidant disclosed by the invention preferably has the following general formula:
wherein R is1Is alkyl, R1The number of carbon atoms is an even number greater than 8.
The invention also provides a polyethylene material, which contains the hindered amine antioxidant.
The polyethylene material of the invention comprises:
100 parts by mass of a polyethylene resin;
0.2-0.36 parts of composite auxiliary agent;
wherein the composite auxiliary agent comprises a main antioxidant, an auxiliary antioxidant, a heat stabilizer and a rheological agent; the main antioxidant is the hindered amine antioxidant.
The polyethylene material is characterized in that the auxiliary antioxidant is preferably one or more of a group consisting of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, dilauryl thiodipropionate and distearyl thiodipropionate.
The polyethylene material is characterized in that the heat stabilizer is one or more of calcium stearate, magnesium stearate, zinc stearate and aluminum stearate.
The polyethylene material of the invention, wherein the rheological agent is preferably a fluorine rheological agent.
The polyethylene material provided by the invention is characterized in that the mass ratio of the main antioxidant to the auxiliary antioxidant to the heat stabilizer to the rheological agent is preferably 1: 0.5-1.5: 0.25-0.75: 0.05-0.15.
The invention has the beneficial effects that:
1. the hindered amine antioxidant can be prepared by two simple organic reactions of amidation condensation and Michael addition reaction, and the reaction condition is mild.
2. The hindered amine antioxidant molecule not only contains two hindered amine antioxidant units, but also contains long-chain alkyl with good compatibility with high polymer materials, so that the hindered amine antioxidant has good compatibility with polymers, good migration resistance and solvent extraction resistance, and can be applied to the anti-aging of various high polymer materials; and the hindered amine antioxidant has light color and is not easy to color.
Drawings
FIG. 1 is an infrared spectrum of a hindered amine antioxidant prepared in example 1 of the present invention;
FIG. 2 is a mass spectrum of a hindered amine antioxidant prepared in example 1 of the present invention;
FIG. 3 is an infrared spectrum of a hindered amine antioxidant prepared in example 7 of the present invention;
FIG. 4 is a mass spectrum of a hindered amine antioxidant prepared in example 7 of the present invention;
FIG. 5 is an infrared spectrum of a hindered amine antioxidant prepared in example 8 of the present invention;
FIG. 6 is a mass spectrum of a hindered amine antioxidant prepared in example 8 of the present invention.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
The invention discloses a hindered amine antioxidant which can be prepared by the following method:
(1) synthesis of intermediate (I): firstly, dissolving a halogenated aniline compound and an accelerant N, N-diisopropylethylamine in tetrahydrofuran, dropwise adding an acyl halide compound at a low temperature (preferably-5 ℃), reacting for a certain time (preferably 3-7 h) at room temperature, and after the reaction is finished, adding a certain amount of saturated NH into the reaction mixture4Stopping the reaction with aqueous Cl solution, extracting the organic phase with ethyl acetate, and passing the supernatant over Na2SO4Drying followed by drying under vacuum provided intermediate (i).
(2) Synthesis of intermediate (ii): dissolving the intermediate (I) in ethanol, N2And (3) protecting, dropwise adding an ethanol solution of chain fatty amine at room temperature, reacting for 60-80 h at 70-90 ℃, concentrating the obtained reaction mixture under vacuum, and purifying the concentrate by silica gel column chromatography to obtain an intermediate (II).
(3) Synthesizing a hindered amine antioxidant: dissolving the intermediate (II) and the 2-naphthylamine compound in methanol, N2Adding catalysts XPhos and Pd under protection2(dba)3With an accelerator K2CO3Reacting for 5-10 h at 70-90 ℃ to obtain a crude hindered amine antioxidant product; dissolving the crude product by using a mixed solvent of ethyl acetate and tetrahydrofuran, washing the solution with water, and carrying out chromatography on the obtained organic phase to obtain the hindered amine antioxidant.
In the step (1), the molar ratio of the halogenated aniline compound to the acyl halide compound is 1: 1.1-1: 1.5, the dosage of the accelerator N, N-diisopropylethylamine is 40% of the total mass of the halogenated aniline compound and the acyl halide compound, the dosage of the solvent tetrahydrofuran is 10-15 times of the total mass of the halogenated aniline compound and the acyl halide compound, and the saturated NH is4The dosage of the Cl aqueous solution is 0.5-1 time of the volume of the reaction solvent, the dosage of the ethyl acetate is 0.8-1.2 times of the volume of the reaction solvent, the temperature of vacuum drying is 30 ℃, and the time of vacuum drying is 24 hours.
In the step (2), the molar ratio of the intermediate (I) to the chain fatty amine is 2:1, the dosage of the solvent ethanol is 9 times of the total mass of the intermediate (I) and the chain fatty amine, the reaction temperature is 70-90 ℃, and the reaction time is 60-80 hours; the vacuum concentration reaction temperature is 50 ℃, and the vacuum concentration reaction time is 5-10 h; the volume ratio of petroleum ether and ethyl acetate used as eluent for chromatography is 1: 10.
In the step (3), the molar ratio of the intermediate (II) to the 2-naphthylamine compound is 1: 2-1: 2.5, the using amount of the solvent methanol is 8-10 times of the total mass of the intermediate (II) and the 2-naphthylamine compound, and the promoter K is2CO3The molar ratio of the dosage to the intermediate (II) is 1: 7-1: 11, and the catalysts are XPhos and Pd2(dba)3The molar ratio of the used amount to the intermediate (II) is 1:10, and the reaction time is 5-10 h; the solvent ethyl acetate used for dissolving the crude product is used for reactionThe volume of the used solvent methanol is 0.5-1.5, and the volume ratio of petroleum ether and ethyl acetate used for eluent for chromatography is 5: 1.
Wherein the invention more specifically discloses an antioxidant
It can be prepared by the following method:
(1) para-bromoaniline and acryloyl chloride are subjected to substitution reaction to generate an intermediate (I);
(2) the intermediate (I) and chain fatty primary amine generate addition reaction of carbon-carbon double bonds to generate an intermediate (II); and
(3) the intermediate (II) and 2-naphthylamine are subjected to substitution reaction to generate a hindered amine antioxidant (III), and the specific reaction formula is as follows:
wherein R is12Is alkyl and has an even number of carbon atoms greater than 8.
The invention also discloses a polyethylene material, wherein the polyethylene material comprises:
100 parts by mass of a polyethylene resin;
0.2-0.36 parts of composite auxiliary agent;
wherein the composite auxiliary agent comprises a main antioxidant, an auxiliary antioxidant, a heat stabilizer and a rheological agent; the main antioxidant is the hindered amine antioxidant.
The polyethylene material of the invention can be prepared by the following method:
in the granulation section of polyethylene resin, adding polyethylene and a composite auxiliary agent with the mass of 1.5-5% of the polyethylene, wherein the composite auxiliary agent is prepared by mixing a main antioxidant, an auxiliary antioxidant, a heat stabilizer and a rheological agent according to the ratio of 1: 0.5-1.5: 0.25-0.75: 0.05-0.15 percent by mass, and the main antioxidant is the hindered amine antioxidant.
The auxiliary antioxidant is one or a mixture of any more of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, dilauryl thiodipropionate and distearyl thiodipropionate. The heat stabilizer is one or a mixture of any two of calcium stearate, magnesium stearate, zinc stearate and aluminum stearate. The rheological agent is a fluorine rheological fluid.
The technical solution of the present invention is explained in detail by the following specific examples.
Examples 1-6 involve reactions:
example 7 relates to the reaction:
example 8 relates to the reaction:
example 1
Synthesis of N- (4-bromophenyl) acryloyl chloride: 60g of p-bromoaniline and 67.6g N, N-diisopropylethylamine were accurately weighed and dissolved in 1.5L of tetrahydrofuran, 34.7g of acryloyl chloride was slowly added dropwise with stirring at 0 ℃, and the reaction was carried out at 25 ℃ for 4 hours. Adding saturated NH into the reaction mixture4Cl solution 1L, quench the reaction, then extract with 3L ethyl acetate, Na2SO4Dehydrating, filtering and drying in vacuum at 30 ℃ to obtain the N- (4-bromophenyl) acrylamide.
Synthesis of 3,3' dodecylamine-bis- (4-bromophenylhydrazine) amide: accurately weighing 60g N- (4-bromophenyl) acryloyl chloride, dissolving in 1.0L ethanol, and dissolving in N2Under protection, 24.6g of dodecylamine is slowly dropped while stirring at 25 ℃, and the reaction is carried out for 72 hours at 85 ℃. The mixed solution after reaction is concentrated in vacuum and purified by silica gel column chromatography, and the eluent petroleum ether and ethyl acetate are 10:1, so that 3,3' -dodecylamine-bis- (4-bromophenylhydrazine) amide is obtained.
3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminobenzene) Synthesis of propionamide: 32.5g of 3,3' -dodecylamine-bis- (4-bromophenylhydrazine) amide and 16.1g of 2-naphthylamine were accurately weighed and dissolved in 600mL of methanol, and 2.4g of XPhos and 28.2g of K were added2CO3And 4.7g of Pd2(dba)3，85℃、N2Reacting for 8 hours at constant temperature. The reaction mixture was concentrated in vacuo; the concentrate was diluted with 700mL of ethyl acetate at room temperature, filtered, washed 3 times with 700mL of distilled water, and dried under vacuum at 50 ℃. Purifying the obtained crude product by a silica gel column chromatography, wherein the eluent petroleum ether: the volume ratio of ethyl acetate is 5:1, and 3,3' -dodecylamine-di- (N- (4-naphthylacetamide) aminobenzene) propionamide is obtained.
The novel hindered amine antioxidant prepared in this example was characterized by infrared spectroscopy and mass spectrometry, and the results are shown in fig. 1 and 2.
As can be seen from fig. 1: wave number of 3340cm-1Is the stretching vibration absorption peak of N-H, and the wave number is 3045cm-1Is a characteristic absorption peak of C-H on a benzene ring, 1812cm-1The position is a broad-band absorption peak generated by the substitution of 1,4 positions of a benzene ring, and the wave number is 2950cm-1And 2922cm-1The characteristic absorption peaks of methyl and methylene respectively appear at the position of 2851cm-1And 2817cm-1The wave number is 1652cm, which is the stretching vibration peak of C-N-1The peak is the absorption peak of the amide bond C ═ O in the stretching vibration. As can be seen from fig. 2, m/z-762.6 is a molecular ion peak of the novel hindered amine antioxidant.
3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminobenzene) propionamide, tris (2, 4-di-tert-butylphenyl) phosphite were mixed in the following ratio of 1:1, stirring at room temperature, mixing for 5-20 minutes, and then sending into a powder extruder for extrusion to obtain the composite additive containing the antioxidant 3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminophenyl) propionamide.
In the granulating section of polyethylene, 0.2% of the above-mentioned compound adjuvant is added, and passed through the extruder to make melt extrusion, wire-drawing and granulating. The polyethylene resin was then tested for melt flow rate, mechanical properties, and oxidation induction period. The results of the physical property test of the polyethylene resin are shown in Table 1.
Example 2
3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminophenyl) propionamide was synthesized according to the reaction in example 1. 3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminophenyl) propionamide, tris (2, 4-di-t-butylphenyl) phosphite, calcium stearate, zinc stearate and fluorine rheology were adjusted in the following manner: 1: 0.5: 0.5: and (3) putting the mixture into a high-speed mixing roll according to the mass ratio of 0.1, stirring the mixture at room temperature, mixing the mixture for 5 to 20 minutes, and then sending the mixture into a powder extruder for extrusion to obtain the composite additive package containing the antioxidant 3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminobenzene) propionamide.
In the granulating section of polyethylene, 0.31% of the above-mentioned compound adjuvant is added, and passed through the extruder to make melt extrusion, wire-drawing and granulating. The polyethylene resin was then tested for melt flow rate, mechanical properties, and oxidation induction period. The results of the physical property test of the polyethylene resin are shown in Table 1.
Example 3
3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminophenyl) propionamide was synthesized according to the reaction in example 1. 3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminophenyl) propionamide, tris (2, 4-di-t-butylphenyl) phosphite, calcium stearate, zinc stearate and fluorine rheology were adjusted in the following manner: 1: 0.75: 0.75: and (3) putting the mixture into a high-speed mixing roll according to the mass ratio of 0.1, stirring the mixture at room temperature, mixing the mixture for 5 to 20 minutes, and then sending the mixture into a powder extruder for extrusion to obtain the composite additive package containing the antioxidant 3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminobenzene) propionamide.
In the granulating section of polyethylene, 0.36% of the above-mentioned compound adjuvant is added, and passed through the extruder to make melt extrusion, wire-drawing and granulating. The polyethylene resin was then tested for melt flow rate, mechanical properties, and oxidation induction period. The results of the physical property test of the polyethylene resin are shown in Table 1.
Example 4
3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminophenyl) propionamide was synthesized according to the reaction in example 1. 3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminobenzene) propionamide, calcium stearate, zinc stearate and fluorine rheological variants were mixed in the following ratio 1: 0.5: 1: and (3) putting the mixture into a high-speed mixing roll according to the mass ratio of 0.1, stirring the mixture at room temperature, mixing the mixture for 5 to 20 minutes, and then sending the mixture into a powder extruder for extrusion to obtain the composite additive package containing the antioxidant 3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) aminobenzene) propionamide.
In the granulating section of polyethylene, 0.26% of the above-mentioned compound adjuvant is added, and passed through the extruder to make melt extrusion, wire-drawing and granulating. The polyethylene resin was then tested for melt flow rate, mechanical properties, and oxidation induction period. The results of the physical property test of the polyethylene resin are shown in Table 1.
Example 5
N- (4-bromophenyl) acryloyl chloride was synthesized according to the reaction in example 1. Accurately weighing 60g N- (4-bromophenyl) acryloyl chloride, dissolving in 1.0L ethanol, and dissolving in N2Under protection, 28.3g of tetradecylamine is slowly added dropwise while stirring at 25 ℃, and the reaction is carried out for 72 hours at 85 ℃. The mixed solution after reaction is concentrated in vacuum and purified by silica gel column chromatography, and the eluent petroleum ether and ethyl acetate are 10:1, so that 3,3' tetradecylamine-bis- (4-bromophenylhydrazine) amide is obtained.
Synthesis of 3,3' -tetradecylamine-bis- (N- (4-naphthylacetamide) aminophenyl) propionamide: 33.9g of 3,3' -tetradecylamine-bis- (4-bromophenylhydrazine) amide and 16.1g of 2-naphthylamine were accurately weighed and dissolved in 600mL of methanol, and 2.4g of XPhos and 28.2g of K were added2CO3And 4.7g of Pd2(dba)3，85℃、N2Reacting for 8 hours at constant temperature. The reaction mixture was concentrated in vacuo; the concentrate was diluted with 700mL of ethyl acetate at room temperature, filtered, washed 3 times with 700mL of distilled water, and dried under vacuum at 50 ℃. Purifying the obtained crude product by a silica gel column chromatography, wherein the eluent petroleum ether: the volume ratio of ethyl acetate was 5: 1.
3,3' -tetradecylamine-bis- (N- (4-naphthylacetamide) aminophenyl) propionamide, tris (2, 4-di-tert-butylphenyl) phosphite were mixed in the following ratio of 1:1, stirring at room temperature, mixing for 5-20 minutes, and then sending into a powder extruder for extrusion to obtain the composite additive containing the antioxidant 3,3' -decatetramine-di- (N- (4-naphthylacetamide) aminophenyl) propionamide.
In the granulating section of polyethylene, 0.2% of the above-mentioned compound adjuvant is added, and passed through the extruder to make melt extrusion, wire-drawing and granulating. The polyethylene resin was then tested for melt flow rate, mechanical properties, and oxidation induction period. The results of the physical property test of the polyethylene resin are shown in Table 1.
Example 6
N- (4-bromophenyl) acryloyl chloride was synthesized according to the synthetic reaction in example 1. Accurately weighing 60g N- (4-bromophenyl) acryloyl chloride, dissolving in 1.0L ethanol, and dissolving in N2And (3) protecting, slowly dropwise adding 35.7g of octadecylamine while stirring at the temperature of 25 ℃, and reacting for 72 hours at the temperature of 85 ℃. The mixture after reaction was concentrated in vacuo and purified by silica gel column chromatography, and the eluent petroleum ether and ethyl acetate were 10:1, to give 3,3' octadecylamine-bis- (4-bromophenylhydrazine) amide.
Synthesis of 3,3' -octadecylamine-bis- (N- (4-naphthylacetamide) aminophenyl) propionamide: accurately weighed 36.7g of 3,3' octadecylamine-bis- (4-bromophenylhydrazine) amide and 16.1g of 2-naphthylamine were dissolved in 600mL of methanol, followed by addition of 2.4g of XPhos and 28.2g of K2CO3And 4.7g of Pd2(dba)3，85℃、N2Reacting for 8 hours at constant temperature. The reaction mixture was concentrated in vacuo; the concentrate was diluted with 700mL of ethyl acetate at room temperature, filtered, washed 3 times with 700mL of distilled water, and dried under vacuum at 50 ℃. Purifying the obtained crude product by a silica gel column chromatography, wherein the eluent petroleum ether: the volume ratio of ethyl acetate was 5: 1.
Mixing 3,3' -octadecylamine-bis- (N- (4-naphthylacetamide) aminobenzene) propionamide and tris (2, 4-di-tert-butylphenyl) phosphite according to the weight ratio of 1:1, stirring at room temperature, mixing for 5-20 minutes, and then sending into a powder extruder for extrusion to obtain the compound additive containing the antioxidant 3,3' -octadecylamine-di- (N- (4-naphthylacetamide) aminophenyl) propionamide.
In the granulating section of polyethylene, 0.2% of the above-mentioned compound adjuvant is added, and passed through the extruder to make melt extrusion, wire-drawing and granulating. The polyethylene resin was then tested for melt flow rate, mechanical properties, and oxidation induction period. The results of the physical property test of the polyethylene resin are shown in Table 1.
Example 7
Synthesis of N- (4-bromophenyl) acrylamide: accurately weighing 60g of p-bromoaniline and 67g of p-bromoaniline6g N, dissolving N-diisopropylethylamine in 1.5L tetrahydrofuran, slowly adding acryloyl chloride 34.7g dropwise while stirring at 0 ℃, and reacting at 25 ℃ for 4 h. Adding saturated NH into the reaction mixture4Cl solution 1L, quench the reaction, then extract with 3L ethyl acetate, Na2SO4Dehydrating, filtering and drying in vacuum at 30 ℃ to obtain the N- (4-bromophenyl) acrylamide.
Synthesis of 3,3' -dodecylamine-bis- (4-bromophenylhydrazine) propionamide: accurately weighing 60g N- (4-bromophenyl) acryloyl chloride, dissolving in 1.0L ethanol, and dissolving in N2Under protection, 24.6g of dodecylamine is slowly dropped while stirring at 25 ℃, and the reaction is carried out for 72 hours at 85 ℃. The mixed solution after reaction is concentrated in vacuum and purified by silica gel column chromatography, and the eluent petroleum ether and ethyl acetate are 10:1, so that 3,3' -dodecylamine-bis- (4-bromophenylhydrazine) propionamide is obtained.
Synthesis of 3,3' -dodecylamine-bis- (N- (1-methyl-4-naphthylacetamide) aminophenyl) propionamide: 32.5g of 3,3' -dodecylamine-bis- (4-bromophenylhydrazine) propionamide and 17.6g of 1-methyl-2-naphthylamine were accurately weighed and dissolved in 600mL of methanol, and then 2.4g of XPhos and 28.2g of K were added2CO3And 4.7g of Pd2(dba)3，85℃、N2Reacting for 8 hours at constant temperature. The reaction mixture was concentrated in vacuo; the concentrate was diluted with 700mL of ethyl acetate at room temperature, filtered, washed 3 times with 700mL of distilled water, and dried under vacuum at 50 ℃. Purifying the obtained crude product by a silica gel column chromatography, wherein the volume ratio of petroleum ether to ethyl acetate serving as eluent is 5:1, so as to obtain the 3,3' -dodecylamine-bis- (N- (1-methyl-4-naphthylacetamide) aminobenzene) propionamide.
The novel hindered amine antioxidant prepared in this example was characterized by infrared spectroscopy and mass spectrometry, and the results are shown in fig. 3 and 4.
As can be seen from fig. 3: 3340cm-1Is the stretching vibration absorption peak of N-H, and the wave number is 3045cm-1Is a characteristic absorption peak of C-H on a benzene ring, 1811cm-1The wave number is 2950cm-1And 2920cm-1The characteristic absorption peaks of methyl and methylene respectively appear at the positions of 2850cm-1And 2810cm-1Is C-N telescopicPeak of vibration, wave number 1655cm-1The peak is the absorption peak of the amide bond C ═ O in the stretching vibration. As can be seen from fig. 4, m/z 789 is the molecular ion peak of the novel hindered amine antioxidant synthesized in example 3.
3,3' -dodecylamine-bis- (N- (1-methyl-4-naphthylacetamide) aminophenyl) propionamide, tris (2, 4-di-tert-butylphenyl) phosphite were mixed in the following ratio of 1:1, stirring at room temperature, mixing for 5-20 minutes, and then sending into a powder extruder for extrusion to obtain the composite additive containing the antioxidant 3,3' -dodecylamine-bis- (N- (1-methyl-4-naphthylacetamide) aminobenzene) propionamide.
In the granulating section of polyethylene, 0.2% of the above-mentioned compound adjuvant is added, and passed through the extruder to make melt extrusion, wire-drawing and granulating. The polyethylene resin was then tested for melt flow rate, mechanical properties, and oxidation induction period. The results of the physical property test of the polyethylene resin are shown in Table 1.
Example 8
Synthesis of N- (2-methyl-4-bromophenyl) acrylamide: 65g of 2-methyl-4-bromoaniline and 67.6g N, N-diisopropylethylamine were accurately weighed and dissolved in 1.5L of tetrahydrofuran, 34.7g of acryloyl chloride was slowly added dropwise with stirring at 0 ℃ and reacted for 4 hours at 25 ℃. Adding saturated NH into the reaction mixture4Cl solution 1L, quench the reaction, then extract with 3L ethyl acetate, Na2SO4Dehydrating, filtering and drying in vacuum at 30 ℃ to obtain the N- (2-methyl-4-bromophenyl) acrylamide.
Synthesis of 3,3' -dodecylamine-bis- (2-methyl-4-bromophenylhydrazine) propionamide: 67g N- (2-methyl-4-bromophenyl) acryloyl chloride was accurately weighed and dissolved in 1.0L ethanol, N2Under protection, 24.6g of dodecylamine is slowly dropped while stirring at 25 ℃, and the reaction is carried out for 72 hours at 85 ℃. The mixed solution after reaction is concentrated in vacuum and purified by silica gel column chromatography, and the eluent petroleum ether and ethyl acetate are 10:1, so that 3,3' -dodecylamine-bis- (2-methyl-4-bromophenylhydrazine) propionamide is obtained.
Synthesis of 3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) 2-methylaminobenzene) propionamide: 34.5g of 3,3' -dodecylamine-bis- (2-methyl-4-bromophenylhydrazine) propionamide and 17.6g of 1-methyl-2-naphthalene are accurately weighedThe amine was dissolved in 600mL of methanol, then 2.4g XPhos, 28.2g of K were added2CO3And 4.7g of Pd2(dba)3，85℃、N2Reacting for 8 hours at constant temperature. The reaction mixture was concentrated in vacuo; the concentrate was diluted with 700mL of ethyl acetate at room temperature, filtered, washed 3 times with 700mL of distilled water, and dried under vacuum at 50 ℃. Purifying the obtained crude product by a silica gel column chromatography, wherein the volume ratio of petroleum ether to ethyl acetate serving as eluent is 5:1, so as to obtain the 3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) 2-methylaminophenyl) propionamide.
As can be seen from fig. 5: wave number is 3342cm-1Is the stretching vibration absorption peak of N-H, and the wave number is 3047cm-1Is a characteristic absorption peak of C-H on a benzene ring, 1810cm-1The wave number is 2952cm-1And 2920cm-1The characteristic absorption peaks of methyl and methylene respectively appear at the positions of 2855cm-1And 2819cm-1The wave number is 1650cm, which is the stretching vibration peak of C-N-1The peak is the absorption peak of the amide bond C ═ O in the stretching vibration. As can be seen from fig. 6, m/z 819 is a molecular ion peak of the novel hindered amine antioxidant synthesized in example 2.
3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) 2-methylaminobenzene) propionamide, tris (2, 4-di-tert-butylphenyl) phosphite were mixed in the following ratio of 1:1, stirring at room temperature, mixing for 5-20 minutes, and then sending into a powder extruder for extrusion to obtain the composite additive containing the antioxidant 3,3' -dodecylamine-bis- (N- (4-naphthylacetamide) 2-methylaminophenyl) propionamide.
In the granulating section of polyethylene, 0.2% of the above-mentioned compound adjuvant is added, and passed through the extruder to make melt extrusion, wire-drawing and granulating. The polyethylene resin was then tested for melt flow rate, mechanical properties, and oxidation induction period. The results of the physical property test of the polyethylene resin are shown in Table 1.
Comparative example 1
Pentaerythritol [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite were mixed in the following ratio of 1:1, stirring at room temperature, mixing for 5-20 minutes, and then sending into a powder extruder for extrusion to obtain the composite additive containing the antioxidant [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
In the granulating section of polyethylene, 0.2% of the above-mentioned compound adjuvant is added, and passed through the extruder to make melt extrusion, wire-drawing and granulating. The polyethylene resin was then tested for melt flow rate, mechanical properties, and oxidation induction period. The results of the physical property test of the polyethylene resin are shown in Table 1.
Comparative example 2
1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and tris (2, 4-di-tert-butylphenyl) phosphite were mixed in the following ratio of 1:1, stirring at room temperature, mixing for 5-20 minutes, and then sending into a powder extruder for extrusion to obtain the composite additive package containing the antioxidant 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
In the granulating section of polyethylene, 0.2% of the above-mentioned compound adjuvant is added, and passed through the extruder to make melt extrusion, wire-drawing and granulating. The polyethylene resin was then tested for melt flow rate, mechanical properties, and oxidation induction period. The results of the physical property test of the polyethylene resin are shown in Table 1.
TABLE 1 analytical test results for polyethylene resins
The polyethylene resins obtained in examples 1 to 7 are different from those in comparative examples 1 and 2 only in the use of antioxidant, and as can be seen from the data in Table 1, the antioxidant used in the examples can significantly improve the oxidation induction period of the polyethylene resin, so that the polyethylene resin has excellent antioxidant performance.
The invention has the beneficial effects that:
1. the hindered amine antioxidant can be prepared by two simple organic reactions of amidation condensation and Michael addition reaction, and the reaction condition is mild.
2. The hindered amine antioxidant molecule not only contains two hindered amine antioxidant units, but also contains long-chain alkyl with good compatibility with high polymer materials, so that the hindered amine antioxidant has good compatibility with polymers, good migration resistance and solvent extraction resistance, and can be applied to the anti-aging of various high polymer materials; and the hindered amine antioxidant has light color and is not easy to color.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A hindered amine antioxidant, characterized in that the hindered amine antioxidant comprises the following structure (I):
wherein R is1Is alkyl, R1Has an even number of carbon atoms greater than 8, R2And R3Has the following general formula (II):
wherein R is4Is a chain hydrocarbon group, R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15Independently selected from hydrogen or alkyl.
2. The hindered amine antioxidant of claim 1, wherein the hindered amine antioxidant has the general formula:
wherein R is1Is alkyl, R1The number of carbon atoms is an even number greater than 8.
3. A polyethylene material comprising the hindered amine antioxidant of any one of claims 1-2.
4. A polyethylene material according to claim 3, characterised in that it comprises:
100 parts by mass of a polyethylene resin;
0.2-0.36 parts of composite auxiliary agent;
wherein the composite auxiliary agent comprises a main antioxidant, an auxiliary antioxidant, a heat stabilizer and a rheological agent; the primary antioxidant is the hindered amine antioxidant according to any one of claims 1 to 3.
5. The polyethylene material according to claim 4, wherein the auxiliary antioxidant is one or more selected from the group consisting of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, dilauryl thiodipropionate and distearyl thiodipropionate.
6. The polyethylene material according to claim 4, wherein the heat stabilizer is one or more selected from the group consisting of calcium stearate, magnesium stearate, zinc stearate and aluminum stearate.
7. The polyethylene material of claim 4, wherein the rheological agent is a fluorine rheological agent.
8. The polyethylene material according to any one of claims 4 to 7, wherein the mass ratio of the primary antioxidant to the secondary antioxidant to the thermal stabilizer to the rheological agent is 1: 0.5-1.5: 0.25-0.75: 0.05-0.15.
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