CN116478451A - Antioxidant with light stability and thermo-oxidative aging resistance and preparation method thereof - Google Patents
Antioxidant with light stability and thermo-oxidative aging resistance and preparation method thereof Download PDFInfo
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 41
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 36
- 230000032683 aging Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000004952 Polyamide Substances 0.000 claims abstract description 15
- 229920002647 polyamide Polymers 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 98
- 238000006243 chemical reaction Methods 0.000 claims description 68
- 238000004821 distillation Methods 0.000 claims description 50
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 239000011261 inert gas Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 20
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 13
- -1 benzamide compound Chemical class 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- YIPHYCQSJTXLFM-UHFFFAOYSA-N 4-hydroxybenzoyl chloride Chemical compound OC1=CC=C(C(Cl)=O)C=C1 YIPHYCQSJTXLFM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001805 chlorine compounds Chemical class 0.000 claims description 6
- 150000003936 benzamides Chemical class 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 230000009435 amidation Effects 0.000 claims description 2
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 238000003878 thermal aging Methods 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001412 amines Chemical group 0.000 abstract description 2
- 150000001408 amides Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 43
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 13
- AIPCSKRJJOUNEM-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzoyl chloride Chemical compound CC(C)(C)C1=CC(C(Cl)=O)=CC(C(C)(C)C)=C1O AIPCSKRJJOUNEM-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- YEXOWHQZWLCHHD-UHFFFAOYSA-N 3,5-ditert-butyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1O YEXOWHQZWLCHHD-UHFFFAOYSA-N 0.000 description 7
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 239000004611 light stabiliser Substances 0.000 description 7
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- VTEDMSWWQJHBBP-UHFFFAOYSA-N 2-dodecylbenzamide Chemical compound CCCCCCCCCCCCC1=CC=CC=C1C(N)=O VTEDMSWWQJHBBP-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
The invention discloses an antioxidant with light stability and thermal oxidative aging resistance and a preparation method thereof, and the product contains hindered phenol and hindered amine structures and has an amide structure, so that the product has excellent compatibility in polyamide and can effectively improve the ageing resistance of the polyamide.
Description
Technical Field
The invention belongs to the field of organic synthesis, and relates to a synthesis process of an antioxidant, which mainly relates to a synthesis method of a 6-amino-N- (2, 6-tetramethyl-4-piperidine) - (ethyl-dodecyl) amide and a 4-hydroxy-alpha, alpha-dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] ethyl-dodecyl ] benzamide compound.
Background
Polyamides are one of five general-purpose engineering plastics that have wide applications in a variety of fields, such as: medical devices, electrical electronics, automobiles, machinery, textiles, and the like. Polyamide raw materials generally exhibit an opaque pale white color and, after oxidation, generally exhibit a yellow, orange and severe reddish brown color, which not only results in a poor appearance of the material, but also causes a sharp decay in the material properties. The addition of the antioxidant can effectively prolong the oxidation period of the polyamide material and reduce the performance loss of the polyamide material. Antioxidants for polyamides, including basf and dow, have also been developed and suitable anti-thermo-oxidative aging agents for polyamides such as 1098, 1010, 1076, and light stabilizers such as 445, 622, 770 have been developed, but there are few references to antioxidants having both anti-thermo-oxidative aging and photo-stability.
He Liming, once et al provide a bisphenol compound synthesized from 2, 6-di-tert-butyl-phenol as a hindered phenol starting material, which requires the addition of various dehydrating agents and has a final efficiency of not more than 70%. The steps are complicated. Meanwhile, the related reactions such as organic solvents and the like are more in participation types, and the steps are complicated.
Liu Junli, zhao Hanjiang and the like provide three synthesis methods of novel structure hindered phenol antioxidants based on 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid, which synthesize various monophenols, bisphenols and polyphenol antioxidants through an organic solvent and aluminum isopropoxide, and the whole method is simpler, but the method has metal elements, which can cause the occurrence of metal ion complexes and the aggravation of oxidation reaction, and the method only describes the synthesis of the antioxidants, and does not evaluate and compare the antioxidant capacity.
Li Keguo, zhang Huijing et Al provide a method of synthesizing a hindered amine light stabilizer containing a hindered phenol structure by adding a supported catalyst MF/gamma-ai 2O3, a supported tin tetrachloride catalyst to carry out the reaction. Compared with the prior synthetic route, the method has better simplification, but has the problems of easy failure after the catalyst is synthesized, higher reaction temperature and multiple organic reagents involved.
Disclosure of Invention
Aiming at the current situation that the current antioxidant has no heat and oxygen resistance and light stability, the invention provides 4-hydroxy-alpha, alpha-dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] ethyl-dodecyl ] benzamide compounds with simple method, higher yield, mild reaction conditions and simple steps and a synthesis method thereof.
In one aspect, the present invention provides an antioxidant having light stability and resistance to thermo-oxidative aging, having the structure shown below:
wherein n is an integer from 1 to 11, wherein R is independently selected from groups having electron-donating effect such as methyl, disubstituted methyl, isobutyl, tert-butyl, preferably tert-butyl groups.
On the other hand, the invention also provides a preparation method of the antioxidant, and the synthetic route comprises the following steps:
(1) Acid chlorination reaction:
(2) Amidation of 4-amino-2, 6-tetramethylpiperidine:
(3) Synthesis of 4-hydroxy- α, α -dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidyl) amino ] ethyl-dodecyl ] benzamide compound:
in the invention, the preparation method comprises the following steps: (1) Synthesizing w-aminoacyl chloride and p-hydroxybenzoyl chloride compounds; (2) Synthesizing 6-amino-N- (2, 6-tetramethyl-4-piperidine) - (ethyl-dodecyl) amide; (3) synthesis of antioxidant.
Wherein:
the w-amino acid has the following structureWherein n is a carbon number of 1 to 11;
w-aminoacyl chloride has the following structure:
wherein n is a carbon number of 1 to 11;
the parahydroxybenzoic acid compound has the following structure:wherein R is independently selected from groups having electron-donating effect such as methyl, disubstituted methyl, isobutyl, tert-butyl, preferably tert-butyl groups.
The parahydroxybenzoyl chloride compound has the following structure：Wherein R is independently selected from groups having electron-donating effect such as methyl, disubstituted methyl, isobutyl, tert-butyl, preferably tert-butyl groups.
The step (1) comprises the following steps: tetrahydrofuran is used as a solvent, a small amount of triethylamine is used as an acid binding agent, triphosgene is dissolved and then mixed with w-amino acid or a p-hydroxybenzoic acid compound, under the condition of inert gas circulation and stirring, temperature rising reaction is carried out, reduced pressure distillation is carried out after the reaction is finished, and residues are collected to obtain w-amino acyl chloride and a p-hydroxybenzoyl chloride compound;
the feeding ratio of the raw materials in the step (1) is as follows: w-amino acid/p-hydroxybenzoic acid compound: triphosgene: triethylamine = 30:10 to 15: 3-6, respectively dissolving w-amino acid/p-hydroxybenzoic acid compound in THF solution.
In the invention, the concentration of the reaction solvent THF is 99.5 percent (AR analytical purity), the concentration of triphosgene is 99 percent, the temperature rise reaction temperature is 25-40 ℃, and the reaction time is 2-3 hours; the reduced pressure distillation temperature is 50-60 ℃, the negative pressure intensity is 0.05-0.1 MPa, the yield of the w-aminoacyl chloride and the parahydroxybenzoyl chloride compound is more than 92%, and the purity is more than or equal to 94%.
The step (2) comprises the following steps: diluting 4-amino-2, 6-tetramethylpiperidine in THF under inert gas to obtain 4-amino-2, 6-tetramethylpiperidine solution, and dripping w-aminoacyl chloride prepared in the step (1) into 4-amino-2, 6-tetramethylpiperidine solution for reaction, the duration is 1-2 h, the reaction time is 1-3 h, stirring is kept during the reaction, the solution is distilled under reduced pressure after the reaction is completed, and residues are collected, wherein the residues are 6-amino-N- (2, 6-tetramethyl-4-piperidine) - (ethyl-dodecyl) amide;
the raw materials in the step (2) are mixed according to the following proportion: w-aminoacyl chloride: 4-amino-2, 6-tetramethylpiperidine=0.98 to 1.02:1, 4-amino-2, 6-tetramethylpiperidine was dissolved in THF.
In the invention, the dripping time is 1-2 h, the reaction temperature is 0-5 ℃, the reaction time is 1-3 h, the reduced pressure distillation temperature is 50-60 ℃, the negative pressure intensity is 0.05-0.1 MPa, the synthesis yield of 6-amino-N- (2, 6-tetramethyl-4-piperidine) - (ethyl-dodecyl) amide is more than 93%, and the purity is more than 97%.
The step (3) comprises the following steps: diluting 6-amino-N- (2, 6-tetramethyl-4-piperidine) - (ethyl-dodecyl) amide in THF, slowly dripping the parahydroxybenzoyl chloride compound into the THF under the protection of inert gas, keeping stirring, carrying out reduced pressure distillation on the solution after the reaction is completed, and collecting residues, wherein the residues are 4-hydroxy-alpha, alpha-dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] ethyl-dodecyl ] benzamide compounds.
The dropping time is 1-2 h, the reaction temperature is 0-5 ℃, the reaction time is 2-4h, the reduced pressure distillation temperature is 50-60 ℃, the negative pressure intensity is 0.05-0.1 MPa, the residual 4-hydroxy-alpha, alpha-dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] ethyl-dodecyl ] benzamide compound is light white solid powder, the yield is more than or equal to 95%, the purity is more than 97%, and the color deepening phenomenon can occur after the compound is placed in the air for a long time.
The feeding ratio of the raw materials in the step (3) is as follows: 6-amino-N- (2, 6-tetramethyl-4-piperidine) - (ethyl-dodecyl) amide: parahydroxybenzoyl chloride compound=1: 1 to 1.05, 6-amino-N- (2, 6-tetramethyl-4-piperidine) - (ethyl-dodecyl) amide is dissolved or dispersed in THF solution.
The specific synthetic route of the invention is as follows:
the yield of the synthesized final product can reach more than 95%, and the yield is calculated as follows:
where I is the yield (%), M is the mass (G) of the product G produced, n is the molar amount (mol) of the reactant F or D, and M is the molar mass (G/mol) of the product G.
Finally, the invention also provides application of the antioxidant in a polyamide composition, wherein the polyamide composition comprises polyamide marks such as PA6 and the like, about 0.05-0.55% of the antioxidant synthesized by the invention is added, and 0.05-0.5% of S9228 phosphite antioxidants are compounded, wherein the preferable combination is 0.2-0.4% of the antioxidant compounded by the invention, 0.1-0.3% of the S9228 antioxidant is compounded, and the more preferable combination is 0.25% of the antioxidant compounded by the invention, and 0.2% of the S9228 antioxidant is compounded.
Compared with the prior antioxidant, the invention has the following advantages:
1) The synthetic route is simple and convenient, and no obvious waste liquid hazard exists;
2) The yield is high, and the product collection rate can reach more than 95 percent;
3) Realizing the recycling of the reaction solvent;
4) The antioxidant effect is obviously better than that of the existing antioxidant, and the yellowness index is obviously reduced after thermal oxidation aging.
Drawings
FIG. 1 is an infrared spectrum of product G in example 5 of the present invention
Detailed Description
The synthesis and performance of the 4-hydroxy-alpha, alpha-dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidyl) amino ] ethyl-dodecyl ] benzamide compounds of the present invention are further described below by way of some specific examples. 3, 5-di-tert-butyl-4-hydroxy-alpha, alpha-dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidyl) amino ] hexyl ] benzamide, 3, 5-di-tert-butyl-4-hydroxy-alpha, the synthesis of α -dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidyl) amino ] nonyl ] benzamide, 3, 5-di-tert-butyl-4-hydroxy- α, α -dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidyl) amino ] dodecyl ] benzamide is exemplified.
It should be noted that the following examples of the present invention are given by way of example only with w-aminocaproic acid, w-aminononanoic acid, w-aminododecanoic acid, and are not intended to limit the scope of the present invention, and that various modifications or adaptations of the present invention may occur to persons skilled in the art after reading the present disclosure, and that these equivalents fall within the scope of the present application as defined in the claims appended hereto.
Unless otherwise specified, reagents, raw materials, and the like involved in the present invention are commercially available common raw materials:
w-aminocaproic acid/w-aminononanoic acid/w-aminododecanoic acid: the purity of Shanghai Ala Latin Biochemical technology Co., ltd is more than 98%;
3, 5-di-tert-butyl-p-hydroxybenzoic acid, shanghai Ala Biochemical technology Co., ltd., purity > 98%;
tetrahydrofuran: AR analytical purity, purity > 99% by Shanghai Michlin Biochemical technologies Co., ltd;
triethylamine: AR analytical purity, purity > 99% by merck, germany;
triphosgene: shanghai Ala Biochemical technology Co., ltd, purity > 99%;
4-amino-2, 6-tetramethylpiperidine: the purity of Shanghai Ala Latin Biochemical technology Co., ltd is more than 98%;
NaOH: the purity of the pharmaceutical product of national pharmaceutical group is higher than 96 percent.
Example 1
(1) W-aminocaproic acid (30 mmol,3.93 g) and 3, 5-di-tert-butyl-p-hydroxybenzoic acid (30 mmol,7.5 g) were dispersed in THF (40 mL) solution, a small amount of triethylamine (3 mmol,0.3 g) was added, triphosgene (10 mmol,2.97 g) was dissolved in THF solution (40 mL), and the mixture was dropped into the solution using a constant pressure dropping funnel, while keeping inert gas flow and stirring, the reaction time was 1h, the reaction temperature was 25 ℃, and after the completion, the distillation under reduced pressure gave residual solutions of w-aminocaproyl chloride and 3, 5-di-tert-butyl-p-hydroxybenzoyl chloride, both in yields of > 89%, purity > 92%, the distillation temperature was 55 ℃, and the liquid after the distillation was collected after the distillation was subjected to negative pressure again to be used as a subsequent experimental solvent.
(2) 4-amino-2, 6-tetramethylpiperidine (25 mmol,3.9 g) was mixed with THF, w-aminocaproyl chloride (25.5 mmol,3.81 g) was slowly dropped into the mixed solution using a constant pressure dropping funnel for 1h at a reaction temperature of 5℃under stirring while keeping inert gas flow, and after completion of the reaction, the residue was distilled under reduced pressure to give 6-amino-N- (2, 6-tetramethyl-4-piperidine) -hexanamide, the reduced distillation temperature was 55℃and the yield was > 84.2% and the purity was > 89%. The liquid after distillation is collected after the negative pressure is carried out again and is used as a solvent for the subsequent experiment.
(3) 3, 5-Di-tert-butyl-p-hydroxybenzoyl chloride (25.5 mmol,6.375 g) was dissolved in THF (40 mL), followed by slowly dropping a solution of 6-amino-N- (2, 6-tetramethyl-4-piperidine) -hexanamide (25 mmol,6.725 g) in THF (40 mL) using a constant pressure dropping funnel, followed by maintaining inert gas flow and stirring for 1 hour, the reaction time was 2 hours, the reaction temperature was 5 ℃, and distillation under reduced pressure was completed to obtain a residual solution of 3, 5-di-tert-butyl-4-hydroxy- α, α -dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] hexyl ] benzamide, the final product yield was > 90.4%, purity > 93%.
Example 2
(1) W-aminododecanoic acid (30 mmol,6.45 g) and 3, 5-di-tert-butyl-p-hydroxybenzoic acid (30 mmol,7.5 g) were respectively dispersed in THF (40 mL), a small amount of triethylamine (4 mmol,0.404 g) was added, triphosgene (12 mmol,3.56 g) was dissolved in THF (40 mL) and was dropped into the mixed solution using a constant pressure dropping funnel, inert gas flow and stirring were maintained during the period, the reaction time was 2.5h, the reaction temperature was 30℃and after the completion of the distillation under reduced pressure, the residual liquids were w-aminododecanoyl chloride and 3, 5-di-tert-butyl-p-hydroxybenzoyl chloride, the yields were > 95%, the purity > 97%, the distillation temperature was 55℃and the liquid after the distillation was collected by distillation under negative pressure was used as a subsequent experimental solvent.
(2) 4-amino-2, 6-tetramethylpiperidine (25 mmol,3.9 g) was mixed with THF, w-aminododecyl chloride (25.5 mmol,6.43 g) was slowly dropped into the mixed solution using a constant pressure dropping funnel for 1.5h, the reaction temperature was 5℃and inert gas was kept flowing and stirring, the reaction was carried out for 1h, and after completion, distillation under reduced pressure was carried out to obtain a residual solution, namely 6-amino-N- (2, 6-tetramethyl-4-piperidine) -dodecylamide, the distillation temperature was 55℃and the final yield was > 95% and the purity was > 97.5%. The liquid after distillation is collected after the negative pressure is carried out again and is used as a solvent for the subsequent experiment.
(3) 3, 5-Di-tert-butyl-p-hydroxybenzoyl chloride (25.5 mmol,6.375 g) was dissolved in THF (40 mL), followed by slowly dropping a solution of 6-amino-N- (2, 6-tetramethyl-4-piperidine) -dodecylamide (25 mmol,8.85 g) in THF (40 mL) using a constant pressure dropping funnel, followed by stirring with inert gas flow for 1 hour, reaction time of 4 hours at 3℃and reduced pressure distillation after completion to give a residual solution of 3, 5-di-tert-butyl-4-hydroxy- α, α -dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] dodecylbenzamide with a final product yield > 96% and purity > 98%.
Example 3
(1) W-aminononanoic acid (30 mmol,5.19 g) and 3, 5-di-tert-butyl-p-hydroxybenzoic acid (30 mmol,7.5 g) were dispersed in THF (40 mL) solution, a small amount of triethylamine (6 mmol,0.6 g) was added, triphosgene (10 mmol,2.97 g) was dissolved in THF solution (40 mL) and dropped into the mixed solution using a constant pressure dropping funnel, inert gas flow and stirring were maintained during the period, the reaction time was 3h, the reaction temperature was 40℃and after the completion of the distillation under reduced pressure, the residual liquids were w-aminononanoyl chloride and 3, 5-di-tert-butyl-p-hydroxybenzoyl chloride, the yield was > 78%, the purity was > 81%, the distillation temperature was 55℃and the liquid after the distillation was collected after the distillation was subjected to a further negative pressure to be used as a subsequent experimental solvent.
(2) 4-amino-2, 6-tetramethylpiperidine (25 mmol,3.9 g) was mixed with THF, w-amino-nonanoyl chloride (25.5 mmol,4.88 g) was slowly dropped into the mixed solution using a constant pressure dropping funnel for 2 hours at a reaction temperature of 0℃under stirring while keeping inert gas flow, and after completion of the reaction, the residue was distilled under reduced pressure to give 6-amino-N- (2, 6-tetramethyl-4-piperidine) -nonanamide, the distillation temperature was 55℃and the final yield was > 91% and the purity was > 89%. The liquid after distillation is collected after the negative pressure is carried out again and is used as a solvent for the subsequent experiment.
(3) 3, 5-Di-tert-butyl-p-hydroxybenzoyl chloride (25.5 mmol,6.375 g) was dissolved in THF (40 mL), followed by slowly dropping a solution of 6-amino-N- (2, 6-tetramethyl-4-piperidine) -nonanamide (25 mmol,6.725 g) in THF (40 mL) using a constant pressure dropping funnel, maintaining inert gas flow and stirring for 2 hours, reaction time 3 hours, reaction temperature 0 ℃, and reduced pressure distillation after completion to give a residual solution of 3, 5-di-tert-butyl-4-hydroxy- α, α -dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] nonyl ] benzamide with a final product yield > 96.7% and purity > 98.1%.
Example 4
(1) W-aminocaproic acid (30 mmol,3.93 g) and 3, 5-di-tert-butyl-p-hydroxybenzoic acid (30 mmol,7.5 g) were dispersed in THF (40 mL) solution, a small amount of triethylamine (3 mmol,0.3 g) was added, triphosgene (15 mmol,4.45 g) was dissolved in THF solution (40 mL), and the mixture was dropped into the solution using a constant pressure dropping funnel, while keeping inert gas flow and stirring, the reaction time was 2h, the reaction temperature was 30 ℃, and after the completion, the distillation under reduced pressure gave residual solutions of w-aminocaproyl chloride and 3, 5-di-tert-butyl-p-hydroxybenzoyl chloride, both in yields > 96%, purity > 98%, the reduced distillation temperature was 55 ℃, and the reduced distillation solution was collected after the negative pressure was again used as a subsequent experimental solvent.
(2) 4-amino-2, 6-tetramethylpiperidine (25 mmol,3.9 g) was mixed with THF, w-aminocaproyl chloride (25.5 mmol,3.81 g) was slowly dropped into the mixed solution using a constant pressure dropping funnel for 1.5h, the reaction temperature was 0 ℃, inert gas was kept flowing and stirring, the reaction was carried out for 3h, and after completion, distillation under reduced pressure was carried out to obtain a residual solution, namely 6-amino-N- (2, 6-tetramethyl-4-piperidine) -hexanamide, the rectification temperature was 55 ℃, the final yield was > 95%, and the purity was > 97%. The liquid after distillation is collected after the negative pressure is carried out again and is used as a solvent for the subsequent experiment.
(3) 3, 5-Di-tert-butyl-p-hydroxybenzoyl chloride (25.5 mmol,6.375 g) was dissolved in THF (40 mL) and then a solution of 6-amino-N- (2, 6-tetramethyl-4-piperidine) -hexanamide (25 mmol,6.725 g) in THF (40 mL) was slowly dropped using a constant pressure dropping funnel, and the reaction was continued for 1 hour with inert gas flow and stirring at a reaction temperature of 3℃for 2 hours, and then distilled under reduced pressure to give a residual solution of 3, 5-di-tert-butyl-4-hydroxy- α, α -dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] hexyl ] benzamide in a final product yield > 97% and purity > 97%.
Example 5
(1) W-aminocaproic acid (30 mmol,3.93 g) and 3, 5-di-tert-butyl-p-hydroxybenzoic acid (30 mmol,7.5 g) were dispersed in THF (40 mL) solution, a small amount of triethylamine (3 mmol,0.3 g) was added, triphosgene (12 mmol,3.56 g) was dissolved in THF solution (40 mL), and the mixture was dropped into the solution using a constant pressure dropping funnel, while keeping inert gas flow and stirring, the reaction time was 2h, the reaction temperature was 30 ℃, and after the completion, the distillation under reduced pressure gave residual solutions of w-aminocaproyl chloride and 3, 5-di-tert-butyl-p-hydroxybenzoyl chloride, both in yields > 98%, purity > 98%, the reduced distillation temperature was 55 ℃, and the reduced distillation liquid was collected after the negative pressure was again used as a subsequent experimental solvent.
(2) 4-amino-2, 6-tetramethylpiperidine (25 mmol,3.9 g) was mixed with THF, w-aminocaproyl chloride (25.5 mmol,3.81 g) was slowly dropped into the mixed solution using a constant pressure dropping funnel for 1.5h, the reaction temperature was 3℃and inert gas was kept flowing and stirring, the reaction was carried out for 3h, and after completion, distillation under reduced pressure was carried out to obtain a residual solution, namely 6-amino-N- (2, 6-tetramethyl-4-piperidine) -hexanamide, the rectification temperature was 55℃and the final yield was > 98.4% and the purity was > 98.5%. The liquid after distillation is collected after the negative pressure is carried out again and is used as a solvent for the subsequent experiment.
(3) 3, 5-Di-tert-butyl-p-hydroxybenzoyl chloride (25.5 mmol,6.375 g) was dissolved in THF (40 mL), followed by slowly dropping a solution of 6-amino-N- (2, 6-tetramethyl-4-piperidine) -hexanamide (25 mmol,6.725 g) in THF (40 mL) using a constant pressure dropping funnel, followed by maintaining inert gas flow and stirring for 1.5h, the reaction time was 4h, the reaction temperature was 3 ℃, and distillation under reduced pressure after completion gave a residual solution of 3, 5-di-tert-butyl-4-hydroxy- α, α -dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] hexyl ] benzamide with a final product yield > 97.8%, purity > 98.6%.
Example 6
(1) W-aminocaproic acid (30 mmol,3.93 g) and 3, 5-di-tert-butyl-p-hydroxybenzoic acid (30 mmol,7.5 g) were dispersed in THF (40 mL) solution, a small amount of triethylamine (6 mmol,0.6 g) was added, triphosgene (15 mmol,4.45 g) was dissolved in THF solution (40 mL), and the mixture was dropped into the solution using a constant pressure dropping funnel, while keeping inert gas flow and stirring, the reaction time was 3h, the reaction temperature was 40 ℃, and after completion, the distillation under reduced pressure gave residual solutions, i.e., w-aminocaproyl chloride and 3, 5-di-tert-butyl-p-hydroxybenzoyl chloride, the yields were both > 78.5%, the purity > 76.8%, the rectification temperature was 55 ℃, and the liquid after rectification was collected after the negative pressure was again as a subsequent experimental solvent.
(2) 4-amino-2, 6-tetramethylpiperidine (25 mmol,3.9 g) was mixed with THF, w-aminocaproyl chloride (25.5 mmol,3.81 g) was slowly dropped into the mixed solution using a constant pressure dropping funnel for 2 hours at a reaction temperature of 0℃under stirring while keeping inert gas flow, and after the reaction for 3 hours, the residue was obtained by distillation under reduced pressure, namely 6-amino-N- (2, 6-tetramethyl-4-piperidine) -hexanamide, at a distillation temperature of 55℃and a final yield of > 93.2% and a purity of > 96.4%. The liquid after distillation is collected after the negative pressure is carried out again and is used as a solvent for the subsequent experiment.
(3) 3, 5-Di-tert-butyl-p-hydroxybenzoyl chloride (25.5 mmol,6.375 g) was dissolved in THF (40 mL), followed by slowly dropping a solution of 6-amino-N- (2, 6-tetramethyl-4-piperidine) -hexanamide (25 mmol,6.725 g) in THF (40 mL) using a constant pressure dropping funnel, followed by maintaining inert gas flow and stirring for 2 hours, the reaction time was 4 hours, the reaction temperature was 0 ℃, and after completion the distillation under reduced pressure gave a residual solution of 3, 5-di-tert-butyl-4-hydroxy- α, α -dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] hexyl ] benzamide with a final product yield > 85.9% and purity > 91%.
Comparative example 1
W-aminocaproic acid (30 mmol,3.93 g) was dispersed in THF (40 mL), triphosgene (15 mmol,4.45 g) was dissolved in THF (40 mL), and the mixture was dropped into the solution using a constant pressure dropping funnel, while keeping inert gas flow and stirring, the reaction time was 3 hours, the reaction temperature was 40 ℃, and after completion, distillation under reduced pressure gave a residue, w-aminocaproyl chloride, with yields of > 78.5%, purity > 76.8%, and the rectification temperature was 55 ℃.
Comparative example 2
4-amino-2, 6-tetramethylpiperidine (25 mmol,3.9 g) was mixed with THF and reacted with w-aminocaproyl chloride (25.5 mmol,3.81 g) in the above THF solution using a constant pressure dropping funnel for 1.5h at a reaction temperature of 3℃under stirring with inert gas flow, and after completion of the reaction, distilled under reduced pressure to give a residual solution, 6-amino-N- (2, 6-tetramethyl-4-piperidine) -hexanamide, at a reduced distillation temperature of 55℃and a final yield of > 48.4% and a purity of > 39.3%.
By comparison, the synthetic route and conditions in the examples can be seen to give the best product synthesis yield and purity.
In order to better illustrate the anti-aging capability of the antioxidant to the polyamide material, the following application examples are described, and it should be noted that the antioxidant 1098, the light stabilizer 770 and the auxiliary antioxidant S9228 are all of common types in the market, the thermo-oxidative aging procedure is carried out in a high-temperature oven, the model is ESPEC-PH (H) -202, the yellowness index testing equipment is an integrating sphere color difference meter, and the model is Hunterlab-VIS.
Application example 1
The synthetic antioxidant in the example 2 is added into PA6 synthetic monomer raw material caprolactam, the mass fraction of which is 0.5 percent, and the mass ratio is 1.5:1, distilled water is used as a catalyst and a pressure supply agent, and the reaction steps are as follows: the temperature was raised to 230℃for 3 hours, then to 260℃and maintained at this temperature for 6 hours, and the pressure was maintained at 1.8MPa, after which the reaction was terminated after the temperature was lowered to room temperature. The PA6 polymer was prepared and the molded sample was subjected to optical testing after thermal oxidative aging at 160℃for 4 hours.
Application example 2
The synthetic antioxidant in the example 3 is added into PA6 synthetic monomer raw material caprolactam, the mass fraction of which is 0.05 percent, and the mass ratio is 1.5:1, distilled water is used as a catalyst and a pressure supply agent, and the reaction steps are as follows: the temperature was raised to 230℃for 3 hours, then to 260℃and maintained at this temperature for 6 hours, and the pressure was maintained at 1.8MPa, after which the reaction was terminated after the temperature was lowered to room temperature. The PA6 polymer was prepared and the molded sample was subjected to optical testing after thermal oxidative aging at 160℃for 4 hours.
Application example 3
The synthetic antioxidant in the example 5 is added into PA6 synthetic monomer raw material caprolactam, the mass fraction of which is 0.25 percent, and the mass ratio is 1.5:1, distilled water is used as a catalyst and a pressure supply agent, and the reaction steps are as follows: the temperature was raised to 230℃for 3 hours, then to 260℃and maintained at this temperature for 6 hours, and the pressure was maintained at 1.8MPa, after which the reaction was terminated after the temperature was lowered to room temperature. The PA6 polymer was prepared and the molded sample was subjected to optical testing after thermal oxidative aging at 160℃for 4 hours.
Application example 4
The synthetic antioxidant in the example 5 is added into PA6 synthetic monomer raw material caprolactam, the mass fraction of which is 0.25 percent, and the auxiliary antioxidant S9228 with the mass fraction of 0.2 percent is added, and the mass ratio is 1.5:1, distilled water is used as a catalyst and a pressure supply agent, and the reaction steps are as follows: the temperature was raised to 230℃for 3 hours, then to 260℃and maintained at this temperature for 6 hours, and the pressure was maintained at 1.8MPa, after which the reaction was terminated after the temperature was lowered to room temperature. The PA6 polymer was prepared and the molded sample was subjected to optical testing after thermal oxidative aging at 160℃for 4 hours.
Application example 5
Adding an antioxidant 1098 into a PA6 synthetic monomer raw material caprolactam, wherein the mass fraction of the caprolactam is 0.25%, and the mass ratio of the caprolactam to the PA6 synthetic monomer raw material caprolactam is 1.5:1, distilled water is used as a catalyst and a pressure supply agent, and the reaction steps are as follows: the temperature was raised to 230℃for 3 hours, then to 260℃and maintained at this temperature for 6 hours, and the pressure was maintained at 1.8MPa, after which the reaction was terminated after the temperature was lowered to room temperature. The PA6 polymer was prepared and the molded sample was subjected to optical testing after thermal oxidative aging at 160℃for 4 hours.
Application example 6
The light stabilizer 770 is added into the PA6 synthetic monomer raw material caprolactam, the mass fraction of which is 0.25 percent, and the mass ratio is 1.5:1, distilled water is used as a catalyst and a pressure supply agent, and the reaction steps are as follows: the temperature was raised to 230℃for 3 hours, then to 260℃and maintained at this temperature for 6 hours, and the pressure was maintained at 1.8MPa, after which the reaction was terminated after the temperature was lowered to room temperature. The PA6 polymer was prepared and the molded sample was subjected to optical testing after thermal oxidative aging at 160℃for 4 hours.
Application example 7
Adding an antioxidant 1098 and a light stabilizer 770 into a PA6 synthetic monomer raw material-caprolactam, wherein the mass fractions are 0.25%, and the mass ratio is 1.5:1, distilled water is used as a catalyst and a pressure supply agent, and the reaction steps are as follows: the temperature was raised to 230℃for 3 hours, then to 260℃and maintained at this temperature for 6 hours, and the pressure was maintained at 1.8MPa, after which the reaction was terminated after the temperature was lowered to room temperature. The PA6 polymer was prepared and the molded sample was subjected to optical testing after thermal oxidative aging at 160℃for 4 hours.
Application example 8
Adding an antioxidant 1098 and a light stabilizer 770 into a PA6 synthetic monomer raw material-caprolactam, wherein the mass fraction of the raw material is 0.25%, adding an auxiliary antioxidant S9228 with the mass fraction of 0.2%, and adding the raw material with the mass ratio of 1.5:1, distilled water is used as a catalyst and a pressure supply agent, and the reaction steps are as follows: the temperature was raised to 230℃for 3 hours, then to 260℃and maintained at this temperature for 6 hours, and the pressure was maintained at 1.8MPa, after which the reaction was terminated after the temperature was lowered to room temperature. The PA6 polymer was prepared and the molded sample was subjected to optical testing after thermal oxidative aging at 160℃for 4 hours.
Application example 9
Polyamide synthetic monomer raw materials and mass ratio of 1.5:1 (as catalyst and pressure feed agent) into a reaction vessel, the reaction steps being: the temperature was raised to 230℃for 3 hours, then to 260℃and maintained at this temperature for 6 hours, and the pressure was maintained at 1.8MPa, after which the reaction was terminated after the temperature was lowered to room temperature. The PA6 polymer was prepared and the molded sample was subjected to optical testing after thermal oxidative aging at 160℃for 4 hours.
The following table shows the comparison of the addition amounts of the antioxidant components and the performance test results in different application examples:
the antioxidant provided by the invention has better effect than 1098 when the weight percentage is added equally, has almost the same effect under the synergistic effect of 1098 and light stabilizer 770, and has better effect after compounding S9228.
The above embodiments are only some specific embodiments related to the present experiment, and the present disclosure is not limited to the above embodiments, but various modifications and changes may be made in the route of the present disclosure, and it should be noted that modifications of modification, disassembly, replacement, combination, etc. of the synthesis steps are still included in the scope of the present disclosure.
Claims (10)
1. An antioxidant with light stability and thermal oxidative aging resistance has the following structure:
wherein n is an integer from 1 to 11, wherein R is independently selected from groups having electron-donating effect such as methyl, disubstituted methyl, isobutyl, tert-butyl, preferably tert-butyl groups.
2. The method of preparing an antioxidant according to claim 1, wherein the method comprises:
(1) Acid chlorination reaction:
(2) Amidation of 4-amino-2, 6-tetramethylpiperidine:
(3) Synthesis of 4-hydroxy- α, α -dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidyl) amino ] ethyl-dodecyl ] benzamide compound:
3. the method of claim 2, wherein step (1) comprises the steps of: tetrahydrofuran is used as a solvent, a small amount of triethylamine is used as an acid binding agent, triphosgene is dissolved and then mixed with w-amino acid or a p-hydroxybenzoic acid compound, the mixture is heated for reaction under the condition of inert gas circulation and stirring, reduced pressure distillation is carried out after the reaction is finished, and residues are collected to obtain w-amino acyl chloride and the p-hydroxybenzoyl chloride compound.
4. The method according to claim 3, wherein the feed ratio of each raw material in the step (1) is: w-amino acid/p-hydroxybenzoic acid compound: triphosgene: triethylamine = 30:10 to 15: 3-6, respectively dissolving w-amino acid/p-hydroxybenzoic acid compound in THF solution; the temperature rise reaction temperature is 25-40 ℃ and the reaction time is 2-3 h; the temperature of reduced pressure distillation is 50-60 ℃, and the negative pressure intensity is 0.05-0.1 MPa.
5. The method according to any one of claims 2 to 4, wherein the step (2) comprises the steps of: diluting 4-amino-2, 6-tetramethylpiperidine in THF under inert gas to obtain 4-amino-2, 6-tetramethylpiperidine solution, and dripping w-aminoacyl chloride prepared in the step (1) into 4-amino-2, 6-tetramethylpiperidine solution for reaction, the duration is 1-2 h, the reaction time is 1-3 h, stirring is kept during the reaction, the solution is distilled under reduced pressure after the reaction is completed, and residues are collected, wherein the residues are 6-amino-N- (2, 6-tetramethyl-4-piperidine) - (ethyl-dodecyl) amide.
6. The method according to claim 5, wherein the raw materials in the step (2) are mixed in the following ratio: w-aminoacyl chloride: 4-amino-2, 6-tetramethylpiperidine=1 to 1.05:1, dissolving 4-amino-2, 6-tetramethylpiperidine in a THF solution; the dripping time is 1-2 h, the reaction temperature is 0-5 ℃, the reaction time is 1-3 h, the reduced pressure distillation temperature is 50-60 ℃, and the negative pressure intensity is 0.05-0.1 Mpa.
7. The method of any one of claims 2 to 6, wherein step (3) comprises the steps of: diluting 6-amino-N- (2, 6-tetramethyl-4-piperidine) - (ethyl-dodecyl) amide in THF, slowly dripping the parahydroxybenzoyl chloride compound into the THF under the protection of inert gas, keeping stirring, carrying out reduced pressure distillation on the solution after the reaction is completed, and collecting residues, wherein the residues are 4-hydroxy-alpha, alpha-dimethyl-N- [6- [ (2, 6-tetramethyl-4-piperidine) amino ] ethyl-dodecyl ] benzamide compounds.
8. The process according to claim 7, wherein the dropping time is 1 to 2 hours, the reaction temperature is 0 to 5 ℃, the reaction time is 2 to 4 hours, the temperature of the reduced pressure distillation is 50 to 60 ℃, and the negative pressure strength is 0.05 to 0.1Mpa.
9. The method according to claim 7 or 8, wherein the raw materials in the step (3) are mixed in the following ratio: 6-amino-N- (2, 6-tetramethyl-4-piperidine) - (ethyl-dodecyl) amide: parahydroxybenzoyl chloride compound=1: 1 to 1.05.
10. Use of the antioxidant with photo-stability and anti-thermal-oxidative aging ability according to claim 1 or the antioxidant with photo-stability and anti-thermal-oxidative aging ability according to any one of claims 2 to 9 in a polyamide composition comprising polyamide and about 0.05 to 0.5 mass% of the antioxidant with photo-stability and anti-thermal-aging ability according to claim 1 or the antioxidant with photo-stability and anti-thermal-oxidative aging ability according to any one of claims 2 to 9, preferably compounded with 0.05 to 0.5 mass% of the S9228 phosphite antioxidant.
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Effective date of registration: 20240208 Address after: 264006 No. 59, Chongqing Street, Yantai Economic and Technological Development Zone, Shandong Province Applicant after: Wanhua Chemical Group Co.,Ltd. Country or region after: China Applicant after: Wanhua chemical (Ningbo) Co.,Ltd. Address before: 315812 Wanhua Industrial Park, 39 Huandao North Road, Daxie Development Zone, Ningbo City, Zhejiang Province Applicant before: Wanhua chemical (Ningbo) Co.,Ltd. Country or region before: China |
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