CN118126088A - Synthesis method of antioxidant 626 with low 2,4 di-tert-butylphenol residue - Google Patents
Synthesis method of antioxidant 626 with low 2,4 di-tert-butylphenol residue Download PDFInfo
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- CN118126088A CN118126088A CN202410245586.1A CN202410245586A CN118126088A CN 118126088 A CN118126088 A CN 118126088A CN 202410245586 A CN202410245586 A CN 202410245586A CN 118126088 A CN118126088 A CN 118126088A
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- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical group CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 78
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 78
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 23
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 18
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims abstract description 16
- XZBIAZWTRRPKCA-UHFFFAOYSA-N CCCCN1C=CN(C)C1C.O Chemical compound CCCCN1C=CN(C)C1C.O XZBIAZWTRRPKCA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000001953 recrystallisation Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims 2
- 230000032798 delamination Effects 0.000 claims 1
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing an antioxidant 626 with low 2, 4-di-tert-butylphenol residue, which takes tributyl phosphite, pentaerythritol and 2, 4-di-tert-butylphenol as raw materials, takes 1-butyl-2, 3-dimethyl imidazole hydroxide as a catalyst to synthesize the antioxidant 626, and then the antioxidant 626 with low 2, 4-di-tert-butylphenol residue is obtained through decane recrystallization. The synthesis method can obtain the antioxidant 626 with low 2,4 di-tert-butylphenol residue, improves the product yield and the stability of the yield, and has excellent product quality.
Description
Technical Field
The invention relates to a synthesis method of an antioxidant 626 with low 2,4 di-tert-butylphenol residue, and belongs to the technical field of chemical industry.
Background
The antioxidant 626, the chemical name of which is bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, is an efficient auxiliary antioxidant of pentaerythritol diphosphite, and is widely applied to PE, PP, PVC, ABS, PC, polyesters and the like.
The existing method for synthesizing the antioxidant 626 comprises the following steps: (1) The antioxidant 168 and pentaerythritol are used as raw materials, and the antioxidant 626 is synthesized under high temperature and high pressure, but the reaction conditions are harsh, the cost is high, and in addition, the byproduct 2, 4-di-tert-butylphenol is produced, so that the residual amount of the 2, 4-di-tert-butylphenol is large, and the product quality is influenced; (2) The antioxidant 626 is synthesized by steps by taking triphenyl phosphite, 2, 4-di-tert-butylphenol and pentaerythritol as raw materials, but byproducts of phenol are produced, so that trace phenol is difficult to remove, and the quality of a product is affected; (3) The antioxidant 626 is synthesized by taking phosphorus trichloride, 2, 4-di-tert-butylphenol and pentaerythritol as raw materials step by step, and no matter the phosphorus trichloride reacts with the 2, 4-di-tert-butylphenol or the phosphorus chloride reacts with the pentaerythritol firstly, the phosphorus trichloride leads to more intermediate products, the purification is difficult and the product yield is reduced; in addition, the content of 2, 4-di-t-butylphenol in the synthesized antioxidant 626 is less than 1%, but the residual amount is high in several thousand ppm.
Disclosure of Invention
At least one of the problems associated with the prior art is that the present invention provides a method for synthesizing an antioxidant 626 having a low residual 2,4 di-tert-butylphenol content.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a synthetic method of an antioxidant 626 with low 2, 4-di-tert-butylphenol residue comprises the steps of taking pentaerythritol, tributyl phosphite and 2, 4-di-tert-butylphenol as raw materials, taking 1-butyl-2, 3-dimethyl imidazole hydroxide as a catalyst to synthesize the antioxidant 626, and then recrystallizing the antioxidant 626 with decane to obtain the antioxidant 626 with low 2, 4-di-tert-butylphenol residue.
Preferably, the synthesis method of the antioxidant 626 with low 2,4 di-tert-butylphenol residue comprises the following steps:
(1) Under the protection of inert gas, tributyl phosphite, pentaerythritol and 1-butyl-2, 3-dimethyl imidazole hydroxide are mixed, stirred and heated for reaction, butanol and unreacted tributyl phosphite are removed by reduced pressure distillation after the reaction is completed, and an intermediate system of pentaerythritol diphosphite is obtained;
(2) Adding 2, 4-di-tert-butylphenol into the intermediate system under the protection of inert gas, continuously stirring and heating for reaction, cooling to 10-15 ℃ after the reaction is completed, crystallizing, filtering to remove filtrate, and obtaining an antioxidant 626;
(3) Adding the antioxidant 626 into n-decane, stirring and heating to 165-170 ℃, maintaining the temperature for 3-5 min, cooling to 10-15 ℃, crystallizing and separating out, and filtering to remove the n-decane to obtain the antioxidant 626 with low 2, 4-di-tert-butylphenol residue.
Preferably, the molar ratio of pentaerythritol to tributyl phosphite is 1:2.05 to 2.1, preferably 1:2.06.
Preferably, the 1-butyl-2, 3-dimethylimidazole hydroxide is added in an amount of 2 to 2.5%, preferably 2.2% by weight of pentaerythritol.
Preferably, the molar ratio of pentaerythritol to 2, 4-di-tert-butylphenol is between 1:2.02 and 2.04, preferably between 1:2.03.
Preferably, the reaction temperature of the step (1) is 130-140 ℃ and the reaction time is 3-4 h.
Preferably, the reaction temperature of the step (2) is 165-175 ℃ and the reaction time is 1.5-2 h.
Preferably, the filtrate in the step (2) is subjected to reduced pressure distillation to recover butanol, extraction and reduced pressure distillation to recover 1-butyl-2, 3-dimethyl imidazole hydroxide.
Preferably, the filtrate in the step (2) is distilled under reduced pressure to recover butanol, hexane and water are added to be uniformly mixed, the mixture is stood for layering, a lower water phase is taken out, and the lower water phase is distilled under reduced pressure to recover 1-butyl-2, 3-dimethyl imidazole hydroxide.
The invention has the beneficial effects that: the tributyl phosphite is used as the raw material, so that the phenomenon that byproducts are difficult to remove can be avoided, the stability of raw material reaction is ensured, the product yield and the stability of the yield are improved, the impurity content is effectively reduced, and the product quality is excellent; meanwhile, n-decane is used for recrystallization, so that the content of 2, 4-di-tert-butylphenol in the product is lower and only tens ppm is achieved, and the yield of the product is also ensured; the invention uses 1-butyl-2, 3-dimethyl imidazole hydroxide as catalyst, effectively improves the reaction efficiency and the product yield, and avoids the generation of a large amount of wastewater without adding acid to neutralize alkali after the reaction is completed.
Detailed Description
The following description of the embodiments of the present invention will be made more complete in terms of the technical solutions in which the invention is practiced, and the described embodiments are merely some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents, instruments and components used are conventional products commercially available without identifying the manufacturer.
Example 1
A synthetic method of an antioxidant 626 with low 2,4 di-tert-butylphenol residue comprises the following specific steps:
(1) Under the protection of inert gas, 68.05g of pentaerythritol, 256.55g of tributyl phosphite and 1.50g of 1-butyl-2, 3-dimethyl imidazole hydroxide are mixed, stirred and heated to 130-140 ℃ for reaction for 3.5h, and butanol and unreacted tributyl phosphite are removed by reduced pressure distillation after the reaction is completed, so that a pentaerythritol diphosphite intermediate system is obtained;
(2) Adding 209.40g of 2, 4-di-tert-butylphenol into the intermediate system under the protection of inert gas, continuously stirring and heating to 165-175 ℃ for reacting for 1.5h, cooling to 10-15 ℃ after the reaction is completed, crystallizing, separating out, filtering and removing filtrate to obtain an antioxidant 626; recovering butanol from the filtrate by reduced pressure distillation, adding hexane and water into the rest liquid, mixing uniformly, standing for layering, taking the lower water phase for reduced pressure distillation, and recovering 1-butyl-2, 3-dimethyl imidazole hydroxide;
(3) Adding the antioxidant 626 into 170g of n-decane, stirring and heating to 165-170 ℃, maintaining the temperature for 4min, cooling to 10-15 ℃, crystallizing and separating out, filtering and removing the recrystallized liquid n-decane to obtain the antioxidant 626 with low 2, 4-di-tert-butylphenol residue, wherein the weight of the antioxidant 626 is 294.46g, and the result is shown in table 1 after measurement.
Example 2
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 1 in that: 257.81g of tributyl phosphite and the rest are the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 298.72g, and the results are shown in Table 1.
Example 3
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 1 in that: 261.56g of tributyl phosphite and the rest are the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 295.73g, and the results are shown in Table 1.
Example 4
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 1 in that: 259.06g of tributyl phosphite and the rest are the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 294.12g, and the results are shown in Table 1.
Example 5
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 2 in that: 208.37g of 2, 4-di-tert-butylphenol and the balance being the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 295.98g, and the results are shown in Table 1.
Example 6
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 2 in that: 210.42g of 2, 4-di-tert-butylphenol and the balance being the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 295.46g, and the results are shown in Table 1.
Example 7
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 2 in that: 1.36g of 1-butyl-2, 3-dimethylimidazole hydroxide and the balance thereof; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 293.56g, and the results are shown in Table 1.
Example 8
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 2 in that: 1.70g of 1-butyl-2, 3-dimethylimidazole hydroxide and the rest are the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 295.52g, and the results are shown in Table 1.
Example 9
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 2 in that: reacting for 3 hours in the step (1), reacting for 1.5 hours in the step (1), and maintaining the temperature in the step (1) for 3 minutes; the rest are the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 297.43g, and the results are shown in Table 1.
Example 10
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 2 in that: reacting for 4 hours in the step (1), reacting for 2 hours in the step (1), and maintaining the temperature in the step (1) for 5 minutes; the rest are the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 298.31g, and the results are shown in Table 1.
Comparative example 1
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 2 in that: 171.08g of triethyl phosphite were used; step (3) recrystallizing the antioxidant 626 by using ethanol, stirring, heating and refluxing for 4min, cooling to 10-15 ℃, and crystallizing out; the rest are the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 277.89g, and the results are shown in Table 1.
Comparative example 2
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 2 in that: 171.08g of triethyl phosphite were used; the rest are the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 284.27g, and the results are shown in Table 1.
Comparative example 3
A method for synthesizing an antioxidant 626 with low 2,4 di-tert-butylphenol residues, which is different from example 2 in that: recrystallizing the antioxidant 626 obtained in the step (2) by using ethanol, stirring, heating and refluxing for 4min, cooling to 10-15 ℃, and crystallizing out; the rest are the same; the weight of the antioxidant 626 having a low residual content of 2, 4-di-t-butylphenol was 286.89g, and the results are shown in Table 1.
Comparative example 4
A synthetic method of an antioxidant 626 with low 2,4 di-tert-butylphenol residue comprises the following specific steps:
(1) Under the protection of inert gas, 256.55g of tributyl phosphite, 68.05g of pentaerythritol and 1.50g of dibutyl tin oxide are mixed, stirred and heated to 130-140 ℃ for reaction for 4.5h, and reduced pressure distillation is carried out after the reaction is completed to obtain a pentaerythritol diphosphite intermediate system;
(2) Adding 209.40g of 2, 4-di-tert-butylphenol into the intermediate system under the protection of inert gas, continuously stirring and heating to 165-175 ℃ for reaction for 3 hours, cooling to 10-15 ℃ after the reaction is completed, crystallizing and separating out, filtering to remove filtrate, recovering butanol from the filtrate by reduced pressure distillation, adding dilute hydrochloric acid into the filtered solid for reaction with dibutyltin oxide, filtering again to remove the filtrate, and washing to neutrality to obtain an antioxidant 626;
(3) Adding the antioxidant 626 into 170g of n-decane, stirring and heating to 165-170 ℃, maintaining the temperature for 4min, cooling to 10-15 ℃, crystallizing and separating out, filtering and removing the recrystallized liquid n-decane to obtain the antioxidant 626 with low 2, 4-di-tert-butylphenol residue, wherein the weight of the antioxidant 626 is 267.94g, and the result is shown in table 1 after measurement.
The product yield was calculated as: the molar mass of antioxidant 626/the molar mass of pentaerythritol is x 100%.
TABLE 1
| Yield (%) | 2,4 Di-tert-butylphenol content (%) | Acid value (mgKOH/g) | |
| Example 1 | 97.39 | 0.0067 | 0.0201 |
| Example 2 | 98.8 | 0.0046 | 0.0168 |
| Example 3 | 97.81 | 0.0058 | 0.0185 |
| Example 4 | 97.28 | 0.0072 | 0.0182 |
| Example 5 | 97.4 | 0.0062 | 0.0197 |
| Example 6 | 97.72 | 0.0076 | 0.0188 |
| Example 7 | 97.09 | 0.0051 | 0.0167 |
| Example 8 | 97.41 | 0.0063 | 0.0208 |
| Example 9 | 98.37 | 0.0067 | 0.0193 |
| Example 10 | 98.66 | 0.0042 | 0.0173 |
| Comparative example 1 | 91.91 | 0.0827 | 0.0254 |
| Comparative example 2 | 94.02 | 0.0049 | 0.0198 |
| Comparative example 3 | 94.89 | 0.0776 | 0.0223 |
| Comparative example 4 | 88.62 | 0.0062 | 0.3015 |
The above table 1 shows that the yield of the antioxidant 626 synthesized by the method is improved, the yield is relatively stable, the impurity content is low, the purity of the antioxidant 626 is more than 99.99%, the n-decane solvent is heated to 165-170 ℃ for recrystallization, and the 2, 4-di-tert-butylphenol wrapped in the antioxidant 626 is fully dissolved, so that the content of the 2, 4-di-tert-butylphenol in the product is less than 0.01%, the residual quantity of the 2, 4-di-tert-butylphenol is effectively reduced, and the quality of the antioxidant 626 is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (9)
1. A synthesis method of an antioxidant 626 with low 2, 4-di-tert-butylphenol residue is characterized in that pentaerythritol, tributyl phosphite and 2, 4-di-tert-butylphenol are used as raw materials, 1-butyl-2, 3-dimethyl imidazole hydroxide is used as a catalyst to synthesize the antioxidant 626, and decane is used for recrystallization to obtain the antioxidant 626 with low 2, 4-di-tert-butylphenol residue.
2. The method for synthesizing the antioxidant 626 with low 2,4 di-tert-butylphenol residue, according to claim 1, wherein the molar ratio of pentaerythritol to tributyl phosphite is 1:2.05-2.1.
3. The method for synthesizing an antioxidant 626 having low 2,4 di-t-butylphenol residue according to claim 1, wherein the amount of 1-butyl-2, 3-dimethylimidazole hydroxide is 2 to 2.5% by weight of pentaerythritol.
4. The method for synthesizing the antioxidant 626 with low 2, 4-di-tert-butylphenol residue according to claim 1, wherein the molar ratio of pentaerythritol to 2, 4-di-tert-butylphenol is 1:2.02-2.04.
5. The method for synthesizing an antioxidant 626 having low 2,4 di-t-butylphenol residues according to any one of claims 1to 4, wherein the specific synthesis method comprises the steps of:
(1) Under the protection of inert gas, tributyl phosphite, pentaerythritol and 1-butyl-2, 3-dimethyl imidazole hydroxide are mixed, stirred and heated for reaction, butanol and unreacted tributyl phosphite are removed by reduced pressure distillation after the reaction is completed, and an intermediate system of pentaerythritol diphosphite is obtained;
(2) Adding 2, 4-di-tert-butylphenol into the intermediate system under the protection of inert gas, continuously stirring and heating for reaction, cooling to 10-15 ℃ after the reaction is completed, crystallizing, filtering to remove filtrate, and obtaining an antioxidant 626;
(3) Adding the antioxidant 626 into n-decane, stirring and heating to 165-170 ℃, maintaining the temperature for 3-5 min, cooling to 10-15 ℃, crystallizing and separating out, and filtering to remove the n-decane to obtain the antioxidant 626 with low 2, 4-di-tert-butylphenol residue.
6. The method for synthesizing an antioxidant 626 having low 2,4 di-t-butylphenol residues according to claim 5, wherein the reaction temperature of the step (1) is 130-140 ℃ and the reaction time is 3-4 hours.
7. The method for synthesizing an antioxidant 626 having low 2,4 di-t-butylphenol residues according to claim 5, wherein the reaction temperature in the step (2) is 165-175 ℃ and the reaction time is 1.5-2 hours.
8. The method for synthesizing the antioxidant 626 with low 2,4 di-tert-butylphenol residue according to claim 5, wherein the filtrate obtained in the step (2) is separated by distillation under reduced pressure, extraction and distillation under reduced pressure in sequence.
9. The method for synthesizing the antioxidant 626 with low 2,4 di-tert-butylphenol residue according to claim 8, wherein the filtrate obtained in the step (2) is distilled under reduced pressure to recover butanol, hexane and water are added to be mixed uniformly, the mixture is stood for delamination, a lower aqueous phase is taken out, and the lower aqueous phase is distilled under reduced pressure to recover 1-butyl-2, 3-dimethylimidazole hydroxide.
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