CN110183364B - Thioether bisphenol acrylate multi-effect antioxidant and preparation method thereof - Google Patents
Thioether bisphenol acrylate multi-effect antioxidant and preparation method thereof Download PDFInfo
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- C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
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Abstract
The invention discloses a thioether bisphenol acrylate multi-effect antioxidant which has a molecular structure shown as the following formula:
the thioether bisphenol acrylate multi-effect antioxidant molecule not only contains hindered phenol functional groups as main antioxidants and thioether bonds as auxiliary antioxidants, but also contains a phenol acrylate structure with a carbon free radical capture function, can play a triple-effect integrated antioxidation role in the processing and using processes of high polymer materials, can better protect the high polymer materials, avoids the degradation and aging of products, solves the problem of poor antioxidation effect of single-function antioxidants on the high polymer materials, and has the advantages of low reaction temperature, low energy consumption, capability of removing by-products by filtering, no wastewater generation, recoverable solvent and environmental protection.
Description
Technical Field
The invention relates to a plastic additive, in particular to a thioether bisphenol acrylate multi-effect antioxidant and a preparation method thereof.
Background
Antioxidants are a class of polymer adjuvants which, when present in only small amounts in polymer systems, retard or inhibit the progress of the polymer oxidation process, thereby preventing the aging of the polymer and extending its useful life, also known as antioxidants. The thermal oxidation process of the organic compound is a series of free radical chain type reactions, under the action of heat or light, chemical bonds of molecules are broken to generate active free radicals, the free radicals can initiate a series of free radical chain type reactions to cause fundamental changes of the structure and the property of the organic compound, and the action mechanism of the antioxidant is to eliminate the free radicals which are just generated to prevent the chain type reactions from proceeding, so that the anti-aging effect is achieved. The common anti-aging mechanism of hindered phenol antioxidants is that functional groups and free radicals are combined, but the functions are single and the anti-aging effect is common.
Disclosure of Invention
The invention provides a thioether bisphenol acrylate multi-effect antioxidant and a preparation method thereof, aiming at the problem that the existing hindered phenol antioxidant has single anti-aging effect.
The technical scheme for solving the technical problems is as follows: a thioether bisphenol acrylate multi-effect antioxidant is characterized by having a molecular structure shown as a formula I:
wherein R is1Is a linear or branched alkyl group of C1-C5, R2Is C1-C5 straight-chain or branched-chain alkyl.
Specifically, the thioether bisphenol acrylate multi-effect antioxidant has a molecular structure shown as a formula a-e:
the invention also relates to a preparation method of the thioether bisphenol acrylate multi-effect antioxidant, which comprises the following steps: dissolving a thioether bisphenol compound in a solvent, adding triethylamine and acrylic acid serving as catalysts, controlling the temperature to be 20-50 ℃, stirring and mixing for 0.5-1.5h, dropwise adding phosphorus oxychloride into a reaction system, controlling the dropwise adding time to be 50-90min, heating to 60-90 ℃ after the dropwise adding is finished, reacting for 1-4h under stirring, carrying out suction filtration on a reaction solution, leaching a filter cake with n-heptane, carrying out reduced pressure distillation on a leaching solution, stirring and crystallizing a distillation residual liquid at 0-5 ℃, carrying out suction filtration again, and collecting the filter cake to obtain the thioether bisphenol compound. The main reactions involved are:
wherein, the weight ratio of the thioether bisphenol compound to the acrylic acid and the phosphorus oxychloride is 1 (1.1-1.4) to 1.1-1.5; the mass ratio of the thioether bisphenol compound to the triethylamine is 1 (4-6); the solvent is one of toluene, xylene, trimethylbenzene, benzene, n-heptane or n-nonane.
The invention has the beneficial effects that: the thioether bisphenol acrylate multi-effect antioxidant molecule not only contains hindered phenol functional groups as main antioxidants and thioether bonds as auxiliary antioxidants, but also contains a phenol acrylate structure with a carbon free radical capture function, can play a triple-effect integrated antioxidation role in the processing and using processes of high polymer materials, can better protect the high polymer materials, avoids the degradation and aging of products, solves the problem of poor antioxidation effect of single-function antioxidants on the high polymer materials, and has the advantages of low reaction temperature, low energy consumption, capability of removing by-products by filtering, no wastewater generation, recoverable solvent and environmental protection.
Drawings
FIG. 1 is a NMR spectrum of compound a of example 1; FIG. 2 is a liquid chromatogram of Compound a of example 1.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
EXAMPLE 1 Synthesis of Compound a
358.5g (1mol) of 2, 2' -thiobis (4-methyl-6-tert-butylphenol) is added into a 3L three-necked bottle, 1000ml of n-heptane, 404g (4mol) of triethylamine and 86.5g (1.2mol) of acrylic acid are added, the temperature is raised to 60 ℃ by stirring, 199g (1.3mol) of phosphorus oxychloride is added dropwise, the temperature is controlled to be 60-80 ℃ by dropwise adding, the dropwise adding time is 1h, and the temperature is raised to 85 ℃ by heating for 1.5h after dropwise adding. After the reaction is finished, slightly cooling and filtering the reaction solution, wherein a filter cake is triethylamine salt, leaching with 500ml of n-heptane, combining organic phases, distilling 1200ml of n-heptane under reduced pressure, stirring the residual solution, cooling and crystallizing, crystallizing at 0-5 ℃, and filtering to obtain 338.3g of a product with the yield of 82%.
EXAMPLE 2 Synthesis of Compound b
Adding 386.5g (1mol) of 2, 2' -thiobis (4-ethyl-6-tert-butylphenol) into a 3L three-necked bottle, adding 1100ml of n-heptane, 505g (5mol) of triethylamine and 93.7g (1.3mol) of acrylic acid, stirring and heating to 65 ℃, beginning to dropwise add 199g (1.3mol) of phosphorus oxychloride, controlling the temperature to be 65-80 ℃ when dropwise add, dropwise adding for 1h, and heating to 85 ℃ after dropwise add and keeping the temperature for 1.5 h. After the reaction is finished, slightly cooling and filtering the reaction solution, wherein a filter cake is triethylamine salt, leaching with 500ml of n-heptane, combining organic phases, distilling out 1300ml of n-heptane under reduced pressure, stirring the residual solution, cooling and crystallizing, and crystallizing at the temperature of 2-5 ℃ to obtain 373g of a product with the yield of 84.6%.
EXAMPLES 3 Synthesis of Compound c
Adding 414.5g (1mol) of 2, 2' -thiobis (4, 6-di-tert-butylphenol) into a 3L three-necked bottle, adding 1100ml of toluene, 535g (5.3mol) of triethylamine and 93.7g (1.3mol) of acrylic acid, stirring and heating to 60 ℃, starting to dropwise add 207g (1.35mol) of phosphorus oxychloride, controlling the temperature to be 65-85 ℃ during dropwise adding, dropwise adding for 1h, and heating to 90 ℃ after dropwise adding and keeping the temperature for 1.5 h. After the reaction is finished, slightly cooling and filtering the reaction solution, wherein a filter cake is triethylamine salt, leaching with 600ml of toluene, combining organic phases, distilling out 1200ml of toluene under reduced pressure, stirring the residual solution, cooling and crystallizing, and crystallizing at 5-10 ℃ to obtain 414.6g of a product with the yield of 88.5%.
EXAMPLE 4 Synthesis of Compound d
Adding 430g (1mol) of 2, 2' -thiobis (4-tert-amyl-6-tert-butylphenol) into a 3L three-necked bottle, adding 1100ml of toluene, 550g (5.5mol) of triethylamine and 96g (1.4mol) of acrylic acid, stirring, heating to 60 ℃, starting to dropwise add 207g (1.35mol) of phosphorus oxychloride, controlling the temperature to be 65-85 ℃ during dropwise addition, dropwise adding for 1h, and heating to 50 ℃ after dropwise addition and preserving heat for 3 h. After the reaction is finished, slightly cooling and filtering the reaction solution, wherein a filter cake is triethylamine salt, leaching with 600ml of toluene, combining organic phases, distilling out 1200ml of toluene under reduced pressure, stirring the residual solution, cooling and crystallizing, crystallizing at 5-10 ℃, and filtering to obtain 414.6g of a product, wherein the yield is 90.5%.
EXAMPLE 5 Synthesis of Compound e
Adding 430g (1mol) of 2, 2' -thiobis (4, 6-dibutylphenol) into a 3L three-necked bottle, adding 1100ml of toluene, 550g (5.5mol) of triethylamine and 96g (1.4mol) of acrylic acid, stirring, heating to 60 ℃, starting to dropwise add 207g (1.35mol) of phosphorus oxychloride, controlling the temperature at 65-85 ℃ during dropwise adding, dropwise adding for 1h, and heating to 50 ℃ after dropwise adding, and keeping the temperature for 3 h. After the reaction is finished, slightly cooling and filtering the reaction solution, wherein a filter cake is triethylamine salt, leaching with 600ml of toluene, combining organic phases, distilling out 1200ml of toluene under reduced pressure, stirring the residual solution, cooling and crystallizing, crystallizing at 5-10 ℃, and filtering to obtain 414.6g of a product with the yield of 91.5%.
The antioxidants prepared in the examples 1 to 5, the antioxidant 1010+ DLTP prepared in the comparative example 1 and the antioxidant 1010+168 prepared in the comparative example 2 are respectively applied to PP products, the samples are prepared according to the national standard GB/T1727-92, long-term thermal oxidation aging experiments (LTTS, GB/T7141-2008) are carried out after the sample preparation is finished, and the performances are compared after the experiments are finished, as shown in Table 1. The results of data comparison in the table show that the long-term thermal oxidative aging performance of the sample added with 0.5% of the product of the invention is about 10 times that of the blank sample, about 1.3 times that of the traditional hindered phenol and thioester antioxidant of comparative example 1, and about 4 times that of the traditional hindered phenol and phosphite antioxidant of comparative example 2, and the product has better antioxidant performance.
TABLE 1 comparison of antioxidant aging resistance of examples and comparative examples
The compound a in example 1 is subjected to nuclear magnetic resonance detection, and the spectrum is shown in figure 1, and the specific analysis is as follows: δ 1.35-9.44(D, 9H, 3CH 3); δ 1.41-9.11(D, 9H, 3CH 3); δ 2.20-3.00(T, 3H, CH 3); δ 2.26-2.99(T, 3H, CH 3); δ 3.70-1.83(S, 2H, ═ CH 2); δ 6.1-0.98(D, H, ═ CH); delta 6.45-0.97(M, H, Ar-OH); delta 6.71-1.56(D, H, Ar-H); delta 6.81-1.00(D, H, Ar-H); delta 7.11-0.99(D, H, Ar-H); delta 7.20-1.02(D, H, Ar-H). From the above data, it can be determined that the molecular structure of the product is consistent with that of the target compound.
The compound a in example 1 is subjected to liquid chromatography detection, the chromatogram is shown in fig. 2, the peak-out retention time of the compound is 10.434min, the purity is 99.574% calculated by a normalization method, and the specific data are shown in table 2.
TABLE 2 liquid chromatogram concentration data for compound a of example 1
| Peak number | Retention time | Area of | Height | Concentration of |
| 1 | 2.673 | 1496 | 197 | 0.006 |
| 2 | 3.137 | 2942 | 713 | 0.012 |
| 3 | 3.247 | 8738 | 755 | 0.037 |
| 4 | 3.625 | 12794 | 1552 | 0.054 |
| 5 | 3.825 | 2746 | 398 | 0.012 |
| 6 | 4.581 | 3017 | 269 | 0.013 |
| 7 | 5.019 | 5626 | 255 | 0.024 |
| 8 | 7.239 | 48152 | 2742 | 0.203 |
| 9 | 8.145 | 6417 | 311 | 0.027 |
| 10 | 9.343 | 9030 | 461 | 0.038 |
| 11 | 10.434 | 23610885 | 1165433 | 99.574 |
| Total of | 23711842 | 1173086 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (2)
1. The thioether bisphenol acrylate multi-effect antioxidant is characterized by having a molecular structure shown as a formula c-e:
2. the preparation method of the thioether bisphenol acrylate multi-effect antioxidant as claimed in claim 1, characterized in that the steps are as follows: dissolving a thioether bisphenol compound in a solvent, adding catalysts triethylamine and acrylic acid, controlling the temperature to be 20-50 ℃, stirring and mixing for 0.5-1.5h, dropwise adding phosphorus oxychloride into a reaction system, controlling the dropwise adding time to be 50-90min, heating to 60-90 ℃ after the dropwise adding is finished, reacting for 1-4h under stirring, carrying out suction filtration on a reaction solution, leaching a filter cake with n-heptane, carrying out reduced pressure distillation on a leaching solution, stirring and crystallizing a distillation residual liquid at 0-5 ℃, carrying out suction filtration again, and collecting the filter cake to obtain the thioether bisphenol compound;
the weight ratio of the thioether bisphenol compound to the acrylic acid and the phosphorus oxychloride is 1 (1.1-1.4) to 1.1-1.5;
the mass ratio of the thioether bisphenol compound to the triethylamine is 1 (4-6);
the solvent is one of toluene, xylene, trimethylbenzene, benzene, n-heptane or n-nonane.
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| JPS58124762A (en) * | 1982-01-16 | 1983-07-25 | Sumitomo Chem Co Ltd | Bisphenol derivative and its preparation |
| JPS58159457A (en) * | 1982-03-18 | 1983-09-21 | Sumitomo Chem Co Ltd | Bisphenol derivative and its preparation |
| JPS63286465A (en) * | 1987-05-19 | 1988-11-24 | Mitsubishi Petrochem Co Ltd | Resin composition |
| JPH0764786B2 (en) * | 1987-12-23 | 1995-07-12 | 住友化学工業株式会社 | Phenolic compounds and stabilizers for butadiene polymers containing the same as active ingredients |
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