CN110862317A - Hindered phenol antioxidant and preparation method thereof - Google Patents
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- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention provides a hindered phenol antioxidant and a preparation method thereof. The antioxidant provided by the invention has proper molecular weight and melting point, and good compatibility and associativity with polymers, can be uniformly dispersed in a high polymer material matrix, and can be used as the antioxidant of a polymer material; meanwhile, the antioxidant has the advantages of good extraction resistance, volatilization resistance, migration resistance and the like, and can fully play the antioxidation role when being applied to polymer materials, thereby improving the antioxidation effect. Moreover, the antioxidant provided by the invention can improve the heat-resistant stability compared with the antioxidant 1010. In addition, the antioxidant provided by the invention has the advantages of low cost of raw materials, high reaction yield and capability of realizing industrial production.
Description
Technical Field
The invention relates to an antioxidant for a high polymer material, in particular to a hindered phenol antioxidant and a preparation method thereof.
Background
During polymerization, granulation, storage, processing and long-term use, the polymer is easily oxidized by oxygen in the air under the action of light and heat, the mechanical property of the polymer is lost, and changes such as color change, cracking, loss of glossiness and the like occur, so that an antioxidant needs to be added to improve the processing stability and the long-term stability of the polymer.
The types of antioxidants are: hindered phenol antioxidants, phosphite antioxidants, thioester antioxidants, and the like. Among them, hindered phenol antioxidants are one of the most widely and effectively used antioxidants, and are widely used in the processing of various polymer products because of their advantages of donating protons to terminate free radicals for autoxidation reaction, having good synergistic effect with auxiliary antioxidants, etc. The existing typical products comprise antioxidant 1010, BHT and the like, wherein the antioxidant 1010 is a hindered phenol antioxidant which has the largest output and is most widely applied at present, but the antioxidant 1010 has poor heat resistance stability and poor extraction resistance when being applied to special engineering plastics with higher processing temperature. The antioxidant BHT has certain toxicity and cancerogenic risk, can cause hepatomegaly, chromosome abnormality and reduction of reproduction rate, and has increasingly higher requirements on safety, health and environmental protection of the antioxidant along with the continuous improvement of the environmental protection standard of the European Union, and increasingly limited application range. Therefore, the market demand for high temperature resistant, nontoxic and environment-friendly hindered phenol antioxidants is increasing.
However, it is difficult to develop a novel antioxidant for polymer, and it is difficult to use the antioxidant as long as the antioxidant is available, and it is difficult to use the antioxidant for polymer materials because of its specific compatibility with the antioxidant, and it is impossible to use any antioxidant as an antioxidant for polymer materials because of various complicated factors such as molecular weight, melting point, compatibility with polymer, and dispersibility. Moreover, even if the antioxidant substance can be used in a polymer material, problems such as migration, volatilization, and extraction of the antioxidant in the polymer material must be considered, and if the good migration resistance, volatilization resistance, and extraction resistance cannot be achieved, the antioxidant effect of the antioxidant cannot be sufficiently exerted, and the antioxidant effect is affected. Therefore, it has been difficult to develop an antioxidant that can be used for a polymer and can sufficiently exert an antioxidant effect. On the basis, the defects of the existing antioxidant are overcome, the heat-resistant stability is improved, and the antioxidant effect is further difficult to improve. Therefore, it is an urgent problem to develop a novel antioxidant having higher antioxidant activity and improved heat stability for use as a polymer.
Disclosure of Invention
In view of the above, the present invention provides a hindered phenol antioxidant and a preparation method thereof, and the hindered phenol antioxidant provided by the present invention can be used for polymer materials, can improve heat resistance stability on the basis of generating good oxygen resistance, and is non-toxic and environment-friendly.
The invention provides a hindered phenol antioxidant which has a structure shown in a formula (1):
wherein R has a structure represented by formula (2):
the invention also provides a preparation method of the hindered phenol antioxidant in the technical scheme, which comprises the following steps:
under the action of a catalyst, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate and xylitol are subjected to esterification reaction to form the hindered phenol antioxidant shown in the formula (1).
Preferably, the catalyst is one or more of sodium methoxide, sodium ethoxide, potassium tert-butoxide, dimethyltin oxide and dibutyltin oxide.
Preferably, the molar ratio of the β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate to the xylitol is (5.0-7.0) to 1.0.
Preferably, the mass ratio of the catalyst to the total material is 0.05-0.2%;
the total material is β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate and xylitol.
Preferably, the temperature of the esterification reaction is 100-195 ℃.
Preferably, the esterification reaction is specifically:
the reaction is carried out for 4-7 h under normal pressure and then for 1-3 h under reduced pressure.
Preferably, the preparation method specifically comprises the following steps:
a) under the action of a catalyst, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate and xylitol are subjected to esterification reaction to obtain a reactant;
b) and (3) cooling the reactant, and adding a solvent for recrystallization to obtain the hindered phenol antioxidant shown in the formula (1).
Preferably, in the step b), the solvent is one or more of methanol, ethanol and isopropanol.
Preferably, in the step a), the reaction is carried out under an inert atmosphere;
in the step b), the temperature is reduced to 25-35 ℃.
The invention provides a hindered phenol antioxidant and a preparation method thereof. The antioxidant provided by the invention has proper molecular weight and melting point, and good compatibility and associativity with polymers, can be uniformly dispersed in a high polymer material matrix, and can be used as the antioxidant of a polymer material; meanwhile, the antioxidant has the advantages of good extraction resistance, volatilization resistance, migration resistance and the like, and can fully play the antioxidation role when being applied to polymer materials, thereby improving the antioxidation effect. Moreover, the antioxidant provided by the invention can improve the heat-resistant stability compared with the antioxidant 1010. In addition, the antioxidant provided by the invention has the advantages of low cost of raw materials, high reaction yield and capability of realizing industrial production.
The test result shows that compared with the conventional antioxidant, the antioxidant provided by the invention can obviously improve the thermal stability and oxidation resistance of the polymer material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 FTIR spectrum of the product obtained in example 1 of the present invention;
FIG. 2 is a 1H-NMR spectrum of the product obtained in example 1 of the present invention.
Detailed Description
The invention provides a hindered phenol antioxidant which has a structure shown in a formula (1):
wherein R has a structure represented by formula (2):
in the above formula (2), the wavy line means the junction of the R groups.
The antioxidant provided by the invention has proper molecular weight and melting point, and good compatibility and associativity with polymers, can be uniformly dispersed in a high polymer material matrix, and can be used as the antioxidant of a polymer material; meanwhile, the antioxidant has the advantages of good extraction resistance, volatilization resistance, migration resistance and the like, and can fully play the antioxidation role when being applied to polymer materials, thereby improving the antioxidation effect. Moreover, the antioxidant provided by the invention can improve the heat-resistant stability compared with the antioxidant 1010. In addition, the antioxidant provided by the invention has the advantages of low cost of raw materials, high reaction yield and capability of realizing industrial production.
The invention also provides a preparation method of the hindered phenol antioxidant in the technical scheme, which comprises the following steps:
under the action of a catalyst, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate and xylitol are subjected to esterification reaction to form the hindered phenol antioxidant shown in the formula (1).
The reaction route is as follows:
in the present invention, the source of the β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate is not particularly limited, and it may be a general commercial product or a preparation method known to those skilled in the art.
In the invention, the antioxidant is prepared by reacting specific xylitol with β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate, compared with other alcohols, the product prepared by reacting xylitol with the acrylic ester has more proper molecular weight, melting point, good compatibility and associativity with polymers, can be uniformly dispersed in a high polymer material matrix, and can be used as the antioxidant of polymer materials, meanwhile, the product has the advantages of good extraction resistance, volatilization resistance, migration resistance and the like, can fully play the role of antioxidation when being applied to the polymer materials, and can generate excellent antioxidation effect, and the antioxidant can also improve the heat resistance stability.
In addition, xylitol is a sweetener extracted from plant materials such as white birch, oak, corncob, bagasse, etc., has wide distribution range in nature, and is widely used in chewing gum, toothpaste for preventing dental caries, cosmetics, food, etc. The commercial xylitol is prepared by hydrolyzing and hydrogenating agricultural plant fiber waste materials (such as corncobs, cane sugar and the like), is a common bio-based polyol, is white crystal powder in appearance, belongs to a green environment-friendly raw material, has the advantages of reproducibility, low price, rich sources, excellent performance and the like, meets the requirements of green chemistry and national sustainable development strategy by adopting the substance as the raw material to synthesize the antioxidant, can relieve the current situation of shortage of domestic industrial raw materials, and has extremely high economical efficiency and good social benefit. The method has profound practical significance for promoting diversification of energy sources and upgrading of renewable energy source industry in China and relieving energy source and environmental pressure.
In the invention, the molar ratio of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate to xylitol is preferably (5.0-7.0) to 1.0, and in some embodiments of the invention, the molar ratio is 5.8: 1.0 or 6.2: 1.0.
In the present invention, the esterification reaction is carried out under the action of a catalyst. The catalyst is preferably one or more of sodium methoxide, sodium ethoxide, potassium tert-butoxide, dimethyltin oxide and dibutyltin oxide; more preferably sodium methoxide. In the present invention, the source of the catalyst is not particularly limited, and may be any commercially available product.
In the invention, the amount of the catalyst is preferably 0.05-0.2% and more preferably 0.1% in the mass ratio of the total materials, wherein the total materials refer to all reaction raw materials β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate and xylitol.
In the present invention, the esterification reaction is preferably carried out under an inert atmosphere. In the present invention, the inert gas for providing the inert atmosphere is not particularly limited, and may be a protective gas known to those skilled in the art, such as nitrogen, argon, helium, or the like. In some embodiments of the invention, the reaction is conducted under a nitrogen atmosphere.
In the invention, the temperature of the esterification reaction is preferably 100-195 ℃; in some embodiments of the invention, the temperature of the reaction is 180 ± 5 ℃ or 190 ± 5 ℃.
In the present invention, the esterification reaction is preferably: the reaction is carried out for 4-7 h under normal pressure and then for 1-3 h under reduced pressure. The reduced pressure is preferably 50mmHg to 5mmHg in absolute pressure. And (3) generating a byproduct methanol gas in the reaction process, preferably continuously reacting for a certain time after the reduced pressure reaction, pumping out the methanol gas generated in the reaction until no methanol is generated, namely ending the reaction. After the above reaction, a reactant was obtained.
In the present invention, after obtaining the reactant, it is preferable to further perform the following treatment: and (3) cooling the reactant, and adding a solvent for recrystallization to obtain the hindered phenol antioxidant shown in the formula (1).
In the invention, the temperature reduction is preferably reduced to 25-35 ℃. In the invention, the solvent adopted for recrystallization is preferably one or more of methanol, ethanol and isopropanol; more preferably isopropanol. In the present invention, after the recrystallization, it is preferable to further perform filtration, washing, and drying; wherein, the detergent used for washing is preferably one or more of methanol, ethanol and isopropanol. The drying temperature is preferably 40-50 ℃. After these post-treatments, a hindered phenol antioxidant represented by the formula (1) is obtained.
The preparation method provided by the invention has the following beneficial effects:
(1) the invention takes the xylitol as the raw material, can smoothly react with β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate, and has high product yield.
(2) The molecular structure of the antioxidant prepared by the invention contains five antioxidant groups, and the antioxidant can play a better antioxidant effect on the basis of meeting the application requirements of polymer materials.
(3) The antioxidant prepared by the invention can improve the heat-resistant stability and can be used under the high-temperature condition.
(4) The xylitol raw material adopted by the invention is a bio-based material, is derived from agricultural plant fiber waste, can be repeatedly regenerated in the biological world, is safer and healthier compared with industrial alcohol materials, and does not consume limited energy resources.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
1.1 preparation
Adding β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate 84.8g (0.29mol), xylitol 7.6g (0.05mol) and catalyst sodium methoxide 0.10g into a 250mL four-mouth bottle provided with an electric stirrer, a thermometer, a condenser and a methanol receiving device, heating and stirring, controlling the temperature to be 180 +/-5 ℃, reacting for 6h under normal pressure, then reacting for 2h under reduced pressure, removing methanol gas generated by the reaction, reacting until no methanol is generated, cooling, recrystallizing with isopropanol, filtering, washing with isopropanol and drying to obtain a product, wherein the appearance of the product is white solid.
1.2 characterization and testing
(1) FTIR test and 1H-NMR test of the obtained product are respectively shown in figure 1 and figure 2, wherein figure 1 is FTIR spectrum of the product obtained in the example 1 of the invention, and figure 2 is 1H-NMR spectrum of the product obtained in the example 1 of the invention. It can be seen that the resulting product has the structure of formula (1).
(2) The yield and purity of the obtained product are calculated and detected, and the result shows that the yield is 90 percent and the purity is 98.5 percent.
(3) The melting point of the obtained product is 75.0-76.2 ℃ through testing.
Example 2
Adding β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate 84.8g (0.29mol), xylitol 7.6g (0.05mol) and catalyst sodium methoxide 0.20g into a 250mL four-mouth bottle provided with an electric stirrer, a thermometer, a condenser and a methanol receiving device, heating and stirring, controlling the temperature to be 190 +/-5 ℃, reacting for 6h under normal pressure, then reacting for 2h under reduced pressure, removing methanol gas generated by the reaction, reacting until no methanol is generated, cooling, recrystallizing with isopropanol, filtering, washing with isopropanol and drying to obtain a product, wherein the appearance of the product is white solid.
The product was tested according to the characterization and testing of example 1, and the result showed that the obtained product has the structure of formula (1). The product yield is 92%, and the purity is 98.6%. The melting point of the product is 75.2-76.6 ℃.
Example 3
Adding 91.0g (0.31mol) of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate, 7.6g (0.05mol) of xylitol and 0.10g of catalyst sodium methoxide into a 250mL four-mouth bottle provided with an electric stirrer, a thermometer, a condenser and a methanol receiving device, heating and stirring, controlling the temperature to be 180 +/-5 ℃, reacting for 7 hours under normal pressure, then reacting for 2 hours under reduced pressure, removing methanol gas generated by the reaction, reacting until no methanol is generated, cooling, recrystallizing with isopropanol, filtering, washing with isopropanol and drying to obtain a product, wherein the appearance of the product is a white solid.
The product was tested according to the characterization and testing of example 1, and the result showed that the obtained product has the structure of formula (1). The product yield is 91% and the purity is 98.7%. The melting point of the product is 75.1-76.0 ℃.
Example 4
1.1 testing of processing stability
0.5g of the product obtained in example 1 is weighed, added to 500g of polypropylene powder, mixed well and extruded in an SHJ-20 twin-screw extruder, the screw temperature is set as follows: TS 1: 200 ℃, TS 2: 210 ℃, TS 3: 230 ℃, TS4-TS 9: 250 ℃, TS 10: at 210 ℃. The pellets were extruded three times and sampled separately to test the melt index (in g/10min) of each extruded pellet. And recording as a test group.
The procedure was followed except that no antioxidant was added. And noted as blank group.
The procedure was followed except that the antioxidant of example 1 was replaced with the antioxidant 1010. Record as antioxidant 1010 group.
The procedure was followed except that the antioxidant of example 1 was replaced with the antioxidant 1076. And is marked as antioxidant 1076 group.
The test results for the above four groups are shown in table 1:
TABLE 1 melt index test results for three extrusions of samples
| Blank group | Antioxidant 1010 group | Antioxidant 1076 group | Test group | |
| One-time extrusion, g/10min | 7.0 | 5.0 | 6.1 | 4.5 |
| Second extrusion, g/10min | 8.7 | 6.2 | 7.0 | 5.2 |
| Three times of extrusion, g/10min | 10.8 | 7.3 | 8.2 | 5.4 |
The test results in table 1 show that, compared with the blank group, the antioxidant 1010 group and the antioxidant 1076 group, the stability of the melt index of the product is significantly improved after the test group is subjected to multiple high-temperature processing, and the antioxidant provided by the invention can significantly improve the processing thermal stability of the material.
1.2 Oxidation resistance test
The four groups of secondary extruded materials are respectively taken to be tested for the oxidation induction period (OIT, unit is min), and the test temperature is 190 ℃ according to the national standard GB/T19466.1-2004. The test results are shown in table 2:
TABLE 2 results of oxidative induction period test of samples
| Blank group | Antioxidant 1010 group | Antioxidant 1076 group | Test group | |
| OIT，min | 1.6 | 6.0 | 1.9 | 7.0 |
Note: the oxidative induction period (OIT) is the time during which the sample begins to undergo autocatalytic oxidation under high temperature oxygen conditions.
As can be seen from the test results in Table 2, compared with the blank group, the antioxidant 1010 group and the antioxidant 1076 group, the test group can effectively prolong the oxidation induction period of the product, and the antioxidant effect of the antioxidant provided by the invention is remarkably improved compared with that of the existing antioxidant.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A hindered phenol antioxidant having a structure represented by formula (1):
wherein R has a structure represented by formula (2):
2. a method for preparing the hindered phenol antioxidant of claim 1, comprising the steps of:
under the action of a catalyst, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate and xylitol are subjected to esterification reaction to form the hindered phenol antioxidant shown in the formula (1).
3. The preparation method according to claim 2, wherein the catalyst is one or more of sodium methoxide, sodium ethoxide, potassium tert-butoxide, dimethyltin oxide and dibutyltin oxide.
4. The preparation method according to claim 2, wherein the molar ratio of β -methyl (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylate to xylitol is (5.0-7.0) to 1.0.
5. The preparation method according to claim 2, wherein the mass ratio of the catalyst to the total material is 0.05-0.2%;
the total material is β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate and xylitol.
6. The method according to claim 2, wherein the temperature of the esterification reaction is 100 to 195 ℃.
7. The preparation method according to claim 2 or 6, characterized in that the esterification reaction is in particular:
the reaction is carried out for 4-7 h under normal pressure and then for 1-3 h under reduced pressure.
8. The preparation method according to claim 2, wherein the preparation method specifically comprises:
a) under the action of a catalyst, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl acrylate and xylitol are subjected to esterification reaction to obtain a reactant;
b) and (3) cooling the reactant, and adding a solvent for recrystallization to obtain the hindered phenol antioxidant shown in the formula (1).
9. The preparation method according to claim 8, wherein in the step b), the solvent is one or more of methanol, ethanol and isopropanol.
10. The method according to claim 8, wherein in the step a), the reaction is carried out under an inert atmosphere;
in the step b), the temperature is reduced to 25-35 ℃.
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| CN113004192A (en) * | 2021-03-08 | 2021-06-22 | 山东省临沂市三丰化工有限公司 | Hindered phenol antioxidant and preparation method thereof |
| WO2021190569A1 (en) * | 2020-03-26 | 2021-09-30 | 曾裕峰 | Low-migration hindered phenol antioxidant compound, preparation method and composition |
| CN115197065A (en) * | 2021-04-08 | 2022-10-18 | 天津利安隆新材料股份有限公司 | Intramolecular compound hindered phenol compound, preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021190569A1 (en) * | 2020-03-26 | 2021-09-30 | 曾裕峰 | Low-migration hindered phenol antioxidant compound, preparation method and composition |
| CN113004192A (en) * | 2021-03-08 | 2021-06-22 | 山东省临沂市三丰化工有限公司 | Hindered phenol antioxidant and preparation method thereof |
| CN115197065A (en) * | 2021-04-08 | 2022-10-18 | 天津利安隆新材料股份有限公司 | Intramolecular compound hindered phenol compound, preparation method and application thereof |
| CN115197065B (en) * | 2021-04-08 | 2024-01-30 | 天津利安隆新材料股份有限公司 | Intramolecular compound hindered phenol compound, preparation method and application thereof |
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