CN112063016A - Preparation method of long-acting phosphite ester antioxidant - Google Patents
Preparation method of long-acting phosphite ester antioxidant Download PDFInfo
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- CN112063016A CN112063016A CN202011275145.4A CN202011275145A CN112063016A CN 112063016 A CN112063016 A CN 112063016A CN 202011275145 A CN202011275145 A CN 202011275145A CN 112063016 A CN112063016 A CN 112063016A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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Abstract
The invention relates to a long-acting phosphite ester antioxidant and a preparation process thereof, wherein the antioxidant is prepared by the following method: mixing phosphite ester antioxidant with hydrolysis resistance agent to obtain long-acting phosphite ester antioxidant; the hydrolysis resisting agent is modified hydrotalcite, in particular to hydrotalcite modified by quaternary ammonium salt type cationic surfactant. According to the invention, the alkaline substance and the hydrolysis resistant agent are utilized to neutralize the acidic substance in the phosphite ester system, so that the occurrence of autocatalysis is avoided, the purpose of hydrolytic stability is achieved, the thermal stability and the service life of the hydrotalcite are improved, and the hydrotalcite is modified by the cationic surfactant so as to improve the organic affinity.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a preparation method of a long-acting phosphite ester antioxidant.
Background
Phosphorus-containing antioxidants are generally regarded at home and abroad in recent years, and are mainly phosphites, the antioxidants are main varieties of antioxidants and auxiliary antioxidants for plastic processing, and the antioxidants can be used as plastic additives to effectively improve the processing stability, heat-resistant stability, color improvement and weather resistance of resin. Wherein the antioxidants 168, 626 and TNP are representative varieties of phosphite antioxidants.
With the wide application of high-performance hindered amine light stabilizers in the 70 s, phosphite ester serving as an auxiliary antioxidant for high polymer materials does not generate harmful negative effects with the hindered amine light stabilizers, and shows good synergistic effects. For this reason, research on the development of phosphite-based secondary antioxidants has attracted worldwide attention over the 80 s. The phosphite ester has the function of peroxide decomposer, can be added with double bonds to chelate metals and Lewis acid, reacts with hydrogen halide, and has good synergistic effect with main antioxidant, so that the phosphite ester can endow high molecular material with thermal stability, passivate harmful metals, slow down the degradation of polymers and have certain light stability. Due to a plurality of advantages, the phosphite antioxidant becomes a polymer with good multifunctional antioxidant and auxiliary antioxidant.
The defects of the existing phosphite antioxidant are mainly reflected in that the existing phosphite antioxidant has strong hygroscopicity, is very easy to hydrolyze and lose efficacy in the processes of storage, processing and use, and simultaneously, the problems of lower solvent recovery rate, high recovery cost, serious environmental pollution and the like in the preparation process of the existing phosphite antioxidant are solved. CN106832412A discloses a modified hydrotalcite to improve the hydrolysis resistance of phosphite antioxidants, but the amount is large and the production cost is high.
Disclosure of Invention
In order to solve the problems of strong hygroscopicity and easy hydrolysis of phosphite antioxidants in the prior art, the invention aims to provide a preparation method of long-acting phosphite antioxidants, which comprises the following steps: mixing phosphite ester antioxidant with hydrolysis resistance agent to obtain long-acting phosphite ester antioxidant;
the hydrolysis resisting agent is modified hydrotalcite, in particular to hydrotalcite modified by quaternary ammonium salt type cationic surfactant.
In the present invention, the quaternary ammonium salt type cationic surfactant is tetradecyltrimethylammonium chloride or tetradecyltrimethylammonium bromide.
In the invention, the preparation method of the hydrolysis resistant agent comprises the following steps: mixing the aqueous solution of the quaternary ammonium salt cationic surfactant with hydrotalcite, stirring at constant temperature for modification, and then carrying out solid-liquid separation and drying to obtain the modified hydrotalcite hydrolysis resisting agent.
In the invention, the weight ratio of the quaternary ammonium salt cationic surfactant to the hydrotalcite is 1: 2-10. The modification temperature is 60-110 ℃, and the modification time is 0.5-2 h.
In the invention, the phosphite ester antioxidant and the hydrolysis resistance agent are mixed and then crushed; preparing long-acting phosphite ester antioxidant with uniform granularity; preferably, the particle size D50 is 10-150 nm.
In the invention, the phosphite ester antioxidant is a non-liquid phosphite ester antioxidant; preferably, the phosphite antioxidant is selected from one or more of tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, and tetrakis (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite.
The invention also provides a long-acting phosphite ester antioxidant which is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that: the hydrolysis resistance agent prepared by the alkaline quaternary ammonium salt cationic surfactant and the hydrotalcite hydrolysis resistance agent is used for neutralizing acidic substances in a phosphite ester system so as to avoid autocatalysis, achieve the aim of hydrolysis stability, improve the thermal stability and prolong the service life of the hydrotalcite, and the hydrotalcite is modified by the quaternary ammonium salt cationic surfactant so as to improve the organic affinity, reduce the problem that the hydrotalcite is easy to generate agglomeration, and improve the oxygen resistance, the compatibility and the long-acting property of the phosphite ester.
Detailed Description
The present invention will be described in detail with reference to the following embodiments, but it should be understood that the scope of the present invention is not limited by these embodiments and the principle of the present invention, but is defined by the claims.
In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable.
The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the examples but also the endpoints of each numerical range in the specification, and ranges in which any combination of the numerical points is disclosed or recited should be considered as ranges of the present invention.
Technical and scientific terms used herein are to be defined only in accordance with their definitions, and are to be understood as having ordinary meanings in the art without any definitions.
A preparation method of a long-acting phosphite antioxidant comprises the following steps: mixing phosphite ester antioxidant with hydrolysis resistance agent to obtain long-acting phosphite ester antioxidant;
the hydrolysis resisting agent is modified hydrotalcite, in particular to hydrotalcite modified by quaternary ammonium salt type cationic surfactant.
According to the invention, the hydrotalcite is modified by adopting the quaternary ammonium salt cationic surfactant to obtain the hydrotalcite with alkalinity, wherein the alkaline substance can neutralize acidic substances such as phosphite ester, phenol and the like generated after hydrolysis of the phosphite ester antioxidant, so that autocatalysis is avoided, the purpose of hydrolytic stability is achieved, and the effect is more long-acting; meanwhile, the organic affinity and the compatibility of the phosphite ester antioxidant are improved, and the problem that the phosphite ester antioxidant is easy to generate agglomeration is reduced.
In the invention, the quaternary ammonium salt cationic surfactant is preferably tetradecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium bromide, the bonding degree of the quaternary ammonium salt cationic surfactant and hydrotalcite is higher, and the prepared modified hydrotalcite has better stability.
The hydrotalcite provided by the invention is hydrotalcite known in the field, such as magnesium aluminum carbonate hydrotalcite, magnesium aluminum nitrate hydrotalcite, zinc aluminum carbonate hydrotalcite, zinc aluminum nitrate hydrotalcite, nickel aluminum carbonate hydrotalcite, nickel aluminum nitrate hydrotalcite and the like.
In the invention, the preparation method of the hydrolysis resistant agent comprises the following steps:
mixing the aqueous solution of the quaternary ammonium salt cationic surfactant with hydrotalcite, stirring at constant temperature for modification, and then carrying out solid-liquid separation and drying to obtain the modified hydrotalcite hydrolysis resisting agent.
Researches show that in the process of preparing the modified hydrotalcite, the activation index of hydrotalcite powder is increased along with the increase of the dosage of the quaternary ammonium salt cationic surfactant; the quaternary ammonium salt cationic surfactant is used in an excessively small amount, and the surface of the powder is not completely treated, so that the aim of modification cannot be fulfilled; in order to obtain the hydrolysis resistant agent with better hydrolysis resistant effect, the weight ratio of the quaternary ammonium salt cationic surfactant to the hydrotalcite is 1:2-10, and preferably 1: 4-6. For example, when the weight ratio is 1:5, the activation index can reach 99.3%, and the hydrotalcite modification effect is better.
Researches show that in the process of preparing the modified hydrotalcite, the modification temperature is too low, and enough energy cannot be provided to ensure that the surface adsorption is completely carried out; and the modification temperature is too high, and the adsorption quantity is also reduced. Preferably, the modification temperature is 60-110 deg.C, and in specific embodiments, the modification temperature can be 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C.
Meanwhile, within the modification temperature range, the modification time is too short, the hydrotalcite powder is not fully contacted with the quaternary ammonium salt cationic surfactant, the modification is incomplete, and the activation index is small, but when the activation index reaches the maximum value, the modification time is increased again, so that the modified groups adsorbed on the surface of the powder are desorbed along with the action of shearing force, and the reduction of the activation index is caused. The research shows that the modification effect is better when the modification time is 0.5-2h, preferably 0.8-1.2h, and more preferably 1.0 h.
In the method for preparing the hydrolysis resistant agent, the solid-liquid separation is a solid-liquid separation method known to those skilled in the art, and for example, centrifugation and filtration can be selected in specific examples. The drying is also known to those skilled in the art, and for example, drying, natural drying, vacuum drying, etc. may be selected as specific examples, and drying is preferred in the present method.
In the method for producing the hydrolysis resistant agent, as a preferred embodiment, an aqueous solution having a concentration of 0.01 to 1g/ml is prepared as the quaternary ammonium salt type cationic surfactant, and in order to obtain a hydrolysis resistant agent having a good hydrolysis resistant effect and sufficiently fit with hydrotalcite, the concentration of the aqueous solution of the quaternary ammonium salt type cationic surfactant is preferably 0.05 to 0.1g/ml, and may be, for example, 0.06g/ml, 0.07g/ml, 0.08g/ml, or 0.09 g/ml.
In a preferred embodiment, deionized water is used to wash the modified hydrotalcite solid before and after drying in order to remove incompletely loaded quaternary ammonium salt cationic surfactant and obtain hydrolysis resistant agent with better stability.
In the invention, in order to ensure the hydrolysis resistance effect, the phosphite ester antioxidant and the hydrolysis resistance agent are mixed and then crushed; preparing long-acting phosphite ester antioxidant with uniform granularity; when the particle size D50 is too large, hydrolysis resistance is affected, and the long-term effect of the phosphite antioxidant is affected. Preferably, the D50 particle size has better hydrolysis resistance at 150nm or less, but from the industrial production point of view, the particle size is preferably 10-150nm, more preferably 60-100nm, and in specific examples can be 70nm, 80nm, 90 nm. As a preferred embodiment, the pulverization may be a pulverization method commonly used in experiments and industry, such as ball milling with a ball mill, pulverization with a pulverizer, or the like.
The phosphite ester antioxidant is a non-liquid phosphite ester antioxidant; can be any non-liquid phosphite antioxidant with easy hydrolysis characteristics known in the art, such as solid powder or granular or crystal or block form phosphite. Preferably, the phosphite antioxidant is one or more of tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626), bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (antioxidant PEP-36), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (antioxidant 9228), and tetrakis (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite (antioxidant P-EPQ).
The above phosphite antioxidants may be prepared by any method known to those skilled in the art, or may be commercially available phosphite antioxidants.
In order to balance economic benefits and hydrolysis resistance effect, the addition amount of the hydrolysis resistance agent in the phosphite antioxidant is 0.4-0.6 wt%. The modified hydrotalcite of the present application can exhibit excellent hydrolysis resistance when added in an amount of 0.4 to 0.6 wt%. Anionic surfactants such as sodium dodecyl sulfate, nonionic surfactants such as stearic acid or alkyl coupling agents, and mixtures thereof have also been tried in the course of research, and it was found that the amount of surfactant used is large when these surfactants are selected to modify hydrotalcite. And the effect of the hydrotalcite which is singly or compositely modified by the anionic surfactant or the nonionic surfactant with the same granularity as that of the hydrotalcite in the application is equivalent to that of the hydrotalcite which is not modified when the addition amount is 0.4 to 0.6 weight percent; the addition amount of the additive is 3-10 wt% to show certain hydrolysis resistance.
In another aspect of the present invention, there is provided a long-acting phosphite antioxidant prepared by the steps of: mixing phosphite ester antioxidant with hydrolysis resistance agent to obtain long-acting phosphite ester antioxidant; the hydrolysis resisting agent is modified hydrotalcite, in particular to hydrotalcite modified by quaternary ammonium salt type cationic surfactant.
Preferably, the quaternary ammonium salt type cationic surfactant is tetradecyltrimethylammonium chloride or tetradecyltrimethylammonium bromide.
The phosphite ester antioxidant is a non-liquid phosphite ester antioxidant; can be any non-liquid phosphite antioxidant with easy hydrolysis characteristics known in the art, such as solid powder or granular or crystal or block form phosphite. Preferably, the phosphite antioxidant is one or more of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (antioxidant PEP-36), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (antioxidant 9228), and tetrakis (2, 4-di-tert-butylphenol) 4,4' -biphenyl diphosphite (antioxidant P-EPQ).
The embodiments described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLES A-EXAMPLE H preparation of hydrolysis resistant agent
Mixing a cationic surfactant: dissolving tetradecyl trimethyl ammonium chloride in a certain amount of deionized water, adding a certain amount of magnesium-aluminum hydrotalcite after dissolving, and adding into a reaction container for stirring at constant temperature; filtering the mixed solution after stirring, and cleaning a filter cake by using deionized water; and drying the washed filter cake in a drying oven at 105 ℃, and drying to obtain the modified hydrotalcite.
Setting 8 examples from example A to example H, respectively controlling 3 main process factors of the amount of the cationic surfactant, the volume of the deionized water, the modification time and the modification temperature to carry out experiments, and detecting the activation index of the hydrotalcite after the modification is finished (measuring the LDH activation index according to the standard HG T2567-2006 of the department of chemical industry). The results are shown in Table 1.
TABLE 1 Main Process parameters and activation index results for modified hydrotalcites of examples A-H
As can be seen from examples a to D in table 1, the activation index of the hydrotalcite powder increases with an increase in the amount of the quaternary ammonium salt type cationic surfactant used and an increase in the concentration of the aqueous solution of the quaternary ammonium salt type cationic surfactant.
It can be seen from examples C, F and G that the activation index increases with the increase of the modification time, but when the activation index reaches the maximum value, the modification group adsorbed on the surface of the powder is desorbed with the action of the shear force by increasing the modification time, and the activation index decreases.
It can be seen from examples E, C and H that the activation index increases with increasing modification temperature, while too high a modification temperature reduces the amount of adsorption.
Example 1
A method for preparing long-acting bis (2,4 di-tert-butylphenyl) pentaerythritol diphosphite, which comprises the following steps:
30G of commercially available bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and 0.15G of the hydrolysis resistant agent from example G were introduced into a ball mill and milled in a ball mill for 2 hours, the milling being carried out with uniform mixing and the rotational speed of the ball mill being controlled at 1000 revolutions per minute. And uniformly mixing to obtain the phosphite ester antioxidant. Particle size D50 of phosphite powder after grinding: 150 +/-10 um.
The phosphite ester antioxidant sample prepared by the above embodiment has a purity of 98.18% by HPLC analysis, and an acid value of 0.07mgKOH/g by titration analysis.
Example 2
A method for preparing long-acting bis (2,4 di-tert-butylphenyl) pentaerythritol diphosphite, which comprises the following steps:
30G of commercially available bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and 0.15G of the hydrolysis resistant agent from example G were introduced into a ball mill and milled in a ball mill for 3.0 hours, the milling being carried out with uniform mixing and the rotational speed of the ball mill being controlled at 1000 rpm. And uniformly mixing to obtain the phosphite ester antioxidant. Particle size D50 of phosphite powder after grinding: 120 +/-10 um.
The phosphite antioxidant sample prepared in the above example has a purity of 98.24% by HPLC analysis, and an acid value of 0.09mgKOH/g by titration analysis.
Example 3
A method for preparing long-acting bis (2,4 di-tert-butylphenyl) pentaerythritol diphosphite, which comprises the following steps:
30G of commercially available bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and 0.15G of the hydrolysis resistant agent from example G were introduced into a ball mill and milled in a ball mill for 5.0 hours, the mixture was mixed homogeneously and the ball mill was rotated at 1000 rpm. And uniformly mixing to obtain the phosphite ester antioxidant. Particle size D50 of phosphite powder after grinding: 90 +/-10 um.
The phosphite ester antioxidant sample prepared by the above embodiment has a purity of 98.21% by HPLC analysis, and an acid value of 0.09mgKOH/g by titration analysis.
Example 4
A method for preparing long-acting bis (2,4 di-tert-butylphenyl) pentaerythritol diphosphite, which comprises the following steps:
30G of commercially available bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and 0.15G of the hydrolysis resistant agent from example G were introduced into a ball mill and milled in a ball mill for a period of 8.0 hours, the milling speed being controlled at 1000 revolutions per minute. And uniformly mixing to obtain the phosphite ester antioxidant. Particle size D50 of phosphite powder after grinding: 70 +/-10 um.
The phosphite ester antioxidant sample prepared by the above embodiment has a purity of 98.19% by HPLC analysis, and an acid value of 0.08mgKOH/g by titration analysis.
Comparative example 1
30g of commercially available bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite (as used in examples 1 to 4) and 0.15g of unmodified hydrotalcite were put into a ball mill and ball-milled and pulverized, and the mixture was uniformly mixed, and ground for 6.0 hours while controlling the rotation speed of the ball mill at 1000 rpm. And uniformly mixing to obtain the phosphite ester antioxidant. Particle size D50 of phosphite powder after grinding: 90 +/-10 nm.
The phosphite ester antioxidant sample prepared by the above embodiment has a purity of 98.17% by HPLC analysis, and an acid value of 0.09mgKOH/g by titration analysis.
Comparative example 2
The same as example 3, except that 0.15g of hydrolysis resistant agent (sodium dodecylsulfate-modified hydrotalcite) prepared according to example 1 of patent CN106832412A was added. The purity was 98.25% by chromatography and the acid value was 0.06mgKOH/g by titration.
Hydrolysis resistance effect experiment:
examples 1-4 and comparative example 1, commercially available bis (2,4 di-t-butylphenyl) pentaerythritol diphosphite (the same commercially available product as used in examples 1-4) were each tested for its initial data and placed under ambient humidity of 60 + -5%, temperature of 25 + -2 deg.C for a week, a month and three months for the major content, 2, 4-phenax content and acid value.
TABLE 2 hydrolysis resistance data
From the data in table 2, it can be seen that the batch added with the hydrolysis resistant agent of the present invention is significantly better than the products obtained from the commercial products, the unmodified hydrotalcite and the sodium dodecyl sulfate modified hydrotalcite after being placed for three months at the temperature of 25 ± 2 ℃ and the ambient humidity of 60 ± 5%, especially the example 3 and the example 4 have better effect, and the most preferable example 3 is from the viewpoint of industrial production.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a long-acting phosphite antioxidant is characterized by comprising the following steps: mixing phosphite ester antioxidant with hydrolysis resistance agent to obtain long-acting phosphite ester antioxidant;
the hydrolysis resisting agent is modified hydrotalcite, in particular to hydrotalcite modified by quaternary ammonium salt type cationic surfactant.
2. The method according to claim 1, wherein the quaternary ammonium salt type cationic surfactant is tetradecyltrimethylammonium chloride or tetradecyltrimethylammonium bromide.
3. The method according to claim 1 or 2, wherein the hydrolysis resistance agent is prepared by a method comprising the steps of: mixing the aqueous solution of the quaternary ammonium salt cationic surfactant with hydrotalcite, stirring at constant temperature for modification, and then carrying out solid-liquid separation and drying to obtain the modified hydrotalcite hydrolysis resisting agent.
4. The production method according to claim 3, wherein the weight ratio of the quaternary ammonium salt cationic surfactant to the hydrotalcite is 1:2 to 10.
5. The process according to claim 3, wherein the modification temperature is 60 to 110 ℃ and the modification time is 0.5 to 2 hours.
6. The method according to claim 3, wherein the concentration of the aqueous solution of the quaternary ammonium salt type cationic surfactant is 0.01 to 1 g/ml.
7. The method according to any one of claims 1, 2,4, 5 and 6, wherein the phosphite antioxidant and the hydrolysis resistance agent are mixed and then pulverized; to obtain long-acting phosphite antioxidant with the particle size D50 of 10-150 nm.
8. The method of any one of claims 1, 2,4, 5, and 6, wherein the phosphite antioxidant is a non-liquid phosphite antioxidant.
9. The method of claim 8, wherein the phosphite antioxidant is selected from one or more of bis (2,4 di-t-butylphenyl) pentaerythritol diphosphite, tris (2, 4-di-t-butylphenyl) phosphite, bis (2, 6 di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, tetrakis (2, 4-di-t-butylphenol) 4,4' -biphenyl diphosphite; and/or the presence of a gas in the gas,
the addition amount of the hydrolysis resistant agent in the phosphite ester antioxidant is 0.4-0.6%.
10. A long-acting phosphite antioxidant prepared by the method of any one of claims 1, 2,4, 5, 6, and 9.
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| CN113604292A (en) * | 2021-09-13 | 2021-11-05 | 常州智高化学科技有限公司 | Modified alcohol detergent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117504A (en) * | 1994-04-05 | 1996-02-28 | 希巴-盖吉股份公司 | Enhancement of the storage stability of organic phosphites and phosphonites |
| CN1281001A (en) * | 1999-07-15 | 2001-01-24 | 奇美实业股份有限公司 | Anti-hydrolysis organophosphoric deoxidant |
| JP2001055572A (en) * | 1999-08-19 | 2001-02-27 | Qimei Industry Co Ltd | Hydrolysis-resistant organophosphorus antioxidant |
| CN106832412A (en) * | 2017-01-17 | 2017-06-13 | 哈尔滨工业大学无锡新材料研究院 | A kind of hydrolysis phosphite ester kind antioxidant |
| WO2020021042A1 (en) * | 2018-07-25 | 2020-01-30 | SI Group Switzerland (Chaa) Gmbh | Composition |
| CN111471328A (en) * | 2020-04-27 | 2020-07-31 | 杭州临安华立塑胶有限公司 | Modification method of hydrotalcite powder and application of hydrotalcite powder in calcium-zinc stabilizer |
-
2020
- 2020-11-16 CN CN202011275145.4A patent/CN112063016B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117504A (en) * | 1994-04-05 | 1996-02-28 | 希巴-盖吉股份公司 | Enhancement of the storage stability of organic phosphites and phosphonites |
| CN1281001A (en) * | 1999-07-15 | 2001-01-24 | 奇美实业股份有限公司 | Anti-hydrolysis organophosphoric deoxidant |
| JP2001055572A (en) * | 1999-08-19 | 2001-02-27 | Qimei Industry Co Ltd | Hydrolysis-resistant organophosphorus antioxidant |
| CN106832412A (en) * | 2017-01-17 | 2017-06-13 | 哈尔滨工业大学无锡新材料研究院 | A kind of hydrolysis phosphite ester kind antioxidant |
| WO2020021042A1 (en) * | 2018-07-25 | 2020-01-30 | SI Group Switzerland (Chaa) Gmbh | Composition |
| CN111471328A (en) * | 2020-04-27 | 2020-07-31 | 杭州临安华立塑胶有限公司 | Modification method of hydrotalcite powder and application of hydrotalcite powder in calcium-zinc stabilizer |
Non-Patent Citations (1)
| Title |
|---|
| 李文彬 佟妍: "《精细化工生产技术》", 31 January 2014, 中国广播电视大学出版社·北京 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113604292A (en) * | 2021-09-13 | 2021-11-05 | 常州智高化学科技有限公司 | Modified alcohol detergent and preparation method thereof |
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