Anhydrous deoxidizer

Abstract

This invention discloses an anhydrous deoxidizer, comprising, by weight, 10-20 parts of a hydroxyl-terminated polybutadiene-maleic anhydride compound, 10-20 parts of modified zeolite, 15-25 parts of modified silica gel, and 45-55 parts of polyethylene terephthalate. The modified silica gel is prepared from silica gel, sorbitol, bis(3-triethoxysilanepropyl) carbonate, and alumina. The modified zeolite is prepared from zeolite, 1-chloroethylcyclohexyl carbonate, maleimide-L-valine-L-citrulline-p-aminobenzyl alcohol, and N,N-dimethylformamide. The anhydrous deoxidizer provided by this invention exhibits excellent deoxidation performance and efficiency.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of deoxidizer, in particular to a kind of anhydrous deoxidizer. BACKGROUND

[0002] 21% oxygen in air, light, temperature and humidity, moisture, microorganism, insect, dust and the like are the main reasons for causing the growth of mold and aerobic bacteria, rancidity and oxidation of oil and fat, and loss of vitamin. The deoxidizer commonly used in market at present is an external control preservative capable of absorbing oxygen in food packaging container. Its antibacterial mechanism is mainly to absorb oxygen in packaging container to inhibit the growth of aerobic bacteria and oxidation of oil contained in food, so as to achieve the purpose of preservation and prolonging shelf life. However, some foods need to maintain dry environment in food packaging by physical, deliquescence or chemical hygroscopicity while deoxidizing, so as to maintain product quality and certain taste. The application of deoxidizer in packaging is developed on the basis of modified atmosphere packaging. The deoxidizer is sealed in a bag with good oxygen resistance to change the composition of gas in the bag, so as to achieve the purpose of prolonging shelf life. It is different from other additives, does not have to be directly added into food, has no toxic effect on food, and can be safely used. It has better deoxidizing effect than vacuum packaging and air packaging, and can maintain oxygen-free state for a long time in the bag, which has good effect on preventing mold, insect, discoloration, fading, oxidation, and can maintain the nutrition, freshness and taste of food. At present, deoxidizer has been widely used in the packaging of various foods.

[0003] The mainstream deoxidizer product in market at present is iron-based deoxidizer, which achieves the effect of oxygen absorption by oxidation of iron powder with oxygen in air. The disadvantage of this technology is that water is needed in the reaction process, which results in that the packaging space cannot achieve dry effect, and has bad influence on some foods and drugs that need to maintain dryness. After oxygen absorption, the current iron-based deoxidizer generates a large amount of heat, which has adverse effect on some products that are greatly affected by temperature. After oxygen absorption, the iron-based deoxidizer generates rust, which produces rust spots on the package and affects the appearance of product. CN116570002A discloses a composite iron-based deoxidizer and its preparation method, which not only has the above-mentioned disadvantages of iron-based deoxidizer, but also has the problem of low deoxidizing efficiency. CN101531726A discloses an oxygen absorber for polyester packaging material and its preparation method, however, it not only has poor deoxidizing performance, but also has low deoxidizing efficiency.

[0004] In summary, through the massive retrieval of the applicant, there is at least the problem of poor deoxidizing performance and low deoxidizing efficiency of the existing oxygen absorber and its preparation method in the art, therefore, it is necessary to develop or improve a kind of anhydrous deoxidizer. SUMMARY

[0005] Based on this, in order to solve the problems of poor deoxidation performance and low deoxidation efficiency of the existing oxygen absorbent and its preparation method, the application provides a kind of anhydrous deoxidizer, and the specific technical solutions are as follows:

[0006] An anhydrous deoxidizer, by mass fraction, comprises 10-20 parts of hydroxyl-terminated polybutadiene-maleic anhydride compound, 10-20 parts of modified zeolite, 15-25 parts of modified silica gel and 45-55 parts of polyethylene terephthalate;

[0007] The preparation raw materials of the modified silica gel include silica gel, sorbitol, bis(3-triethoxysilylpropyl) carbonate and aluminum oxide;

[0008] The preparation raw materials of the modified zeolite include zeolite, 1-chloroethyl cyclohexyl carbonate, maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol and N,N-dimethylformamide.

[0009] Further, the preparation method of the hydroxyl-terminated polybutadiene-maleic anhydride compound comprises the following steps:

[0010] The hydroxyl-terminated polybutadiene is added into a four-necked flask, then maleic anhydride and cyclohexane are added, after stirring uniformly, γ-alumina is added, then the temperature is raised to 80-85℃ for 2.5-3.5h, and water is separated out by using a water trap during the reaction, then the obtained product is cooled, washed, filtered and distilled to obtain the hydroxyl-terminated polybutadiene-maleic anhydride compound.

[0011] Further, the mass ratio of the hydroxyl-terminated polybutadiene, the maleic anhydride and the cyclohexane is 25-35:25-35:10-20.

[0012] Further, the preparation method of the modified zeolite comprises the following steps:

[0013] Under argon atmosphere, the zeolite is added into N,N-dimethylformamide, stirred uniformly at a speed of 150-250r / min, then 1-chloroethyl cyclohexyl carbonate and maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol are added, stirred at a speed of 200-300r / min, then the temperature is raised to 110-120℃ for 3.1-3.5h, then cooled, and then dried at 60-80℃ for 6-8h to obtain the modified zeolite.

[0014] Further, the mass ratio of the zeolite, 1-chloroethyl cyclohexyl carbonate, maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol and N,N-dimethylformamide is 70-90:5-15:5-15:90-110.

[0015] Further, the preparation method of the modified silica gel comprises the following steps:

[0016] The silica gel is added into sorbitol, stirred uniformly at a speed of 300-400 r / min, then bis(3-triethoxysilane propyl) carbonate and alumina are added, nitrogen is introduced, stirred uniformly at a speed of 500-600 r / min, then continue to stir, heated to 80-90℃ for 5-7 h, dried after cooling, to obtain the modified silica gel.

[0017] Further, the mass ratio of the silica gel, sorbitol, bis(3-triethoxysilane propyl) carbonate and alumina is 45-55:25-35:5-15:5-15.

[0018] The technical solution further provides a preparation method of anhydrous deoxidizer, comprising the following steps:

[0019] The polyethylene terephthalate is subjected to drying treatment, then mixed uniformly with hydroxyl-terminated polybutadiene-maleic anhydride compound and cobalt acetate catalyst in a high-speed stirrer, extruded through a double-screw extruder, cooled, granulated, then broken by a high-speed crusher, screened, to obtain 60-80 mesh A particles;

[0020] The A particles, modified zeolite and modified silica gel are mixed uniformly, then added into a high-speed powdering machine, to obtain 80-120 mesh B powder, then the B powder is placed in an oven, dried at 70-90℃ for 0.5-1 h, to obtain the anhydrous deoxidizer.

[0021] Further, the drying treatment is performed at a drying temperature of 110-130℃ for 20-28 h.

[0022] Further, the vacuum degree of the double-screw extruder is 0.05-0.11 MPa.

[0023] The anhydrous deoxidizing agent provided by the technical scheme has excellent deoxidizing performance and deoxidizing efficiency. Specifically, the anhydrous deoxidizing agent is based on an end-hydroxyl polybutadiene-maleic anhydride compound and polyethylene terephthalate, and a certain proportion of modified zeolite and a certain proportion of modified silica gel are added, so that the anhydrous deoxidizing agent has excellent deoxidizing performance and deoxidizing efficiency. More specifically, the modified zeolite is modified by maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol and 1-chloroethyl cyclohexyl carbonate, and the modified zeolite has a significant oxygen absorption effect due to the macromolecular chain and multiple multi-electron groups. The silica gel modified by sorbitol, bis(3-triethoxysilylpropyl) carbonate and aluminum oxide has more Si-O and Al-O polar bonds, and part of the Si-O and Al-O polar bonds are bonded with the polar functional groups of bis(3-triethoxysilylpropyl) carbonate. The Si-O and Al-O polar bonds and the polar functional groups of the modified silica gel interact with the macromolecular chain polar functional groups of the modified zeolite, so that the deoxidizing performance and deoxidizing efficiency of the obtained anhydrous deoxidizing agent are excellent. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is a reaction path of the end-hydroxyl polybutadiene-maleic anhydride compound. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical scheme and advantages of the present application more clear and explicit, the present application will be further described in detail below in combination with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the protection scope of the present application.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0027] The anhydrous deoxidizing agent provided by the technical scheme has excellent deoxidizing performance and deoxidizing efficiency. Specifically, the anhydrous deoxidizing agent is based on an end-hydroxyl polybutadiene-maleic anhydride compound and polyethylene terephthalate, and a certain proportion of modified zeolite and a certain proportion of modified silica gel are added, so that the anhydrous deoxidizing agent has excellent deoxidizing performance and deoxidizing efficiency. More specifically, the modified zeolite is modified by maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol and 1-chloroethyl cyclohexyl carbonate, and the modified zeolite has a significant oxygen absorption effect due to the macromolecular chain and multiple multi-electron groups. The silica gel modified by sorbitol, bis(3-triethoxysilylpropyl) carbonate and aluminum oxide has more Si-O and Al-O polar bonds, and part of the Si-O and Al-O polar bonds are bonded with the polar functional groups of bis(3-triethoxysilylpropyl) carbonate. The Si-O and Al-O polar bonds and the polar functional groups of the modified silica gel interact with the macromolecular chain polar functional groups of the modified zeolite, so that the deoxidizing performance and deoxidizing efficiency of the obtained anhydrous deoxidizing agent are excellent.

[0028] The preparation raw materials of the modified silica gel include silica gel, sorbitol, bis(3-triethoxysilylpropyl) carbonate and aluminum oxide.

[0029] The raw material for preparing the modified zeolite comprises zeolite, 1-chloroethyl cyclohexyl carbonate, maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol and N,N-dimethylformamide.

[0030] In one of the embodiments, the method for preparing the hydroxyl-terminated polybutadiene-maleic anhydride compound comprises the following steps:

[0031] The hydroxyl-terminated polybutadiene is added into a four-necked flask, then maleic anhydride and cyclohexane are added, after stirring uniformly, γ-alumina is added, then the temperature is raised to 80-85℃ for 2.5-3.5h, during the reaction, a water trap is used to separate water, then the product is cooled, washed, filtered and distilled to obtain the hydroxyl-terminated polybutadiene-maleic anhydride compound.

[0032] In one of the embodiments, the mass ratio of the hydroxyl-terminated polybutadiene, the maleic anhydride and the cyclohexane is 25-35:25-35:10-20.

[0033] In one of the embodiments, the method for preparing the modified zeolite comprises the following steps:

[0034] Under argon atmosphere, the zeolite is added into N,N-dimethylformamide, stirred uniformly at a speed of 150-250r / min, then 1-chloroethyl cyclohexyl carbonate and maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol are added, stirred at a speed of 200-300r / min, then the temperature is raised to 110-120℃ for 3.1-3.5h, then cooled, and dried at 60-80℃ for 6-8h to obtain the modified zeolite.

[0035] In one of the embodiments, the mass ratio of the zeolite, 1-chloroethyl cyclohexyl carbonate, maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol and N,N-dimethylformamide is 70-90:5-15:5-15:90-110.

[0036] In one of the embodiments, the method for preparing the modified silica gel comprises the following steps:

[0037] The silica gel is added into sorbitol, stirred uniformly at a speed of 300-400r / min, then bis(3-triethoxysilylpropyl) carbonate and alumina are added, nitrogen is introduced, stirred uniformly at a speed of 500-600r / min, then the temperature is raised to 80-90℃ for 5-7h, after cooling, dried to obtain the modified silica gel.

[0038] In one of the embodiments, the mass ratio of the silica gel, sorbitol, bis(3-triethoxysilane propyl) carbonate and alumina is 45-55:25-35:5-15:5-15.

[0039] In one of the embodiments, the present application provides a preparation method of the anhydrous deoxidizer, which comprises the following steps:

[0040] The polyethylene terephthalate is subjected to drying treatment, and then is uniformly mixed with a hydroxyl-terminated polybutadiene-maleic anhydride compound and a cobalt acetate catalyst in a high-speed mixer, is extruded through a double-screw extruder, is cooled and granulated, and then is broken and screened through a high-speed crusher to obtain 60-80 mesh A particles;

[0041] The A particles, modified zeolite and modified silica gel are uniformly mixed, and then are added into a high-speed powdering machine to obtain 80-120 mesh B powder, and then the B powder is dried in an oven at 70-90℃ for 0.5-1h to obtain the anhydrous deoxidizer.

[0042] In one of the embodiments, the drying treatment is performed at a drying temperature of 110-130℃ for 20-28h.

[0043] In one of the embodiments, the double-screw extruder has a vacuum degree of 0.05-0.11MPa.

[0044] The embodiments of the present application will be described in detail below with reference to specific examples.

[0045] Example 1:

[0046] Preparation of the hydroxyl-terminated polybutadiene-maleic anhydride compound: 30 parts of hydroxyl-terminated polybutadiene are added into a four-necked flask, and then 30 parts of maleic anhydride and 15 parts of cyclohexane are added, and then γ-alumina is added after uniform stirring, and then the temperature is raised to 82℃ for reaction for 3h, and then a water separator is used to separate water during the reaction, and then the obtained product is washed, filtered and distilled to obtain the hydroxyl-terminated polybutadiene-maleic anhydride compound.

[0047] Preparation of the modified zeolite: 80 parts of zeolite are added into 100 parts of N,N-dimethylformamide under an argon atmosphere, and then stirred uniformly at a speed of 200r / min, and then 10 parts of 1-chloroethyl cyclohexyl carbonate and 10 parts of maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol are added and stirred at a speed of 250r / min, and then the temperature is raised to 115℃ for reaction for 3.3h, and then cooled, and then dried at 70℃ for 7h to obtain the modified zeolite.

[0048] Preparation of modified silica gel: 50 parts of silica gel was added into 30 parts of sorbitol, stirred uniformly at a speed of 350 r / min, then 10 parts of bis(3-triethoxysilane propyl) carbonate and 10 parts of alumina were added, nitrogen was introduced, and stirring was continued at a speed of 550 r / min, then the temperature was raised to 85°C and reaction was carried out for 6 h, and after cooling, drying was carried out to obtain modified silica gel;

[0049] Preparation of anhydrous deoxidizer: 50 parts of polyethylene terephthalate was dried at 120°C for 24 h, then mixed uniformly with 15 parts of hydroxyl-terminated polybutadiene-maleic anhydride compound and cobalt acetate catalyst in a high-speed stirrer, extruded through a double-screw extruder, cooled, granulated, then broken by a high-speed pulverizer and sieved to obtain 80-mesh A particles, wherein the vacuum degree of the double-screw extruder was 0.08 MPa; the above A particles, 15 parts of modified zeolite and 20 parts of modified silica gel were mixed uniformly, then added into a high-speed powdering machine to obtain 100-mesh B powder, and then the B powder was placed in an oven and dried at 80°C for 0.8 h to obtain anhydrous deoxidizer, which was sealed with aluminum foil bag and ready for use.

[0050] Example 2:

[0051] The other parts are the same as in Example 1, except that the modified zeolite is prepared as follows: under an argon atmosphere, 80 parts of zeolite was added into 100 parts of N,N-dimethylformamide, stirred uniformly at a speed of 200 r / min, then 5 parts of 1-chloroethyl cyclohexyl carbonate and 5 parts of maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol were added, stirred at a speed of 250 r / min, then the temperature was raised to 115°C and reaction was carried out for 3.3 h, then cooled, and then dried at 70°C for 7 h to obtain the modified zeolite.

[0052] Example 3:

[0053] The other parts are the same as in Example 1, except that the modified zeolite is prepared as follows: under an argon atmosphere, 80 parts of zeolite was added into 100 parts of N,N-dimethylformamide, stirred uniformly at a speed of 200 r / min, then 15 parts of 1-chloroethyl cyclohexyl carbonate and 15 parts of maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol were added, stirred at a speed of 250 r / min, then the temperature was raised to 115°C and reaction was carried out for 3.3 h, then cooled, and then dried at 70°C for 7 h to obtain the modified zeolite.

[0054] Comparative Example 1:

[0055] Preparation of the hydroxyl-terminated polybutadiene-maleic anhydride compound: 30 parts of hydroxyl-terminated polybutadiene is added into a four-necked flask, then 30 parts of maleic anhydride and 15 parts of cyclohexane are added, γ-alumina is added after stirring, then the temperature is raised to 82℃ and reacted for 3h, a water separator is used to separate water during the reaction, then it is cooled, the obtained product is washed, filtered and distilled to obtain the hydroxyl-terminated polybutadiene-maleic anhydride compound;

[0056] Preparation of the anhydrous deoxidizer: 50 parts of polyethylene terephthalate is dried at 120℃ for 24h, then mixed with 15 parts of the hydroxyl-terminated polybutadiene-maleic anhydride compound and a cobalt acetate catalyst in a high-speed stirrer, extruded through a double-screw extruder, cooled, granulated, then crushed and sieved by a high-speed crusher to obtain 80-mesh A particles, wherein the vacuum degree of the double-screw extruder is 0.08MPa; the above A particles, 15 parts of zeolite and 20 parts of silica gel are mixed uniformly, then added into a high-speed powdering machine to obtain 100-mesh B powder, then the B powder is placed in an oven and dried at 80℃ for 0.8h to obtain the anhydrous deoxidizer, which is sealed with an aluminum foil bag and can be used.

[0057] Comparative Example 2:

[0058] Preparation of the hydroxyl-terminated polybutadiene-maleic anhydride compound: 30 parts of hydroxyl-terminated polybutadiene is added into a four-necked flask, then 30 parts of maleic anhydride and 15 parts of cyclohexane are added, γ-alumina is added after stirring, then the temperature is raised to 82℃ and reacted for 3h, a water separator is used to separate water during the reaction, then it is cooled, the obtained product is washed, filtered and distilled to obtain the hydroxyl-terminated polybutadiene-maleic anhydride compound;

[0059] Preparation of the modified silica gel: 50 parts of silica gel is added into 30 parts of sorbitol, stirred uniformly at a speed of 350r / min, then 10 parts of bis(3-triethoxysilylpropyl) carbonate and 10 parts of alumina are added, nitrogen is introduced, stirred uniformly at a speed of 550r / min, then continue to stir, the temperature is raised to 85℃ and reacted for 6h, then dried after cooling to obtain the modified silica gel;

[0060] Preparation of the anhydrous deoxidizer: 50 parts of polyethylene terephthalate was dried at 120°C for 24 hours, then mixed with 15 parts of the hydroxyl-terminated polybutadiene-maleic anhydride compound and a cobalt acetate catalyst in a high-speed mixer, extruded through a twin-screw extruder, cooled, granulated, then broken up with a high-speed pulverizer and sieved to obtain 80-mesh A granules, wherein the vacuum degree of the twin-screw extruder was 0.08 MPa; the above A granules, 15 parts of zeolite and 20 parts of modified silica gel were mixed uniformly, then added to a high-speed powdering machine to obtain 100-mesh B powder, then the B powder was placed in an oven and dried at 80°C for 0.8 hours to obtain the anhydrous deoxidizer, which was sealed in an aluminum foil bag and ready for use.

[0061] Comparative Example 3:

[0062] Preparation of the hydroxyl-terminated polybutadiene-maleic anhydride compound: 30 parts of hydroxyl-terminated polybutadiene was added to a four-necked flask, then 30 parts of maleic anhydride and 15 parts of cyclohexane were added, then γ-alumina was added after stirring uniformly, then the temperature was raised to 82°C and reacted for 3 hours, during the reaction, a water separator was used to separate water, then the product was cooled, washed, filtered and distilled to obtain the hydroxyl-terminated polybutadiene-maleic anhydride compound;

[0063] Preparation of the modified zeolite: 80 parts of zeolite was added to 100 parts of N,N-dimethylformamide under an argon atmosphere, stirred uniformly at a speed of 200 r / min, then 10 parts of 1-chloroethyl cyclohexyl carbonate and 10 parts of maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol were added and stirred at a speed of 250 r / min, then the temperature was raised to 115°C and reacted for 3.3 hours, then cooled, then dried at 70°C for 7 hours to obtain the modified zeolite;

[0064] Preparation of the anhydrous deoxidizer: 50 parts of polyethylene terephthalate was dried at 120°C for 24 hours, then mixed with 15 parts of the hydroxyl-terminated polybutadiene-maleic anhydride compound and a cobalt acetate catalyst in a high-speed mixer, extruded through a twin-screw extruder, cooled, granulated, then broken up with a high-speed pulverizer and sieved to obtain 80-mesh A granules, wherein the vacuum degree of the twin-screw extruder was 0.08 MPa; the above A granules, 15 parts of zeolite and 20 parts of modified silica gel were mixed uniformly, then added to a high-speed powdering machine to obtain 100-mesh B powder, then the B powder was placed in an oven and dried at 80°C for 0.8 hours to obtain the anhydrous deoxidizer, which was sealed in an aluminum foil bag and ready for use.

[0065] The anhydrous deoxidizers obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were tested for deoxidation performance and deoxidation efficiency, and the test results are shown in Table 1.

[0066] Table 1:

[0067] Item Deoxidation amount (ml / g) Deoxidation time (h) Example 1 125 35 Example 2 107 43 Example 3 105 47 Comparative Example 1 53 190 Comparative Example 2 65 151 Comparative Example 3 78 136

[0068] As can be seen from Table 1, since the raw materials for preparing the anhydrous deoxidizer of Examples 1-3 contain modified zeolite and modified silica gel at the same time, the deoxidation capacity is as high as 105 ml / g or more, and the time to reach the deoxidation capacity is as low as 47 h or less. The deoxidation performance and deoxidation efficiency of the anhydrous deoxidizer provided by the technical scheme of the present application are both very excellent. Specifically, the anhydrous deoxidizer provided by the above technical scheme, on the basis of hydroxyl-terminated polybutadiene-maleic anhydride compound and polyethylene terephthalate, adds a certain proportion of modified zeolite and a certain proportion of modified silica gel, so that it has excellent deoxidation performance and deoxidation efficiency at the same time. More specifically, the zeolite is modified by maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol and 1-chloroethyl cyclohexyl carbonate, and benefits from its macromolecular chain and multiple multi-electron groups. The obtained modified zeolite has a significant oxygen absorption effect. The silica gel modified by sorbitol, bis(3-triethoxysilylpropyl) carbonate and alumina has more abundant Si-O and Al-O polar bonds, and part of which can be linked with the polar functional groups of bis(3-triethoxysilylpropyl) carbonate. The Si-O and Al-O polar bonds and the polar functional groups of the modified silica gel interact with the macromolecular chain polar functional groups of the modified zeolite, so that the deoxidation performance and deoxidation efficiency of the obtained anhydrous deoxidizer are both very excellent.

[0069] Figure 1 The reaction path of the hydroxyl-terminated polybutadiene-maleic anhydride compound.

[0070] The technical features of the above-described embodiments can be combined in any manner. In order to make the description concise, not all possible combinations of the technical features in the above-described embodiments are described, however, as long as the combinations of the technical features do not exist contradictions, they should be considered as the scope of the present disclosure.

[0071] The above-described embodiments only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the protection scope of the present application patent should be subject to the appended claims.

Claims

1. An anhydrous deoxidizer, characterized by comprising, 10~20 parts of a hydroxyl-terminated polybutadiene-maleic anhydride compound, 10~20 parts of a modified zeolite, 15~25 parts of a modified silica gel, and 45~55 parts of polyethylene terephthalate by mass; The modified silica gel is prepared from silica gel, sorbitol, bis(3-triethoxysilane propyl) carbonate, and alumina; The modified silica gel is prepared by the following steps: The silica gel is added to the sorbitol and stirred at a speed of 300~400 r / min until uniform, then the bis(3-triethoxysilane propyl) carbonate and alumina are added, nitrogen is introduced, and the mixture is stirred at a speed of 500~600 r / min until uniform, then the mixture is continuously stirred, heated to 80~90℃, and reacted for 5~7 h, then the mixture is cooled and dried to obtain the modified silica gel; The modified zeolite is prepared from zeolite, 1-chloroethyl cyclohexyl carbonate, maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol, and N,N-dimethylformamide; The modified zeolite is prepared by the following steps: The zeolite is added to the N,N-dimethylformamide under an argon atmosphere and stirred at a speed of 150~250 r / min until uniform, then the 1-chloroethyl cyclohexyl carbonate and maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol are added and stirred at a speed of 200~300 r / min, then the mixture is heated to 110~120℃ and reacted for 3.1~3.5 h, then the mixture is cooled and dried at 60~80℃ for 6~8 h to obtain the modified zeolite; The hydroxyl-terminated polybutadiene-maleic anhydride compound is prepared by the following steps: The hydroxyl-terminated polybutadiene is added to a four-necked flask, then the maleic anhydride and cyclohexane are added, the mixture is stirred until uniform, then the γ-alumina is added, the mixture is heated to 80~85℃ and reacted for 2.5~3.5 h, water is separated out using a water trap during the reaction, then the mixture is cooled, and the resulting product is washed, filtered, and distilled to obtain the hydroxyl-terminated polybutadiene-maleic anhydride compound.

2. The anhydrous deoxidizer of claim 1, wherein The mass ratio of the hydroxyl-terminated polybutadiene, the maleic anhydride, and the cyclohexane is 25~35:25~35:10~20.

3. The anhydrous deoxidizer of claim 1, wherein The mass ratio of the zeolite, 1-chloroethyl cyclohexyl carbonate, maleimide hexanoyl-L-valine-L-citrulline p-aminobenzyl alcohol, and N,N-dimethylformamide is 70~90:5~15:5~15:90~110.

4. The anhydrous deoxidizer of claim 1, wherein The mass ratio of the silica gel, sorbitol, bis(3-triethoxysilane propyl) carbonate, and alumina is 45~55:25~35:5~15:5~15.

5. A process for the preparation of anhydrous deoxidizer characterized in that, The preparation method is used to prepare the anhydrous deoxidizer according to any one of claims 1~4, and the preparation method comprises the following steps: The polyethylene terephthalate is dried, then mixed with the hydroxyl-terminated polybutadiene-maleic anhydride compound and the cobalt acetate catalyst in a high-speed stirrer, extruded through a double-screw extruder, cooled, granulated, then broken and sieved using a high-speed crusher to obtain 60~80 mesh A particles; The A particles, modified zeolite and modified silica gel are mixed uniformly, then added into a high-speed powdering machine to obtain 80-120 mesh B powder, and then the B powder is placed in an oven and dried at 70-90 DEG C for 0.5-1h to obtain the anhydrous deoxidizer.

6. The production method according to claim 5, wherein The drying treatment condition is that the drying temperature is 110-130 DEG C and the drying time is 20-28h.

7. The preparation method according to claim 5, characterized in that, The vacuum degree of the double-screw extruder is 0.05-0.11MPa.

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