Aqueous emulsion antioxidant and method of making and use thereof

Abstract

The application provides a kind of high efficiency water-based emulsion antioxidant and its preparation method and application, the high efficiency water-based emulsion antioxidant, including oil-soluble antioxidant, emulsifier, defoaming agent, deionized water;The emulsifier is the combination of anionic surfactant, non-ionic surfactant and / or protective colloid.This application has the beneficial effect that: the high efficiency water-based emulsion antioxidant of the application utilizes the synergistic effect of emulsifier to make it compatible with emulsion polymerization polymer, has good anti-aging performance, and the effective utilization rate of the emulsion antioxidant is high, and the stability is high, can be stored for a long time.The high efficiency water-based emulsion antioxidant of the application is a water-based environmentally friendly product, which avoids the dust pollution and explosion risk caused by direct addition of solid antioxidant, avoids the problem of poor compatibility of traditional liquid antioxidant polyemulsion polymerization polymer system, and improves resource utilization.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of fine chemical industry, and particularly relates to a water-based emulsion antioxidant, a preparation method and application thereof. BACKGROUND

[0002] Emulsion polymerization is to disperse monomers in water to form an emulsion by means of emulsifiers and mechanical stirring, and then to add an initiator to initiate polymerization of the monomers. The polymers prepared by emulsion polymerization mainly include latex and its products (including but not limited to natural latex, nitrile rubber latex, styrene-butadiene latex, styrene-butadiene-vinylpyridine latex, chloroprene latex, isoprene latex, natural latex, etc.), emulsion polymerized rubber (including but not limited to emulsion polymerized styrene-butadiene rubber, nitrile rubber, chloroprene rubber, etc.), and other polymers containing specific functional groups (including but not limited to ABS, ASA, MBS, polymethacrylate and its copolymer, polyvinyl chloride, polyvinyl acetate and its copolymer, polytetrafluoroethylene, etc.). The global annual production of polymers by emulsion polymerization is in the tens of millions of tons, so emulsion polymerization is increasingly important for the production of polymers.

[0003] However, the polymers prepared by emulsion polymerization will inevitably be affected by oxygen, light, heat and mechanical stress during synthesis, processing, transportation, storage and use, resulting in free radicals and aging degradation. Therefore, anti-aging agents are added before use. Most conventional anti-aging agents are oil-soluble products, which have poor compatibility with water, low effective utilization rate, and with the increasing environmental protection requirements, water-based antioxidants are gradually favored by society.

[0004] At present, the water-based antioxidant products on the market are mainly prepared from solid antioxidants, which limits the application of liquid antioxidant water-based products. Therefore, it is imperative to develop a preparation process for water-based antioxidant products that can be prepared from both solid and liquid antioxidants. In addition, the particle size of the water-based antioxidant for emulsion polymerization is relatively large, and the addition amount of the antioxidant is at the level of several thousandths, which is not conducive to the entry of the water-based antioxidant into the polymer micelles to play a targeted protective role in the polymer, and the anti-aging effect is seriously affected. Therefore, it is particularly important to develop an emulsion antioxidant with small particle size, fast moving rate, and the ability to enter the polymer micelles to prevent polymer aging and improve the coverage of the antioxidant. In addition, conventional water-based emulsion antioxidants have poor stability and are prone to delamination, precipitation and oil floating, which is not conducive to use and long-term storage. Therefore, it is very important to prepare a water-based emulsion antioxidant with high stability for the use of emulsion polymerization polymers. SUMMARY

[0005] The main purpose of the present application is to provide a water-based emulsion with small particle size, high stability, long storage time and good anti-aging performance, as well as a preparation method and application thereof.

[0006] The first aspect of the present application provides an aqueous emulsion antioxidant, comprising an oil-soluble antioxidant, an emulsifier, an antifoaming agent and water.

[0007] The oil-soluble antioxidant comprises at least one compound represented by general formula I;

[0008]

[0009] wherein:

[0010] R1 is C1-C4 alkyl;

[0011] R2 and R3 are each independently selected from one of C1-C4 alkyl, -CH2-S-R4 or -CH2-CH2-COO-R4; R4 is C8-C 18 or C8-C 12 alkyl;

[0012] The emulsifier comprises one or more of an anionic surfactant, a nonionic surfactant and a protective colloid.

[0013] When the anionic surfactant and the nonionic surfactant are used in combination as described in the present application, the molecules of the two types of surfactants are alternately adsorbed on the surface of the latex particles, and the nonionic surfactant molecules are 'wedged' between the anionic surfactant molecules. In this way, on the one hand, the distance between the surfactant molecules on the surface of the latex particles is increased, and on the other hand, the electrostatic tension on the surface of the latex particles is greatly reduced due to the electrostatic shielding effect of the nonionic surfactant, and the adsorption firmness of the emulsifier on the surface of the latex particles is increased, so that the stability of the polymer emulsion is improved. At the same time, the anionic surfactant relies mainly on electrostatic repulsion to stabilize the emulsion, and the nonionic surfactant relies mainly on hydration. If the two types of emulsifiers are used in combination, even if there is a large electrostatic repulsion between the latex particles, a thick hydration layer is also formed on the surface of the latex particles, and the double effect of the two results in a very stable emulsion.

[0014] The protective colloid molecules described in the present application are adsorbed on the surface of the latex particles to form a hydration layer with a certain thickness, which can prevent the latex particles from colliding with each other and coalescing. At the same time, since the protective colloid is dissolved in the water phase, the viscosity of the system is increased, which also increases the resistance to collision between the latex particles, further making the emulsion more stable.

[0015] As a preferred embodiment of the above-mentioned aqueous emulsion antioxidant, it comprises the following raw materials in parts by weight: oil-soluble antioxidant 10-70 parts, emulsifier 3-30 parts, antifoaming agent 0.001-1 part, deionized water 30-70 parts.

[0016] In a preferred embodiment of the above-mentioned aqueous emulsion antioxidant, the compound represented by general formula I includes at least one compound represented by general formulas Ia-Ig;

[0017] The structural formula of the compound described in general formula Ia is:

[0018]

[0019] The structural formula of the compound of general formula Ib is:

[0020]

[0021] The structural formula of the compound represented by general formula Ic is:

[0022]

[0023] The structural formula of the compound represented by general formula Id is:

[0024]

[0025] The structural formula of the compound represented by general formula Ie is:

[0026]

[0027] The structural formula of the compound represented by the general formula If is:

[0028]

[0029] The structural formula of the compound represented by general formula Ig is:

[0030]

[0031] Where: R is C7-C 18 At least one of the alkyl groups, preferably, R is C7-C9, C 12 -C 18 At least one of the alkyl groups;

[0032] According to some embodiments of the aqueous emulsion antioxidant described in this application, the oil-soluble antioxidant is a C7-C9 mixed ester of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid;

[0033] According to some embodiments of the aqueous emulsion antioxidant described in this application, the oil-soluble antioxidant is a C13-15 branched and straight-chain alkyl ester of 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid.

[0034] According to some embodiments of the aqueous emulsion antioxidant described in this application, the oil-soluble antioxidant is 4,6-bis(octylthiomethyl)o-cresol;

[0035] According to some embodiments of the water-based emulsion antioxidant described in the present application, the oil-soluble antioxidant is 2,4-di-tert-butyl-6-n-octylthio-methylene phenol.

[0036] According to some embodiments of the water-based emulsion antioxidant described in the present application, the emulsifier comprises or consists of an anionic surfactant, a non-ionic surfactant and a protective colloid; or the emulsifier comprises or consists of an anionic surfactant and a non-ionic surfactant.

[0037] According to some embodiments of the water-based emulsion antioxidant described in the present application, the emulsifier comprises or consists of an anionic carboxylate, an anionic sulfate, a non-ionic ether and a protective colloid.

[0038] According to some embodiments of the water-based emulsion antioxidant described in the present application, the emulsifier comprises or consists of an anionic sulfate and a non-ionic higher fatty alcohol.

[0039] According to some embodiments of the water-based emulsion antioxidant described in the present application, the anionic surfactant comprises at least one of a carboxylate surfactant, a sulfate surfactant, a sulfonate surfactant, a phosphate surfactant;

[0040] According to some embodiments of the water-based emulsion antioxidant described in the present application, the carboxylate surfactant is a fatty alcohol polyoxyethylene ether carboxylate, an oleate soap, a ricinoleate soap, a rosin acid soap, a fatty acid soap or a tall oil soap;

[0041] According to some embodiments of the water-based emulsion antioxidant described in the present application, the sulfate surfactant is a polyoxyethylene alkyl phenol ether sulfate, a fatty alcohol polyoxyethylene ether sulfate or an aralkyl phenol polyoxyethylene ether sulfate;

[0042] According to some embodiments of the water-based emulsion antioxidant described in the present application, the sulfonate surfactant is an alkyl sulfonate, an alkyl benzene sulfonate, an alkyl naphthalene sulfonate, an alkyl succinate sulfonate, a succinate disodium sulfonate mixture, a fatty amide taurate, such as sodium dodecyl sulfonate, a polyoxyethylene alkyl ether sulfonate or a fatty amide sarcosinate;

[0043] According to some embodiments of the water-based emulsion antioxidant described in the present application, the phosphate surfactant is a fatty acid polyoxyethylene ether phosphate, a polyoxyethylene alkyl phenol ether phosphate or an alkyl polyoxyethylene ether phosphite monoester and diester.

[0044] The non-ionic surfactant is at least one of an ester, an ether or a higher fatty alcohol;

[0045] According to some embodiments of the water-based emulsion antioxidant of the present application, the ester is polyoxyethylene carboxylate, polyol carboxylate or polyoxyethylene polyol carboxylate;

[0046] According to some embodiments of the water-based emulsion antioxidant of the present application, the ether is polyoxyethylene alkyl aryl ether, polyethylene alkyl ether, fatty alcohol polyoxyethylene ether, fatty alcohol and ethylene oxide condensate;

[0047] According to some embodiments of the water-based emulsion antioxidant of the present application, the higher fatty alcohol is cetyl alcohol, stearyl alcohol, C 16-17 The branched fatty alcohol or polyoxyethylene stearyl alcohol.

[0048] According to some embodiments of the water-based emulsion antioxidant of the present application, the protective colloid is at least one of polyvinyl alcohol, sodium polymethacrylate, polyethylene glycol, polyvinyl pyrrolidone, hydroxyethyl cellulose, hydroxymethyl cellulose, xanthan gum, gelatin, gum arabic.

[0049] According to some embodiments of the water-based emulsion antioxidant of the present application, the emulsifier includes potassium castor oil soap, sodium fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether and xanthan gum. The emulsifier is particularly suitable for the oil-based antioxidant of formula Ia, Ib, Ic, Id, If.

[0050] According to some embodiments of the water-based emulsion antioxidant of the present application, the emulsifier includes cetyl alcohol / stearyl alcohol / C 16-17 The branched fatty alcohol / polyoxyethylene stearyl alcohol, sodium dodecyl sulfonate. The emulsifier is particularly suitable for the oil-based antioxidant of formula Ia, Ib, Ic, Id, If.

[0051] According to some embodiments of the water-based emulsion antioxidant of the present application, the defoaming agent is at least one of silicone oil, high carbon alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylamine ether, polyoxypropylene glycerol ether, polyoxypropylene.

[0052] In a second aspect of the present application, a preparation method of the water-based emulsion antioxidant is provided, and the preparation method is phase transfer method or ultrasonic dispersion method.

[0053] Preferably, the phase transfer method comprises the following steps:

[0054] (1) adding an emulsifier to an oil-soluble antioxidant in a heated and heat-preserved state to obtain a mixture system;

[0055] (2) adding water, preferably deionized water, to the mixture system obtained in step (1), and after the addition is completed, carrying out heat preservation and cooling treatment, and then adding a defoaming agent to obtain the high-efficiency water-based emulsion antioxidant;

[0056] More preferably, the ultrasonic dispersion method comprises the following steps:

[0057] a. Heating the oil-soluble antioxidant and adding an emulsifier, stirring and mixing uniformly;

[0058] b. Adding water, preferably deionized water, to the mixture obtained in step a, stirring uniformly to obtain an aqueous antioxidant system;

[0059] c. Ultrasonic dispersion of the aqueous antioxidant system obtained in step b, stirring and cooling treatment, then adding an antifoaming agent and discharging to obtain the high-efficiency aqueous emulsion antioxidant.

[0060] According to some embodiments of the preparation method described in the present application, in step (1), the emulsifier is added to the oil-soluble antioxidant at a heating and holding temperature of 50-180°C, and stirred at a stirring speed of 30-600 rpm for 10-60 min; preferably, the emulsifier comprises anionic surfactant, non-ionic surfactant and protective colloid;

[0061] According to some embodiments of the preparation method described in the present application, in step (2), deionized water is added dropwise to the mixture obtained in step (1) at a stirring temperature of 50-100°C and a stirring speed of 300-3000 rpm, and after the system becomes thin and yogurt-like, the stirring speed is reduced to 30-600 rpm;

[0062] After the addition of deionized water is completed, it is kept for 30 min-60 min, and cooled to a temperature less than 50°C, and then an antifoaming agent is added and discharged.

[0063] According to some embodiments of the preparation method described in the present application, in step a, the oil-soluble antioxidant is heated to 30-70°C;

[0064] According to some embodiments of the preparation method described in the present application, the emulsifier comprises anionic surfactant and non-ionic surfactant;

[0065] According to some embodiments of the preparation method described in the present application, in step c, the ultrasonic dispersion temperature is controlled below 80°C, and the ultrasonic dispersion time is 30 min; the ultrasonically dispersed system is cooled to below 50°C at a stirring speed of 300 rpm, and an antifoaming agent is added and discharged.

[0066] When a phase transfer method is used to prepare the aqueous emulsion antioxidant, the emulsifier is a combination of anionic carboxylate, anionic sulfate, non-ionic ether and protective colloid;

[0067] When the water-based emulsion antioxidant prepared by the ultrasonic dispersion method is used, the emulsifier is a combination of anionic sulfate and non-ionic high-grade fatty alcohol.

[0068] In a third aspect of the present application, a polymer material is provided, which contains the water-based emulsion antioxidant of the first aspect of the present application or the water-based emulsion antioxidant prepared by the preparation method of the second aspect of the present application.

[0069] According to some embodiments of the polymer material of the present application, the polymer material is rubber and latex, and can be specifically selected from one or more of nitrile rubber latex, styrene butadiene rubber latex, styrene butadiene pyridine rubber latex, chloroprene rubber latex, isoprene rubber latex, natural rubber latex, emulsion polymerized butadiene styrene rubber, nitrile rubber, chloroprene rubber, ABS, ASA, MBS, polymethacrylate and its copolymer, polyvinyl chloride, polyvinyl acetate and its copolymer, and polytetrafluoroethylene.

[0070] The present application has the following beneficial effects: the efficient water-based emulsion antioxidant of the present application has good compatibility with emulsion polymerized polymers due to the synergistic effect of the emulsifier, has good anti-aging performance, has high effective utilization rate, has high stability, and can be stored for a long time.

[0071] The efficient water-based emulsion antioxidant of the present application is a water-based environmentally friendly product, which avoids dust pollution and explosion risk caused by direct addition of solid antioxidants, avoids the problem of poor compatibility of traditional liquid antioxidant emulsion polymerized polymer systems, and improves resource utilization rate. BRIEF DESCRIPTION OF DRAWINGS

[0072] Figure 1 The particle size diagram of the water-based emulsion antioxidant obtained in Example 2 of the present application. DETAILED DESCRIPTION

[0073] In order to make the purpose, technical scheme and advantages of the present application more clear and explicit, the present application is further described in detail below in combination with examples and drawings. The specific examples described herein are only used to explain the present application and do not constitute any limitation on the present application. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present disclosure. Such structures and technologies are also described in many publications.

[0074] The sources of some raw materials used in the examples of the present application are as follows:

[0075] 3,5-di-tert-butyl-4-hydroxybenzene propionic acid C7-C9 mixed ester (RIANOX 1135): Tianjin Li'an Longxin Material Co., Ltd., CAS No: 125643-61-0;

[0076] Potassium ricinoleate soap: Tianjin Li'anlong New Material Co., Ltd., CAS No: 8013-05-6;

[0077] Sodium fatty alcohol ether sulfate: Zanyu Technology Group Co., Ltd., CAS No: 9004-82-4;

[0078] Fatty alcohol polyoxyethylene ether: Suzhou Yuantai Run Chemical Co., Ltd., CAS No: 52292-17-8;

[0079] Xanthan gum: Hubei Qi Fei Pharmaceutical Chemical Co., Ltd., CAS No: 11138-66-2;

[0080] Polyoxyethylene polyoxypropanol amine ether: Hubei Chengfeng Chemical Co., Ltd.;

[0081] 3,5-bis(1,1-dimethyl ethyl)-4-hydroxybenzene propionic acid C13-15 branched and linear alkyl ester (RIANOX 1315): Tianjin Li'anlong New Material Co., Ltd., CAS No: 171090-93-0;

[0082] Octadecanol: Shanghai Baite Chemical Co., Ltd., CAS No: 112-92-5;

[0083] Sodium dodecyl sulfate: Jinan Daorong Chemical Co., Ltd., CAS No: 151-21-3;

[0084] Polyoxypropylene glycerol ether: Jining Tangyi Chemical Co., Ltd., CAS No: 25791-96-2;

[0085] 4,6-bis(octylthiomethyl) o-cresol (RIANOX 1520): Tianjin Li'anlong New Material Co., Ltd., CAS No: 110553-27-0.

[0086] Example 1

[0087] An aqueous emulsion antioxidant includes the following raw materials by weight: oil-soluble antioxidant, emulsifier, defoaming agent, deionized water;

[0088] Oil-soluble antioxidant: (3,5-di-tert-butyl-4-hydroxybenzene propionic acid C7-C9 mixed ester (RIANOX 1135)) 50 parts by weight;

[0089] Emulsifier: potassium ricinoleate soap 3 parts by weight, sodium fatty alcohol ether sulfate 3 parts by weight, fatty alcohol polyoxyethylene ether 2 parts by weight, and xanthan gum 1 part by weight;

[0090] Defoaming agent: polyoxyethylene polyoxypropanol amine ether 1 part by weight;

[0091] Prepared by phase transfer method, including the following steps:

[0092] (1) In the reaction kettle, 50 parts of oil-soluble antioxidant 3,5-di-tert-butyl-4-hydroxybenzene propionic acid C7-C9 mixed ester (RIANOX 1135) was added, heated to maintain the temperature at 70°C, and low-speed stirring was started at 30-600 rpm to mix evenly;

[0093] (2) 3 parts of potassium castor oil soap, 3 parts of fatty alcohol polyoxyethylene ether sodium sulfate, 2 parts of fatty alcohol polyoxyethylene ether, and 1 part of xanthan gum were added to the reaction kettle, and stirring was started at 600 rpm to mix evenly with the antioxidant melt, and the stirring time was 10-60 min;

[0094] (3) At 70°C, high-speed stirring was started at 3000 rpm, and 40 parts of deionized water was added dropwise to the reaction kettle, and after the aqueous system became thin, the stirring rate was reduced to 600 rpm;

[0095] (4) After the water was added, the aqueous emulsion was kept at 30 min, then cooled to below 50°C, 1 part of defoaming agent polyoxyethylene polyoxypropyl alcohol amine ether was added, and the stable high-efficiency aqueous emulsion antioxidant was obtained.

[0096] Example 2

[0097] An aqueous emulsion antioxidant, comprising the following raw materials by weight: oil-soluble antioxidant, emulsifier, defoaming agent, deionized water;

[0098] The oil-soluble antioxidant is: 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzene propionic acid C 13-15 branched and linear alkyl ester (RIANOX 1315) 50 parts by weight;

[0099] The emulsifier is: octadecanol 1 part by weight, sodium dodecyl sulfate 2 parts by weight;

[0100] The defoaming agent is: polyoxypropylene glycerol ether 0.001 parts by weight;

[0101] Prepared by ultrasonic dispersion method, comprising the following steps:

[0102] a. In the reaction kettle, 50 parts of oil-soluble antioxidant 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzene propionic acid C13-15 branched and linear alkyl ester (RIANOX 1315) was added, and the temperature was raised to 50°C;

[0103] b. Add 1 part of octadecanol and 2 parts of sodium dodecyl sulfate, stir evenly, then add 47 parts of deionized water, and continue stirring for 30 min;

[0104] c. Then the aqueous antioxidant system was placed in an ultrasonic dispersion machine below 80°C for 30 min.

[0105] d. The ultrasonically dispersed waterborne antioxidant is cooled to below 50°C under a stirring speed of 300 rpm, and an antifoaming agent is added before discharge to obtain a waterborne emulsion antioxidant with high stability.

[0106] The particle size distribution of the aqueous emulsion antioxidant obtained in Example 2 is shown in the attached figure. Figure 1 As shown;

[0107] From the appendix Figure 1 It can be seen that the overall particle size of the obtained aqueous emulsion antioxidant is in the micro-nano range, with a small particle size and a very narrow particle size distribution range.

[0108] Example 3

[0109] An aqueous emulsion antioxidant differs from Example 1 in that the oil-soluble antioxidant used is 4,6-bis(octylthiomethyl)o-cresol (RIANOX 1520).

[0110] Example 4

[0111] An aqueous emulsion antioxidant differs from Example 2 in that the oil-soluble antioxidant used is 2,4-di-tert-butyl-6-n-octylthiomethylphenol.

[0112] Example 5

[0113] An aqueous emulsion antioxidant differs from Example 2 in that the oil-soluble antioxidant used is 4,6-bis(octylthiomethyl)o-cresol (RIANOX 1520).

[0114] Comparative Example 1

[0115] A water-based emulsion antioxidant differs from the water-based emulsion antioxidant described in Example 1 in that the emulsifier used is 2 parts by weight of gum arabic (nonionic emulsifier), 5 parts by weight of stearic acid (anionic surfactant), and 1 part by weight of xanthan gum.

[0116] Comparative Example 2

[0117] An aqueous emulsion antioxidant differs from the aqueous emulsion antioxidant described in Example 2 in that the emulsifier used is 2 parts by weight of N-dodecyl dimethylamine (cationic surfactant) and 1 part by weight of cetyl alcohol.

[0118] Comparative Example 3

[0119] An aqueous emulsifier differs from the aqueous emulsion antioxidant described in Example 1 in that the oil-soluble antioxidant used is bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

[0120] Comparative Example 4

[0121] An aqueous emulsion antioxidant, which is different from the aqueous emulsion antioxidant described in Example 2 in that the oil-soluble antioxidant used is pentaerythritol di-distearyl phosphite.

[0122] Performance study of the aqueous emulsion antioxidant described in the present application:

[0123] The test method is as follows:

[0124] 1. Volume average particle size: Bettersize 2600 laser particle size distribution instrument is used to test the particle size of the aqueous emulsion antioxidant;

[0125] 2. Centrifugal stability: centrifugation is carried out at a speed of 5000 rpm for 30 min, and whether there is supernatant or precipitate is observed;

[0126] 3. Storage stability: standing at room temperature, and observing whether there is supernatant or sedimentation in the emulsion;

[0127] 4. Anti-aging performance: a certain amount of emulsion antioxidant is added into the butadiene-styrene latex and mixed uniformly, the mixed latex is made into a film, and the film is aged at 150℃ for 3h, and the film color is tested.

[0128] The test results are shown in Table 1:

[0129] Table 1

[0130]

[0131] As can be seen from Table 1, the high-efficiency aqueous emulsion antioxidant described in the present application has small particle size, high stability, and good high-aging performance. The aqueous emulsions described in Comparative Examples 1 and 2 have significantly large particle size, low centrifugal stability and storage stability, and poor anti-aging performance due to the use of emulsifiers other than those in the present application. The aqueous emulsions described in Comparative Examples 3 and 4 have large particle size, low stability, and poor anti-aging performance due to the use of other oil-soluble antioxidants.

[0132] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed in the present application, and all fall within the protection scope of the present application.

Claims

1. An aqueous emulsion antioxidant, comprising an oil-soluble antioxidant, an emulsifier, an antifoaming agent and water; the oil-soluble antioxidant is one of the compounds shown in general formula Ia-Ig, the emulsifier comprises anionic carboxylate, anionic sulfate, nonionic ether and protective colloid; wherein the anionic carboxylate is selected from ricinoleate soap, the anionic sulfate is selected from fatty alcohol polyoxyethylene ether sulfate, the nonionic ether is fatty alcohol polyoxyethylene ether, and the protective colloid is selected from xanthan gum. wherein: R is at least one of C7-C 18 alkyl; the emulsifier is composed of anionic carboxylate, anionic sulfate, nonionic ether and protective colloid.

4. An aqueous emulsion antioxidant, comprising an oil-soluble antioxidant, an emulsifier, an antifoaming agent and water; the oil-soluble antioxidant is one of the compounds shown in general formula Ia-Ig, 2. The aqueous emulsion antioxidant according to claim 1, characterized in that, said R is C7-C9, C 12 -C 18 at least one of alkyl.

3. The aqueous emulsion antioxidant of claim 1, wherein the emulsifier comprises anionic sulfate and nonionic higher fatty alcohol; the emulsifier is composed of anionic sulfate and nonionic higher fatty alcohol. the oil-soluble antioxidant is 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid C7-C9 mixed ester; or the oil-soluble antioxidant is 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid C13-15 branched and linear alkyl ester; or the oil-soluble antioxidant is 4,6-bis(octylthiomethyl) o-cresol; or the oil-soluble antioxidant is 2,4-di-tert-butyl-6-n-octylthio-methylphenol. wherein: R is at least one of C7-C 18 alkyl; the oil-soluble antioxidant is 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid C7-C9 mixed ester, or 4,6-bis(octylthiomethyl) o-cresol. Among them, non-ionic higher fatty alcohol is cetyl alcohol, stearyl alcohol, C 16-17 Fatty alcohol or polyoxyethylene octadecanol.

5. The aqueous emulsion antioxidant of claim 4, wherein said R is C7-C9, C 12 -C 18 at least one of alkyl.

6. The aqueous emulsion antioxidant of claim 4, wherein the oil-soluble antioxidant is 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid C13-15 branched and linear alkyl ester, or 4,6-bis(octylthiomethyl) o-cresol, or 2,4-di-tert-butyl-6-n-octylthio-methylphenol.

7. The aqueous emulsion antioxidant according to any one of claims 1 to 6, characterized in that, The raw materials include oil-soluble antioxidant 10-70 parts, emulsifier 3-30 parts, antifoaming agent 0.001-1 part, and deionized water 30-70 parts.

8. The aqueous emulsion antioxidant of claim 1, wherein The antifoaming agent is at least one of silicone oil, high-carbon alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylamine ether, polyoxypropylene glycerol ether, and polyoxypropylene.

9. The aqueous emulsion antioxidant of claim 4, wherein, The preparation method is phase transfer method.

10. The aqueous emulsion antioxidant of any one of claims 1-6, wherein, The phase transfer method comprises the following steps:

11. The aqueous emulsion antioxidant of any one of claims 1-6, wherein, (1) adding an emulsifier to the oil-soluble antioxidant in a heating and holding state to obtain a mixture system; 12. A process for the preparation of the aqueous emulsion antioxidant of claim 1, characterized in that, (2) adding water to the mixture system obtained in step (1), and after the addition is completed, carrying out holding and cooling treatment, then adding an antifoaming agent and a protective colloid to discharge, to obtain the aqueous emulsion antioxidant.

13. The preparation method according to claim 12, characterized in that, in step (1), the emulsifier is added to the oil-soluble antioxidant in a heating and holding state at a temperature of 50-180°C, and stirring is carried out at a stirring speed of 30-600 rpm for 10-60 min; in step (2), deionized water is added dropwise to the mixture system obtained in step (1) under the conditions of a stirring temperature of 50-100°C and a stirring speed of 300-3000 rpm, and the stirring speed is reduced to 30-600 rpm. ​ ​ ​ After the deionized water is added, the temperature is kept and then cooled to less than 50℃, and then a defoaming agent and a protective colloid are added and discharged.

14. A process for the preparation of the aqueous emulsion antioxidant of claim 4, characterized in that, The preparation method is an ultrasonic dispersion method, The ultrasonic dispersion method comprises the following steps: a. heating the oil-soluble antioxidant and adding an emulsifier and mixing uniformly; b. adding water to the mixture obtained in step a to obtain an aqueous antioxidant system; c. ultrasonic dispersion of the aqueous antioxidant system obtained in step b, then cooling treatment, and then adding a defoaming agent and discharging to obtain the aqueous emulsion antioxidant.

15. The preparation method according to claim 14, characterized in that, in step a, the oil-soluble antioxidant is heated to 30-70℃; in step c, the ultrasonic dispersion system is stirred at a stirring temperature of 50-70℃ for 30 min, then cooled to below 50℃, and then a defoaming agent is added and discharged.

16. A high molecular material, characterized by, The aqueous emulsion antioxidant contains the aqueous emulsion antioxidant according to any one of claims 1-11 or the aqueous emulsion antioxidant prepared by the preparation method according to any one of claims 12-15.

17. The polymeric material of claim 16, wherein, The high molecular material is rubber and latex.

18. The polymeric material of claim 17, wherein, The high molecular material is selected from one or more of natural latex, nitrile-butadiene latex, styrene-butadiene latex, styrene-butadiene-vinylpyridine latex, chloroprene latex, isoprene latex, emulsion polymerized styrene-butadiene rubber, nitrile rubber, chloroprene rubber, ABS, ASA, MBS, polymethyl acrylate and copolymers thereof, polyvinyl chloride, polyvinyl acetate and copolymers thereof, and polytetrafluoroethylene. The high molecular material is selected from one or more of natural latex, nitrile-butadiene latex, styrene-butadiene latex, styrene-butadiene-vinylpyridine latex, chloroprene latex, isoprene latex, emulsion polymerized styrene-butadiene rubber, nitrile rubber, chloroprene rubber, ABS, ASA, MBS, polymethyl acrylate and copolymers thereof, polyvinyl chloride, polyvinyl acetate and copolymers thereof, and polytetrafluoroethylene.

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