CN103172967B - For the Solid mixture antioxidant and preparation method thereof of resin - Google Patents

Abstract

The invention is used in the technical field of solid mixture antioxidant for resin and its preparation method, and the preparation of synthetic material antioxidant products. In order to overcome the problems of poor dispersibility, inconvenient use, and low antioxidant efficiency of solid powder antioxidants in ABS latex, a solid mixture antioxidant was prepared for use in the process of emulsion graft polymerization to produce ABS latex, specifically It involves selecting a phenolic main antioxidant, a sulfide auxiliary antioxidant and a terminator to form a composite antioxidant, adding an emulsifier and a rubber oil blending agent, melting and dissolving under heating conditions A liquid mixture is formed, stirred by a high-speed shearing machine to form a homogenized mixed solution, and the solid mixture antioxidant of the present invention is obtained after cooling. The dosage form of the solid mixture antioxidant can be a tablet or a barrel product, which is convenient for storage , transportation and winter use in cold regions.

Description

Solid mixture antioxidant for resin and preparation method thereof

technical field

The invention belongs to the technical field of preparation of antioxidant products for synthetic materials, and in particular relates to the process of preparing a solid mixture antioxidant for emulsion graft polymerization to produce ABS latex.

Background technique

Among ABS resins, that is, butadiene, styrene, and acrylonitrile terpolymers, the polybutadiene component is most affected by thermal oxidation, which plays a decisive role in the aging of the overall material. Butadiene rubber particles are aging Degradation occurs first in the process, and it will react with oxygen in the air when exposed to the air, making it age. In addition, the ABS grafted powder has to go through the drying process. The powder particles have a large specific surface. Drying is generally carried out at 110°C to 130°C, which increases the contact time with hot air. Under this condition, the powder particles It is prone to partial oxidation and yellowing, and after high-temperature screw granulation, its physical and mechanical properties are damaged to varying degrees due to thermal aging. The anti-aging problem of ABS resin is relatively prominent. Under the action of heat, light and oxygen at ambient temperature, ABS resin will gradually turn yellow, harden and become brittle. At higher temperatures, it can cause coking and blackening. In order to inhibit or delay its oxidative degradation during production, processing and use, it is necessary to add suitable antioxidants.

The choice of antioxidant species is crucial.

Appropriate antioxidants can effectively improve the anti-aging performance of the resin and prolong the service life; commonly used are: 2,6-di-tert-butyl-4-methylphenol (BHT), 2,2′-methylene bis (4-Ethyl-6-tert-butylphenol) (Antioxidant 425); 2,2′-Methylenebis(4-methyl-6-tert-butylphenol) (Antioxidant 2246) 2 ,2′-methylenebis(4,6-di-tert-butylphenol); 2,2′-ethylenebis(4,6-di-tert-butylphenol), β-(4-hydroxy-3,5 -n-octadecyl di-tert-butylphenyl)propionate (antioxidant 1076); tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester (antioxidant 1010); triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (antioxidant 245). Phosphite antioxidants include: tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168); (trinonylphenyl) phosphite (antioxidant TNPP); Pentaerythritol Distearate Phosphite (Antioxidant 619); Bis(2,4-Di-tert-Butylphenyl) Pentaerythritol Diphosphite (Antioxidant 626). Thioether antioxidants include: bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide; 2,2'-thioethylene glycol bis[β-(3,5-di-tert Butyl-4-hydroxyphenyl) propionate]; 4,4'-thiobis(2-methyl-6-tert-butylphenol); 2,2'-thiobis(4-methyl- 6-tert-butylphenol); 4,4'-thiobis(2,6-di-tert-butylphenol); 4,4'-thiobis(6-tert-butyl-m-cresol); Thiobis Dilauryl propionate (DLTDP); Diisotridecyl thiodipropionate (DTDTP); Dioctadecyl thiodipropionate (DSTDP).

The addition of antioxidants and the choice of dosage form are also important.

Appropriate antioxidant addition method and antioxidant dosage form are based on the principle that it can be easily miscible in ABS latex. After coagulation and dehydration, the uniformly dispersed ABS graft powder will play an antioxidant role, otherwise it will make some The antioxidant remains in the wastewater or is attached to the surface of the ABS grafted powder, resulting in low use efficiency of the antioxidant.

Using emulsion type antioxidant, after coagulation and dehydration of the latex, the antioxidant can be evenly dispersed in the ABS grafted powder, and the use efficiency of the antioxidant is high; the dispersibility of the solid powder in the ABS latex is very poor , the use efficiency of antioxidants is very low; therefore, for the use of solid crystalline antioxidants, antioxidants with low melting points are often selected, which can be melted in hot water at 60-80°C, and stirred after adding dispersant Disperse, and then add to ABS latex, can properly improve the use efficiency of solid antioxidant, such as the antioxidant 245, DLTDP melted in hot water, add potassium rosinate soap to make a water mixture antioxidant. The use of solid powder antioxidants in ABS latex is limited to varying degrees.

During the aging process, the toughness of ABS grafted powder decreases, the rigidity increases, and the appearance color gradually turns yellow and deepens. Especially, the increase of heating temperature will accelerate the progress. Therefore, the temperature is usually set above 180°C, and the accelerated aging test is carried out for evaluation. The anti-aging performance of ABS grafted powder, the longer the discoloration time, the better its anti-oxidation performance.

In the production process of ABS grafted powder, the emulsion antioxidant is easy to use and can be directly added to the ABS latex, which is convenient for latex and antioxidant emulsion to mix and disperse evenly, and can exert a good antioxidant effect.

CN102181072A discloses a method for preparing a compound antioxidant for ABS latex, using Wingstay-L and diisotridecyl thiodipropionate (DTDTP) as raw materials, high-speed homogeneous emulsification to prepare an emulsion antioxidant . Liquid type antioxidant, the antioxidant exists in the form of liquid particles, uniformly dispersed in the emulsion, and has a particularly good compatibility with the polymer in the ABS latex. After coagulation, the effective composite antioxidant components can be evenly dispersed In the ABS grafted powder, the performance of the antioxidant is greatly improved.

Although ABS emulsion type antioxidant has many advantages, in winter in cold regions, the ambient temperature reaches minus 30°C, and it is easy to freeze during transportation. It is difficult to accurately measure when used, and when added to ABS latex, the dispersion performance will deteriorate, which will bring great inconvenience to the transportation and storage of emulsion antioxidants. Therefore, ABS resin manufacturers located in this area also need to have solid dosage forms of antioxidants for use in winter.

Fine Chemical Industry, 2002, 19 (5) discloses composite antioxidant YHK-1, put trinonylphenyl phosphite and dispersant A in the reactor, stir evenly and heat up to a certain temperature, add certain The ratio of antioxidant 245, its shortcoming is that the hot water melts the antioxidant and uses it after emulsification, which makes the production process cumbersome.

Plastic Science and Technology, 2007, 35 (8) proposed to use antioxidant 1076, T501, trinonylphenyl sulfide phosphite, and anti-hydrolysis stabilizer to form an emulsion antioxidant to be used in ABS latex. The effects of 1076 and T501 as main antioxidants are not very good.

China Plastics, 2008, 22 (4) discloses that the emulsion compounded with antioxidant 245 and DLTDP is used in ABS latex. The emulsifier is melted in hot water, then stirred and mixed and then added to the ABS latex. This technology is used by ABS resin manufacturers.

Contents of the invention

The water-emulsion antioxidant can be uniformly dispersed in the ABS grafted powder, and the usage efficiency of the antioxidant is higher. Although the emulsion antioxidant has many advantages, the raw materials selected for the preparation of an emulsion antioxidant need to be in a liquid state after combination, so the selected antioxidant species are limited by a narrow range, and some are very suitable for ABS grafting. Powder anti-aging solid state antioxidants cannot be used after being made into water-emulsion antioxidants, such as antioxidant 245, etc.

According to the aging behavior characteristics of the ABS grafted powder and the synergistic effect of the antioxidant, the present invention optimizes the formula of the ternary composite antioxidant, and the prepared solid mixture antioxidant of the present invention has a melting point of 30-45 °C, it is easy to melt in the ABS latex at 50-60 °C and make the antioxidant component uniformly dispersed in the graft powder.

In order to overcome the problems of poor dispersibility, inconvenient use and low antioxidant efficiency of solid antioxidants in ABS latex, the present invention prepares a solid mixture antioxidant for use in the process of producing ABS latex, which has antioxidant efficiency High, low cost, easy to use, and easy to store, transport and use in winter in cold regions.

The solid mixture antioxidant for ABS resin and the preparation method thereof of the present invention are carried out according to the following steps: select a phenolic primary antioxidant, a thioether auxiliary antioxidant and a terminator to compound the composition Composite antioxidant, add emulsifier and rubber oil blending agent, form a liquid mixture after melting and dissolving under heating conditions, use high-speed shearing machine to stir, form a mixed liquid in a homogenized state, and obtain the solid mixture anti-oxidant of the present invention after cooling Oxygen. The dosage form of the solid mixture antioxidant of the present invention can be a lozenge or a bottled product.

The method for preparing solid mixture antioxidant of the present invention, carry out according to the following steps:

Add a phenolic primary antioxidant, a thioether secondary antioxidant, a terminator antioxidant, emulsifier and rubber oil blending agent into the blending kettle in proportion, stir, heat up, melt and dissolve A liquid mixture is formed, stirred by a high-speed shearing machine to form a homogenized mixed liquid, cooled to room temperature, and the solid mixture antioxidant of the present invention is obtained.

The mixing ratio of the phenolic primary antioxidant, thioether secondary antioxidant, terminator, emulsifier, and rubber oil blending agent is based on mass ratio, phenolic primary antioxidant: sulfide secondary antioxidant Agent = 1:1, phenolic primary antioxidant: terminator type antioxidant = 1: 0.10 ~ 0.25; phenolic primary antioxidant: emulsifier = 1: 0.12 ~ 0.16; phenolic primary antioxidant: rubber oil Blending agent=1:0.10～0.20.

The phenolic primary antioxidants described therein are: 2,6-di-tert-butyl-4-methylphenol; 2,2′-ethylene bis(4,6-di-tert-amylphenol); 2,2 '-Ethylenebis(4,6-di-tert-butylphenol); 2,2'-methylenebis(4,6-di-tert-amylphenol); 2,2'-methylenebis(4, 6-di-tert-butylphenol); 2,2′-methylenebis(4-ethyl-6-tert-butylphenol); 2,2′-methylenebis(4-methyl-6-tert butylphenol); Propionic acid] pentaerythritol ester, triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate.

The thioether auxiliary antioxidants described therein are: bis(4-tert-butylbenzyl) sulfide, bisbenzyl sulfide, bis(tetradecyl) thiodipropionate, thiodipropionate Bis(isotridecyl alcohol) ester; thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1035), bis(3,5- Di-tert-butyl-4-hydroxybenzyl)sulfide; 4,4'-thiobis(2-methyl-6-tert-butylphenol); 2,2'-thiobis(4-methyl- 6-tert-butylphenol); 4,4'-thiobis(2,6-di-tert-butylphenol); 4,4'-thiobis(6-tert-butyl-m-cresol); Thiobis Dilauryl Propionate; Dioctadecyl Thiodipropionate.

The terminator antioxidants described therein are hydroxylamine compounds: N,N-bis(octadecyl)hydroxylamine, N,N-bis(p-tert-butylbenzyl)hydroxylamine, N,N-bis(m-methyl) Benzyl) hydroxylamine, N,N-dilauryl hydroxylamine, N,N-bis(tetradecyl)hydroxylamine, N,N-bis(hexadecyl)hydroxylamine, N-hexadecyl-N-decyl N,N-dialkylhydroxylamine products prepared by direct oxidation of octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-bis(hydrogenated tallow)amine, N,N-bis (Benzylthiomethyl)hydroxylamine, N,N-Dibenzylhydroxylamine.

Wherein said rubber oil blending agent is: naphthenic rubber oil, trade name KN4008.

The emulsifier described therein is: a complex of nonylphenol polyoxyethylene ether and disproportionated potassium abietate soap, the compounding ratio is calculated by mass ratio, nonylphenol polyoxyethylene ether: disproportionated potassium abietate soap=1:3.0; The mass concentration of disproportionated potassium abietate is 80%.

In the method for preparing the solid mixture antioxidant described therein, the heating temperature is 100-130°C.

Advantages of the present invention

1. The present invention optimizes the formula of the ternary composite antioxidant according to the aging behavior characteristics of the ABS grafted powder and the synergistic effect of the antioxidant, and the prepared solid mixture antioxidant of the present invention has a melting point of 30 ～45℃, it is easy to melt in ABS latex at 50～60℃, and the antioxidant components can be uniformly dispersed in it.

2. Terminating dosage form antioxidants can not only capture free radicals, but also decompose hydroperoxides, which are multifunctional stabilizers. First, it can provide an active hydrogen atom to form a free radical with a stable structure, and then this free radical captures the carbon free radicals and alkoxy free radicals that cause polymer degradation, thereby terminating the autoxidation process of the polymer , and because hydroxylamine contains nitrogen and oxygen atoms with unshared electrons at the same time, it can capture multiple free radicals at the same time. Compared with the traditional binary stabilizer system, the terminator type antioxidant has high activity and can show excellent antioxidant effect in a relatively low concentration range, and because the existence of phenolic substances is avoided, the polymer and NOx etc. Discoloration occurs when the gas is in contact, effectively preventing the discoloration of the ABS grafted powder.

3. The antioxidation performance of the solid mixture antioxidant of the present invention is obviously better than the compound formulation system of DLTDP and antioxidant 245 used in the traditional technology, and in contrast, the solid mixture antioxidant has good oxidation resistance, and is superior in ABS Good dispersion in latex, high antioxidant usage efficiency, less dosage, low cost, and convenient use can replace emulsion antioxidants and can be used in winter in cold regions.

Detailed ways

The phenolic primary antioxidant used in the present invention, terminator, rubber oil blending agent, p-tert-butyl benzyl chloride, hydroxylamine hydrochloride, sodium carbonate, m-methyl benzyl bromide, bis-benzyl sulfide, ethanol, n-hexyl Alkane, tetrabutylammonium bromide, nonylphenol polyoxyethylene ether (TX-10), polyethylene glycol PEG-400) are commercially available industrial products, and the specifications are industrial superior products; disproportionated potassium abietic acid soap is commercially available Selling industrial products, the mass concentration is 80%.

The preparation method of two (4-tert-butylbenzyl) sulfides of sulfide auxiliary antioxidant in the present invention:

In a GSHB type 1000mL glass reactor with a magnetic stirrer, add 160 grams of 98.5% p-tert-butyl benzyl chloride, 120 grams of n-hexane, tetrabutylammonium bromide: nonylphenol polyoxyethylene ether = 1: 0.5 emulsifier 3.3 grams, phase transfer catalyst (polyethylene glycol PEG-400) 1.3 grams, 20% Na ₂ S aqueous solution 169 grams. Nitrogen replacement, stirring, and temperature rise. When the temperature in the system rises to 50-52° C., keep the reaction for 240 minutes, and the reaction ends. Cool down to 25-28°C, let stand to separate layers, collect the organic phase, distill 50 g of n-hexane under reduced pressure, precipitate crystals after cooling down, filter, wash, and dry to obtain a white crystalline product at 54.3-56.1°C, which is the antioxidant bis (4-tert-butylbenzyl)sulfide.

In the present invention, the preparation method of N,N-bis(m-methylbenzyl)hydroxylamine of the terminator type antioxidant:

In a reactor with a stirrer, a thermometer and a reflux condenser, 11.6 g of hydroxylamine hydrochloride, 40 g of sodium carbonate, 58 g of m-methylbenzyl bromide, and 90 g of ethanol were added. Nitrogen replacement, heating, stirring, heating up to 43-46°C, heat preservation reaction for 30-40min. Then raise the temperature to 65-70°C and keep the temperature for 40-60min. After the reaction is completed, wash with water, filter, wash the crystalline product with 80-90% ethanol solution, and dry to obtain N,N-bis(m-methylbenzyl)hydroxylamine as a white crystalline product with a melting point of 71-74°C.

The following non-limiting examples 1 to 3 are used to illustrate the present invention, rather than to limit the present invention, within the spirit of the present invention and the scope of protection of the claims, any amendments and changes made to the present invention belong to the present invention scope of protection.

1. Preparation of solid mixture antioxidant

Example 1

100g triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (antioxidant 245), 100g bis(4-tert-butylbenzyl)sulfur Add ether, 25g N,N-bis(p-tert-butylbenzyl)hydroxylamine, 4g nonylphenol polyoxyethylene ether, 12g disproportionated abietic acid potassium soap, 20g rubber oil blending agent into the beaker, heat to 100-130°C, Stir and melt evenly, homogeneously pre-emulsify for 30 minutes under a high-speed shearing machine, the temperature drops to 20-25°C, and after solidification, the solid mixture antioxidant of the present invention is obtained, with a melting point of 33-45°C, namely Example 1# antioxidant .

Example 2

Mix 100g of antioxidant 245, 100g of bisbenzyl sulfide, 15g of N,N-bis(m-methylbenzyl)hydroxylamine, 3g of nonylphenol polyoxyethylene ether, 9g of disproportionated potassium rosinate soap, and 10g of rubber oil Add the agent into a beaker, heat to 100-130°C, stir and melt evenly, pre-emulsify homogeneously under a high-speed shear for 30 minutes, and drop the temperature to 20-25°C, and obtain the solid mixture antioxidant of the present invention after solidification, with a melting point of 31 ～42 ℃, promptly embodiment 2# antioxidant.

Example 3

100g of antioxidant 245, 100g of bis(4-tert-butylbenzyl)sulfide, 10g of N,N-bis(m-methylbenzyl)hydroxylamine, 3.5g of nonylphenol polyoxyethylene ether, and 10.5g of disproportionated Potassium rosinate soap and 15g of rubber oil blending agent are added to a beaker, heated to 100-130°C, stirred and melted evenly, homogeneously pre-emulsified for 30min under a high-speed shearing machine, the temperature is lowered to 20-25°C, and the present invention is obtained after solidification The melting point of the solid mixture antioxidant is 30-44°C, that is, the antioxidant of Example 3#.

Comparative example 1

According to the ABS resin production process of Xinhu (Changzhou) Petrochemical Co., Ltd., mix 100g of antioxidant 245, 100g of antioxidant dilauryl thiodipropionate, and 200g of 15% potassium abietate soap, and heat to 75-85°C , fully stirred to obtain the antioxidant mixed solution, that is, the comparative example 1# antioxidant.

Comparative example 2

The commercially available polymeric hindered phenol/thioester compound emulsion antioxidant OCTOLITE806 is comparative example 2# antioxidant.

Comparative example 3

Shanghai Langli Chemical Co., Ltd. produces a polymeric hindered phenol/thioester compound emulsion antioxidant, which is comparative example 3# antioxidant.

2. Experimental method for testing the oxidation performance of ABS samples

1. Oxidation induction period

Using a DSC200PC differential scanning calorimeter, put a sample of ABS grafted powder with a mass of (15.0±0.5) mg in an aluminum dish, pass nitrogen gas at (50±5) mL/min, and control the heating rate 20°C/min, heating up to 160°C. Keep the temperature constant for 3 minutes, replace the nitrogen with oxygen, and keep the temperature at 160°C until the maximum exothermic signal appears. The recorded time is the oxidation induction period in minutes.

2. Hot air aging test

Put the ABS grafted powder in an aluminum dish with a thickness of about 5mm, put it into the LR016A thermal oxygen aging box for hot air aging test, set the aging test temperature at 180°C, set the ventilation conditions, and observe the appearance of the powder regularly For the color change, record the time min when the powder turns dark brown, and set it as the coking time. The longer the coking time, the better the anti-oxidation performance of the sample.

Three, ABS sample preparation method

Weigh 50.0g of ABS latex (produced by Changzhou Xinhu Petrochemical Co., Ltd., with a solid content of 42%) and add it to a beaker, quantify it successively, and add 0.14g of the solid mixture antioxidant of Examples 1 to 3# of the present invention; comparative example 1# Antioxidant 0.28g, heat up to 60°C at an appropriate stirring speed for use; another analytical reagent H ₃ PO ₄ 0.64g, MgSO ₄ 2.22g, deionized water 102.33g were placed in a 250mL reflux device In the flask, heat up to 90°C and stir at a speed of 250r/min; when the temperature of the mixture in the beaker rises to 90°C, add the preheated ABS latex within 2 minutes; maintain the temperature at 90°C and keep it warm for 30 minutes; after the polymer particles are completely precipitated , filtered, washed with deionized water until nearly neutral, and vacuum-dried at 50-60°C to obtain ABS grafted powder samples with antioxidant added, Examples 1-3#; Comparative Example 1#.

4. Aging test results

Table 1 Oxidation induction period and coking time

The aging test results show that 50g of ABS latex is added with 0.14g of the solid mixture antioxidant prepared in Examples 1-3# of the present invention to obtain 3 samples. The oxidation induction period at 160°C is 76-82 minutes, significantly higher than the 55-65 minutes of comparative examples 1-3#; in the hot air aging test at 180°C, add the solid mixture prepared by Examples 1-3# of the present invention Antioxidant, get 3 samples. The coking time is 322-351 minutes, significantly higher than the 210-246 minutes of Comparative Examples 1-3#. Therefore, it can be considered that the antioxidant performance of the 1-3# solid mixture antioxidants prepared by the present invention is better than that of the antioxidants used in the comparative examples 1-3#.

Claims (7)

1. be used for the preparation method of the solid mixture antioxidant of resin, it is characterized in that carrying out according to the following steps: Add a phenolic primary antioxidant, a thioether secondary antioxidant, a terminator antioxidant, emulsifier and rubber oil blending agent into the blending kettle in proportion, stir, heat up, melt and dissolve forming a liquid mixture, stirring with a high-speed shearing machine to form a homogenized mixed solution, cooling to room temperature, and obtaining the solid mixture antioxidant; Among them, the proportion of phenolic primary antioxidant and terminal dosage antioxidant is calculated by mass ratio, primary antioxidant: terminal dosage antioxidant = 1: 0.10~0.25; The terminator antioxidants described therein are hydroxylamine compounds: N,N-bis(octadecyl)hydroxylamine, N,N-bis(p-tert-butylbenzyl)hydroxylamine, N,N-bis(m-methyl) Benzyl) hydroxylamine, N,N-dilauryl hydroxylamine, N,N-bis(tetradecyl)hydroxylamine, N,N-bis(hexadecyl)hydroxylamine, N-hexadecyl-N-decyl N,N-dialkylhydroxylamine products prepared by direct oxidation of octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-bis(hydrogenated tallow)amine, N,N-bis (Benzylthiomethyl)hydroxylamine, N,N-Dibenzylhydroxylamine. 2. the preparation method of the solid mixture antioxidant that is used for resin according to claim 1 is characterized in that wherein said phenolic main antioxidant and sulfide auxiliary antioxidant and emulsifier and rubber oil are blended The mixing ratio of additives is calculated by mass ratio, phenolic primary antioxidant: sulfide secondary antioxidant = 1: 1; phenolic primary antioxidant: emulsifier = 1: 0.12~0.16; phenolic primary antioxidant : Rubber oil blending agent = 1: 0.10~0.20. 3. the preparation method for the solid mixture antioxidant of resin according to claim 1, is characterized in that wherein said phenolic main antioxidant is: 2,6-di-tert-butyl-4-methyl Phenol; 2 ,2′-Ethylenebis(4,6-di-tert-amylphenol); 2 ,2′-Ethylenebis(4,6-di-tert-butylphenol); 2 ,2′-Methylene Bis(4,6-di-tert-amylphenol); 2 ,2′-methylenebis(4,6-di-tert-butylphenol); 2 ,2′-methylenebis(4-ethyl-6 -tert-butylphenol); 2 ,2′-methylenebis(4-methyl-6-tert-butylphenol); β-(4-hydroxy-3,5-di-tert-butylphenyl)propanoic acid N-octadecyl ester, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5 -methylphenyl) propionate. 4. the preparation method for the solid mixture antioxidant of resin according to claim 1 is characterized in that wherein said sulfide auxiliary antioxidant is: two (4-tert-butylbenzyl) sulfide , bisbenzyl sulfide, ditetradecyl thiodipropionate, di(isotridecyl alcohol) thiodipropionate; thiodiethylene bis[3-(3,5-di-tert Butyl-4-hydroxyphenyl)propionate (antioxidant 1035), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; 4,4' ^- thiobis(2- methyl-6-tert-butylphenol); 2,2' ^- thiobis(4-methyl-6-tert-butylphenol); 4,4' ^- thiobis(2,6-di-tert-butyl phenol); 4,4' ^- thiobis(6-tert-butyl-m-cresol); dilauryl thiodipropionate; dioctadecyl thiodipropionate. 5. The solid mixture antioxidant for resin according to claim 1 and the preparation method thereof, wherein said rubber oil blending agent is: naphthenic rubber oil. 6. the preparation method for the solid mixture antioxidant of resin according to claim 1 is characterized in that wherein said emulsifier is: the complex of nonylphenol polyoxyethylene ether and disproportionated abietate potassium soap, The mixing ratio is calculated by mass ratio, nonylphenol polyoxyethylene ether: disproportionated potassium abietate soap = 1:3.0; the mass concentration of disproportionated potassium abietate is 80%. 7. The method for preparing the solid mixture antioxidant for resin according to claim 1, characterized in that the heating temperature in the method for preparing the solid mixture antioxidant is 100-130°C.