CN103242478B - Acrylate agglomerant and preparation method thereof, and method for modifying ASA (acrylonitrile-styrene-acrylate) resin with agglomerant - Google Patents

Abstract

The invention discloses an acrylic ester agglomerating agent, a preparation method thereof and a method for modifying ASA resin through the agglomerating agent, wherein the raw material of the acrylic agglomerating agent is composed of 12-14 parts by mass of acrylate , 3-4 parts of unsaturated acid, 0.5-0.7 part of compound emulsifier, 80-85 part of deionized water, 0.05-0.15 part of initiator; mix acrylate, unsaturated acid, compound emulsifier and deionized Mix with water, stir and emulsify, heat up to 70°C after emulsification, add initiator, keep warm for 3 hours to obtain a milky white emulsion, which is the agglomeration agent. The raw material components of the agglomerating agent of the invention are simple, the agglomerating agent has good modification effect, can increase the apparent particle size of basic latex particles and ASA resin in a short time, and can effectively improve the impact resistance of the ASA resin.

Description

A kind of acrylate agglomerating agent and its preparation method and the method for modifying ASA resin by agglomerating agent

1. Technical field

The invention relates to an acrylic ester agglomerating agent and its application, in particular to an acrylic agglomerating agent, a preparation method thereof and a method for modifying ASA resin through the agglomerating agent.

2. Background technology

ASA resin refers to acrylonitrile (A), styrene (S) and acrylate (A) ternary graft copolymer, ABS resin refers to acrylonitrile (A), butadiene (B) and styrene (S) Ternary graft copolymer. The study found that when preparing ASA or ABS resin materials by the emulsion grafting method, it is very necessary to control the particle size of the base latex to prepare products with excellent properties. Over the years, there have been reports of increasing the size of the base latex particles, both physically and chemically, all of which can increase the size of the latex particles. However, due to high energy consumption, unsatisfactory agglomeration effect, and long agglomeration cycle, it has not been able to get considerable development and attention.

In recent years, the research and application reports of polymer agglomeration methods have emerged continuously. The application of polymer latex method can make latex with small particle size into latex with large particle size, and can improve the related properties of the product. The agglomeration principle of the polymer latex method is to use the agglomerating agent to partially destroy the surfactant of the agglomerating agent, so that it can be fused into relatively large latex particles, so as to achieve the purpose of enlarging the particle size, and enlarging the particle size can make the dispersion The apparent particle size of the rubber phase in the resin phase is significantly increased, thereby improving its impact resistance. Therefore, the polymer latex agglomeration method has received widespread attention in the preparation of large particle size latex. This method has a short agglomeration cycle, good agglomeration effect, simple agglomeration operation and easy control of the agglomeration process.

According to the latest data, the particle size of small particle latex can be increased to 200-700nm by using the copolymer of ethylenic monomer or unsaturated ester and α, β unsaturated acid as agglomerating agent. Lin Runxiong et al reported the synthesis of large particle size styrene butadiene latex by latex agglomeration method, which can make the average particle size reach 295nm; Reported with CNPC Lanzhou Chemical Industry Research Center that propylene ester agglomerating agent was used to prepare latex with an average particle size above 400nm; Daqing Petrochemical Company used agglomerating agent latex to produce ABS products with a particle size of 600nm.

Although the preparation and application of acrylate agglomerating agents have been reported in the literature, they are still in the empirical stage, and there is no very mature theory to follow. Moreover, the use of acrylate agglomerating agents to prepare modified ASA resins and use them to improve the mechanical properties of resins has not been reported.

3. Contents of the invention

The present invention aims to provide an acrylic ester agglomerating agent and its preparation method and a method for modifying ASA resin through the agglomerating agent. The technical problem to be solved is to increase the latex particle size of ASA and improve the Mechanical properties of the resin.

The present invention solves technical problem and adopts following technical scheme:

The acrylic ester agglomerating agent of the present invention, its raw material constitutes by mass parts:

12-14 parts of acrylate, 3-4 parts of unsaturated acid, 0.5-0.7 parts of compound emulsifier, 80-85 parts of deionized water, 0.05-0.15 parts of initiator;

Further preferred are:

13 parts of acrylate, 3.3 parts of unsaturated acid, 0.6 part of compound emulsifier, 83 parts of deionized water, and 0.10 part of initiator.

The unsaturated acid is acrylic acid;

The compounded emulsifier is obtained by compounding an anionic emulsifier and a nonionic emulsifier at a mass ratio of 1:1;

The initiator is a water-soluble initiator, preferably potassium persulfate.

The acrylate is butyl acrylate.

The mass ratio of the acrylate to the unsaturated acid is 4:1.

The anionic emulsifier is sodium dodecyl sulfate (SDS), and the nonionic emulsifier is Triton X-100.

The water-to-oil ratio in the agglomerating agent is 5:1. Water in the water-to-oil ratio refers to water phase substances, that is, deionized water and initiator potassium persulfate; oil refers to oil phase substances, that is, acrylates, unsaturated acids and compound emulsifiers.

The synthesis method of the acrylate agglomerating agent of the present invention is to mix acrylate, unsaturated acid, compound emulsifier and deionized water according to the ratio, stir and emulsify, heat up to 70°C after emulsification, add initiator, and keep warm for reaction The milky white emulsion obtained in 3 hours is the agglomeration agent.

Utilize the method for modified ASA resin of acrylate agglomerating agent of the present invention, each raw material is constituted by mass parts:

Butyl acrylate (BA) 6-10 parts, styrene (St) 20-27 parts, acrylonitrile (AN) 7-8 parts, acrylate agglomerating agent 2.0-8.0 parts, deionized water 50.0-60.0 parts, Potassium persulfate (KPS) 0.08-0.12 parts, sodium dodecyl sulfate (SDS) 0.2-0.7 parts, sodium bicarbonate 0.08-0.16 parts, cross-linking agent 0.20-0.40 parts, tertiary dodecyl mercaptan 0.02- 0.08 copies;

The crosslinking agent is selected from tripropylene glycol diacrylate (TPGDA) or 1,6-hexanediol diacrylate (HDDA).

Each raw material is preferably in parts by mass:

6-10 parts of butyl acrylate, 21.32-26.5 parts of styrene, 7.2-7.9 parts of acrylonitrile, 2.72-8.0 parts of acrylate agglomerating agent, 52.9-60.0 parts of deionized water, 0.096-0.12 parts of potassium persulfate, ten 0.31-0.7 parts of sodium dialkyl sulfate, 0.09-0.16 parts of sodium bicarbonate, 0.22-0.32 parts of crosslinking agent, and 0.032-0.08 parts of tertiary dodecyl mercaptan.

Utilize the method for modified ASA resin of acrylate agglomerating agent of the present invention to operate according to the following steps:

1) First add 60-70% butyl acrylate, 10-20% deionized water, 25-35% sodium lauryl sulfate, 30-40% potassium persulfate and all carbonic acid to the reactor Sodium hydrogen, react at 65-80°C for 3 hours under the protection of nitrogen;

2) Add the remaining amount of butyl acrylate, 10-20% deionized water, 15-25% sodium lauryl sulfate, 20-25% potassium persulfate, 10-15% % of styrene, 6-7% of acrylonitrile and all cross-linking agents, reacted at 65-80°C for 3 hours under the protection of nitrogen;

3) Add an acrylate agglomerating agent to the reaction solution in step 2), and react at 45-65°C for 1 hour under the protection of nitrogen;

4) Add the remaining amount of styrene, the remaining amount of acrylonitrile, the remaining amount of deionized water, the remaining amount of sodium lauryl sulfate, the remaining amount of potassium persulfate and all the t Dodecyl mercaptan, react at 65-80°C for 5 hours under the protection of nitrogen, filter after demulsification and dry at 40-50°C for 24 hours to obtain modified ASA resin powder.

The demulsification is to add a sodium chloride aqueous solution with a mass concentration of 2% to the reaction liquid, and the ratio of the volume of the sodium chloride aqueous solution to the volume of the ASA emulsion is 4:1.

The modified ASA resin powder was injection molded to obtain a resin sample, and the tensile properties were tested according to GB/T1040.2-2006, and the impact properties were tested according to GB1843-2008.

The preparation method of the present invention is not only suitable for laboratory preparation (250ml, 500ml reactors), but also successfully enlarged to 1000ml and 2000ml reactors.

The raw material components of the agglomerating agent of the invention are simple, the agglomerating agent has good modification effect, can increase the apparent particle size of basic latex particles and ASA resin in a short time, and can effectively improve the impact resistance of the ASA resin.

4. Specific implementation methods

Example 1:

1. The raw materials of the agglomerating agent are composed of:

Butyl acrylate: 13 parts,

Acrylic acid: 3.3 parts,

Compound emulsifier: 0.60 parts,

Deionized water: 83 parts,

Initiator potassium persulfate: 0.10 parts;

The compound emulsifier is obtained by compounding SDS and Triton X-100 at a mass ratio of 1:1.

2. Preparation of agglomerating agent

Add n-butyl acrylate, acrylic acid, compound emulsifier and deionized water into the reaction kettle according to the ratio, stir and emulsify, heat up to 70°C after emulsification, add initiator potassium persulfate, control the temperature at 70°C and keep it warm for 3 hours. The obtained milky white latex is the agglomerating agent.

3. Composition and mass fraction of PBA latex:

Butyl acrylate: 39.63 parts,

Deionized water: 59.45 parts,

Initiator potassium persulfate: 0.11 parts,

Compound emulsifier: 0.79 parts.

The compound emulsifier is obtained by compounding SDS and Triton X-100 at a mass ratio of 1:1.

4. Preparation of PBA latex

1) First add 0.26 parts of compound emulsifier and 19.88 parts of deionized water to the reaction kettle, stir quickly to dissolve it fully, then add 13.21 parts of butyl acrylate, emulsify for half an hour, heat up to 78 °C, and add 0.04 parts of initiator Potassium persulfate, after the reaction is carried out until there is no reflux, the temperature is raised to 81° C., and the reaction is kept for one hour to obtain the seed emulsion.

2) Add the mixed solution of the remaining amount of butyl acrylate, the remaining amount of compound emulsifier, the remaining amount of initiator potassium persulfate and the remaining amount of deionized water to the reaction solution in step 1), and the dropping rate is controlled at There was no obvious reflux on the wall of the reaction bottle. After the feeding was completed, the reaction temperature was kept constant. After 3 hours of reaction, the temperature was raised to 85° C., matured for half an hour, and cooled to discharge.

5. Preparation of large particle size PBA latex

Add an agglomerating agent to the PBA latex prepared in step 4 at a volume ratio of 9:1 between the PBA latex and the agglomerating agent, control the temperature at 45-65° C., and react for 1 hour under nitrogen protection. After diluting the emulsion, the particle size distribution of the latex particles was measured using a Zeta potential analyzer.

Example 2:

The preparation method of this implementation is the same as that of Example 1, except that no agglomerating agent is used to enlarge its particle size, that is, step 5 is omitted. After the emulsion was diluted, the particle size distribution of the PBA latex particles was measured by a Zeta potential analyzer.

Example 3:

1. The composition and mass parts of the agglomerating agent are:

Butyl acrylate: 13 parts,

Acrylic acid: 3.3 parts,

Deionized water: 83 parts,

Initiator potassium persulfate: 0.10 parts,

Compound emulsifier: 0.60 parts.

The compound emulsifier is obtained by compounding SDS and Triton X-100 at a mass ratio of 1:1.

2. Preparation of agglomerating agent:

Add butyl acrylate, acrylic acid, deionized water and compound emulsifier into the reaction kettle according to the proportioning amount, stir and emulsify, heat up to 70°C after emulsification, add initiator potassium persulfate, control the temperature at 70°C and keep it warm for 3 hours to obtain Milky white latex is the agglomerating agent.

3. Raw materials and mass parts of modified ASA resin:

Butyl acrylate: 8.4 parts,

Styrene: 21.32 parts,

Acrylonitrile: 10.68 parts,

Agglomerating agent: 2.72 parts,

Deionized water: 60 parts,

Potassium persulfate: 0.096 parts,

Sodium lauryl sulfate: 0.32 parts,

Sodium bicarbonate: 0.10 parts,

Cross-linking agent HDDA: 0.22 parts,

Tertiary dodecyl mercaptan: 0.048 parts.

4. Preparation of modified ASA resin:

1) First, add 67% butyl acrylate, 13% deionized water, 28% sodium lauryl sulfate, 35% potassium persulfate and all sodium bicarbonate to the reactor, under nitrogen protection React at 65-80°C for 3 hours;

2) Add the remaining amount of butyl acrylate, 13% deionized water, 17% sodium lauryl sulfate, 22% potassium persulfate, 12% styrene, 6.25% Acrylonitrile and all the crosslinking agent HDDA were reacted at 65-80°C for 3 hours under the protection of nitrogen;

3) Add an agglomerating agent to the reaction solution in step 2), control the temperature at 45-65°C, and react for 1 hour under nitrogen protection;

4) Add the remaining amount of styrene, the remaining amount of acrylonitrile, the remaining amount of deionized water, the remaining amount of sodium lauryl sulfate, the remaining amount of potassium persulfate and all the t Dodecyl mercaptan was reacted at 65-80°C for 5 hours under nitrogen protection to obtain ASA emulsion;

5) Add 4 times the volume of 2% sodium chloride aqueous solution to the ASA emulsion prepared in step 4), demulsify the ASA emulsion at normal temperature and pressure, filter and dry at 45°C for 24 hours to obtain modified ASA Resin powder.

After injection molding the modified ASA resin powder, the resin sample was prepared, and the tensile properties were tested according to GB/T1040.2-2006, and the impact properties were tested according to GB1843-2008.

Example 4:

This example repeats Example 3, except that no agglomerating agent is added, that is, step 3 is omitted).

Example 5:

Step 1) and step 2) of this embodiment are the same as in Embodiment 3.

3. Raw materials and mass parts of modified ASA resin:

Butyl acrylate: 6.0 parts,

Styrene: 23.12 parts,

Acrylonitrile: 7.68 parts,

Agglomerating agent: 4.72 parts,

Deionized water: 57.60 parts,

Potassium persulfate: 0.11 parts,

Sodium lauryl sulfate: 0.31 parts,

Sodium bicarbonate: 0.09 parts,

Cross-linking agent HDDA: 0.32 parts,

Tertiary dodecyl mercaptan: 0.050 parts.

4. Preparation of modified ASA resin:

1) First, add 67% butyl acrylate, 13% deionized water, 28% sodium lauryl sulfate, 35% potassium persulfate and all sodium bicarbonate to the reactor, under nitrogen protection React at 65-80°C for 3 hours;

2) Add the remaining amount of butyl acrylate, 13% deionized water, 17% sodium lauryl sulfate, 22% potassium persulfate, 12% styrene, 6.25% Acrylonitrile and all cross-linking agents HDDA were reacted at 65-80°C for 3 hours under the protection of nitrogen;

3) Add an agglomerating agent to the reaction solution in step 2), and react at 45-65°C for 1 hour under the protection of nitrogen;

4) Add the remaining amount of styrene, the remaining amount of acrylonitrile, the remaining amount of deionized water, the remaining amount of sodium lauryl sulfate, the remaining amount of potassium persulfate and all the t Dodecyl mercaptan was reacted at 65-80°C for 5 hours under nitrogen protection to obtain ASA emulsion;

5) Add 4 times the volume of 2% sodium chloride aqueous solution to the ASA emulsion prepared in step 4), demulsify the ASA emulsion at normal temperature and pressure, filter and dry at 45°C for 24 hours to obtain modified ASA Resin powder.

After injection molding the modified ASA resin powder, the resin sample was prepared, and the tensile properties were tested according to GB/T1040.2-2006, and the impact properties were tested according to GB1843-2008.

Embodiment 6:

This example repeats Example 5, except that no agglomerating agent is added, that is, step 3 is omitted).

Embodiment 7:

Step 1) and step 2) of this embodiment are the same as in Embodiment 3.

3. Raw materials and mass parts of modified ASA resin:

Butyl acrylate: 10.0 parts,

Styrene: 23.2 parts,

Acrylonitrile: 7.2 parts,

Agglomerating agent: 6.5 parts,

Deionized water: 56.0 parts,

Potassium persulfate: 0.096 parts,

Sodium lauryl sulfate: 0.42 parts,

Sodium bicarbonate: 0.12 parts,

Cross-linking agent HDDA: 0.22 parts,

Tertiary dodecyl mercaptan: 0.048 parts.

4. Preparation of modified ASA resin:

1) First, add 67% butyl acrylate, 13% deionized water, 28% sodium lauryl sulfate, 35% potassium persulfate and all sodium bicarbonate to the reactor, under nitrogen protection React at 65-80°C for 3 hours;

2) Add the remaining amount of butyl acrylate, 13% deionized water, 17% sodium lauryl sulfate, 22% potassium persulfate, 12% styrene, 6.25% Acrylonitrile and all cross-linking agents HDDA were reacted at 65-80°C for 3 hours under the protection of nitrogen;

3) Add an agglomerating agent to the reaction solution in step 2), and react at 45-65°C for 1 hour under the protection of nitrogen;

4) Add the remaining amount of styrene, the remaining amount of acrylonitrile, the remaining amount of deionized water, the remaining amount of sodium lauryl sulfate, the remaining amount of potassium persulfate and all the t Dodecyl mercaptan was reacted at 65-80°C for 5 hours under nitrogen protection to obtain ASA emulsion;

5) Add 4 times the volume of 2% sodium chloride aqueous solution to the ASA emulsion prepared in step 4), demulsify the ASA emulsion at normal temperature and pressure, filter and dry at 45°C for 24 hours to obtain modified ASA Resin powder.

The modified ASA resin powder was injection molded to obtain a resin sample, and the tensile properties were tested according to GB/T1040.2-2006, and the impact properties were tested according to GB1843-2008.

Embodiment 8:

This example repeats Example 7, except that no agglomerating agent is added, that is, step 3 is omitted).

Embodiment 9:

Step 1 and step 2 of this embodiment are the same as embodiment 3.

3. Raw materials and mass parts of modified ASA resin:

Butyl acrylate: 9.4 parts,

Styrene: 26.5 parts,

Acrylonitrile: 7.9 parts,

Agglomerating agent latex: 8.0 parts,

Deionized water: 52.9 parts,

Potassium persulfate: 0.12 parts,

Sodium lauryl sulfate: 0.7 parts,

Sodium bicarbonate: 0.16 parts,

Cross-linking agent HDDA: 0.24 parts,

Tertiary dodecyl mercaptan: 0.08 parts.

4. Preparation of modified ASA resin:

1) First, add 67% butyl acrylate, 13% deionized water, 28% sodium lauryl sulfate, 35% potassium persulfate and all sodium bicarbonate to the reactor, under nitrogen protection React at 65-80°C for 3 hours;

2) Add the remaining amount of butyl acrylate, 13% deionized water, 17% sodium lauryl sulfate, 22% potassium persulfate, 12% styrene, 6.25% Acrylonitrile and all cross-linking agents HDDA were reacted at 65-80°C for 3 hours under the protection of nitrogen;

3) Add an agglomerating agent to the reaction solution in step 2), and react at 45-65°C for 1 hour under the protection of nitrogen;

4) Add the remaining amount of styrene, the remaining amount of acrylonitrile, the remaining amount of deionized water, the remaining amount of sodium lauryl sulfate, the remaining amount of potassium persulfate and all the t Dodecyl mercaptan was reacted at 65-80°C for 5 hours under nitrogen protection to obtain ASA emulsion;

5) Add 4 times the volume of 2% sodium chloride aqueous solution to the ASA emulsion prepared in step 4), demulsify the ASA emulsion at normal temperature and pressure, filter and dry at 45°C for 24 hours to obtain modified ASA Resin powder.

The modified ASA resin powder was injection molded to obtain a resin sample, and the tensile properties were tested according to GB/T1040.2-2006, and the impact properties were tested according to GB1843-2008.

Example 10:

This example repeats Example 9, except that no agglomerating agent is added, that is, step 3 is omitted).

Table 1 shows the particle size test results of PBA latex and ASA grafted latex prepared by conventional emulsion polymerization method and PBA latex and ASA grafted latex prepared by agglomeration latex method. It can be clearly seen from Table 1 that the particle size of PBA latex is 109% larger than the particle size of latex particles prepared by conventional emulsion polymerization after agglomeration modification by acrylate agglomerating agent latex, and after grafting, both The apparent particle size difference of the grafted ASA latex is relatively large, and the particle size of the ASA latex obtained by the modification of the agglomeration method will increase by nearly 50%.

Table 1 Agglomerated/non-agglomerated latex particle size comparison

model particle size Remark Embodiment 2-PBA latex 133nm Without agglomerating agent Example 4-ASA Latex 208nm Without agglomerating agent Embodiment 1-PBA latex 278nm Add agglomeration agent Example 3-ASA Latex 304nm Add agglomeration agent

Table 2 shows the test results of the mechanical properties of the ASA resin prepared by conventional emulsion polymerization; Table 3 shows the test results of the tensile mechanical properties of the agglomerating agent modified ASA resin of the present invention. From the results of tensile mechanical properties measured in Table 2 and Table 3, it can be known that the tensile strength of ASA resin prepared by latex agglomeration method is higher than that of ASA resin prepared by conventional emulsion polymerization method.

Table 2

table 3

Table 4 is a comparison of the notched impact strength of the ASA resin prepared by the modification of the agglomerating agent and the ASA resin prepared by the conventional emulsion polymerization method. It can be seen from Table 4 that the notched impact strength of the modified ASA resin of the present invention is significantly higher than that of the ASA resin prepared by the conventional emulsion polymerization method, and the notched impact strength can be increased by 42.5% after being modified by the agglomerating agent.

Table 4 Comparison of notched impact strength of agglomerated/unagglomerated ASA resin

model angle ( ^o ) Absorption work (J) Toughness (KJ/m ² ) Embodiment 4-ASA resin -150.12 0.120 3.764 Embodiment 6-ASA resin -150.03 0.207 6.483 Embodiment 8-ASA resin -150.12 0.246 7.709 Without agglomerating agent - average -150.09 0.191 5.985 Embodiment 3-ASA resin -150.12 0.426 6.293 Embodiment 5-ASA resin -150.12 0.201 9.379 Embodiment 7-ASA resin -150.12 0.272 13.317 Add agglomerating agent - average -150.12 0.300 8.526

Table 5 is a comparison of the impact strength of the modified ASA resin of the present invention and the ASA resin prepared by conventional emulsion polymerization. From the measured results in Table 5, it can be seen that the impact strength of the modified ASA resin of the present invention is significantly higher than that of the ASA resin prepared by conventional emulsion polymerization, and the non-notched impact strength can be increased by 81.7% after agglomeration modification.

Table 5 Comparison of impact strength of agglomerated/unagglomerated ASA resin

model angle ( ^o ) Absorption work (J) Toughness (KJ/m ² ) Embodiment 4-ASA resin -150. 03 1.991 49.775 Embodiment 6-ASA resin -150.03 0.877 21.925 Embodiment 8-ASA resin -150.12 1.317 32.925 Without agglomerating agent - average -150.06 1.395 34.875 Embodiment 3-ASA resin -150. 21 1.731 41.730 Embodiment 5-ASA resin -150.12 3.066 76.650 Embodiment 7-ASA resin -150.03 2.867 71.675 Add agglomerating agent - average -150.12 2.555 63.352

Claims (2)

1. a method for acrylic acid esters agglomerating agent modified ASA resin, is characterized in that each raw material constitutes by mass parts: 6-10 parts of butyl acrylate, 20-27 parts of styrene, 7-8 parts of acrylonitrile, 2.0-8.0 parts of acrylate agglomerating agent, 50.0-60.0 parts of deionized water, 0.08-0.12 parts of potassium persulfate, ten 0.2-0.7 parts of sodium dialkyl sulfate, 0.08-0.16 parts of sodium bicarbonate, 0.20-0.40 parts of crosslinking agent, 0.02-0.08 parts of tertiary dodecyl mercaptan; The crosslinking agent is selected from tripropylene glycol diacrylate or 1,6-hexanediol diacrylate; The operation steps of acrylate agglomerating agent modified ASA resin are as follows: 1) First add 60-70% butyl acrylate, 10-20% deionized water, 25-35% sodium lauryl sulfate, 30-40% potassium persulfate and sodium bicarbonate to the reactor , reacted at 65-80°C for 3 hours under nitrogen protection; 2) Add the remaining amount of butyl acrylate, 10-20% deionized water, 15-25% sodium lauryl sulfate, 20-25% potassium persulfate, 10-15% % of styrene, 6-7% of acrylonitrile and cross-linking agent, reacted at 65-80°C for 3 hours under the protection of nitrogen; 3) adding an acrylate agglomerating agent to the reaction liquid in step 2), and reacting at 45-65° C. for 1 hour under the protection of nitrogen; 4) In the reaction solution of step 3), add the styrene of surplus, the acrylonitrile of surplus, the deionized water of surplus, the sodium lauryl sulfate of surplus, the potassium persulfate of surplus and all the tertiary Dodecyl mercaptan, reacted at 65-80°C for 5 hours under the protection of nitrogen, filtered and dried after demulsification to obtain acrylate agglomerating agent modified ASA resin; The raw material of described acrylate agglomerating agent constitutes by mass parts: 12-14 parts of acrylate, 3-4 parts of unsaturated acid, 0.5-0.7 parts of compound emulsifier, 80-85 parts of deionized water, 0.05-0.15 parts of initiator; The unsaturated acid is acrylic acid; The compounded emulsifier is obtained by compounding an anionic emulsifier and a nonionic emulsifier at a mass ratio of 1:1; The initiator is a water-soluble initiator; The synthetic method of described acrylate agglomerating agent is: Mix acrylate, unsaturated acid, compound emulsifier and deionized water according to the ratio, stir and emulsify, heat up to 70°C after emulsification, add initiator, keep warm for 3 hours to obtain a milky white emulsion, which is the acrylic agglomerating agent . 2. method according to claim 1, is characterized in that each raw material constitutes by mass parts: 6-10 parts of butyl acrylate, 21.32-26.5 parts of styrene, 7.2-7.9 parts of acrylonitrile, 2.72-8.0 parts of acrylate agglomerating agent, 52.9-60.0 parts of deionized water, 0.096-0.12 parts of potassium persulfate, ten 0.31-0.7 parts of sodium dialkyl sulfate, 0.09-0.16 parts of sodium bicarbonate, 0.22-0.32 parts of crosslinking agent, and 0.032-0.08 parts of tertiary dodecyl mercaptan.