Preparation method of MBS resin

Abstract

The invention belongs to the technical field of high polymer material synthesis and preparation, and particularly relates to a preparation method of MBS (methyl methacrylate-butadiene-styrene) resin, which comprises the following steps: by taking styrene, acrylate monomers and toughened rubber particles as raw materials, under the combined action of an antioxidant, an initiator and a chain transfer agent, optimizing the technical process and adjusting the technical parameters, thereby obtaining the MBS resin. Three-stage key process steps of internal circulation prepolymerization, polymerization in a second-stage reactor and grafting in a static mixer are set, and the feeding proportion of reaction materials, catalytic materials and the like, and the reaction temperature, the stirring speed, the retention time, the solid content proportion and the like of each process step are accurately controlled. The prepared MBS resin is pure, low in odor, uniform in rubber particle distribution, adjustable in rubber content, high in grafting rate, good in transparency, low in haze and good in impact resistance. Compared with a traditional emulsion polymerization method, the preparation method has the advantages that the technological process is shortened, the operation stability is good, the investment and production cost is reduced, the environmental pollution is reduced, and the preparation method has good market prospects and application and popularization values.

Description

Technical Field

[0001] The invention belongs to the field of polymer material synthesis and preparation technology, and specifically relates to a preparation method of MBS resin. Background Art

[0002] MBS resin is a terpolymer obtained by copolymerizing acrylate monomers (usually methyl methacrylate, MMA), butadiene (BD), and styrene monomers (usually styrene, St). MBS resin has good high impact resistance, transparency, surface finish and easy processing properties, and is mostly used as a modifier for plastics such as PVC.

[0003] There are two production methods for MBS resin: emulsion polymerization and suspension polymerization. The production is mainly based on emulsion polymerization. The basic process of preparing MBS by emulsion polymerization is: butadiene and styrene are emulsified in water and emulsifier as monomers, polymerized under the initiation of initiator to prepare styrene-butadiene latex (SBR latex), and then styrene and methyl methacrylate are added for emulsion graft polymerization to obtain MBS resin grafted latex, and finally MBS powder is obtained after condensation, dehydration and drying. In the entire production process of MBS resin, the synthesis technology of SBR latex, the synthesis technology of MBS resin latex and the condensation technology of MBS resin latex are the three key technologies and difficulties in MBS production. Problems of emulsion polymerization: ① The molecular weight distribution of the rubber particles of the prepared MBS resin is wide and the dispersibility is poor; ② The product is not pure enough, with high yellowness and high haze; ③ The emulsion polymerization process is long, the energy consumption is large, and the production cost is high; ④ There are many types of additives and the environmental pollution is large. Therefore, in order to solve the problems existing in the MBS production process system in the prior art, such as long process flow, high energy consumption, high production cost and environmental pollution, wide molecular weight distribution of rubber particles of the prepared MBS resin, poor dispersibility, and impure products, it is urgent to develop a preparation method of MBS resin. Summary of the invention

[0004] In order to solve the problems of the MBS production process system in the prior art, such as long process flow, high energy consumption, high production cost, environmental pollution, wide molecular weight distribution of rubber particles of the prepared MBS resin, poor dispersibility, impure products, etc., the present invention proposes a continuous bulk preparation method of MBS resin. The preparation method of the present invention is green and pollution-free, has a simple process flow, low energy consumption, can effectively reduce production costs, and the obtained MBS resin product is pure, has high transparency, low haze, and good impact resistance.

[0005] A method for preparing MBS resin comprises the following steps:

[0006] S1. Preparation of reaction materials: prepare a mixed solution of styrene, acrylate monomer, toughening rubber, solvent and antioxidant in proportion, stir thoroughly to ensure that the toughening rubber particles are completely dissolved, and add initiator and chain transfer agent to the mixed solution; place the mixed materials in a three-stage static mixer in turn for prepolymerization, the reaction temperature is between 100-110° C., the stirring speed is 10-25 r / min, the prepolymerization residence time is 0.5-1.5 hours, and the solid content at the outlet is controlled at 12-15%;

[0007] S2, pumping the material after the prepolymerization reaction in step S1 into a primary plug flow reactor, controlling the reaction temperature to 100-110°C, the stirring speed to 15-30r / min, the residence time to 0.5-2.0 hours, and the solid content of the material at the outlet to 40%-45%;

[0008] S3, the material is pumped from the primary plug flow reactor to the secondary plug flow reactor, the reaction temperature is controlled at 110-120°C, the stirring speed is 5-12r / min; the material residence time is 1.5-2.5 hours, and the solid content of the material at the outlet is 55%-60%;

[0009] S4. The material is pumped from the secondary plug flow reactor to the static mixing reactor, and the temperature of the upper and middle zones of the static mixing reactor is controlled to be 90-100°C, and the reaction temperature of the lower zone is controlled to be 120-130°C; the material residence time is 1.0-2.0 hours, and the solid content of the material at the outlet is 80%-85%; after the material reaches the conversion rate, it is post-processed and granulated to obtain high-performance MBS resin.

[0010] Furthermore, the toughening rubber is selected from at least one of styrene-butadiene copolymer rubber, styrene-isoprene-butadiene ternary integrated rubber, amine functionalized styrene-butadiene copolymer rubber, and amine functionalized styrene-isoprene-butadiene copolymer integrated rubber; preferably styrene-butadiene copolymer rubber.

[0011] Furthermore, the solvent is selected from toluene or ethylbenzene.

[0012] Furthermore, the initiator is not particularly limited and can be used alone or in combination. The initiator is selected from one or more of 2,2'-azobisisobutyronitrile, dilauroyl peroxide, and dibenzoyl peroxide.

[0013] Furthermore, the chain transfer agent is selected from chain transfer agents commonly used in free radical polymerization, including but not limited to at least one of n-butyl mercaptan, isobutyl mercaptan, n-dodecyl mercaptan, and tert-dodecyl mercaptan, preferably n-dodecyl mercaptan.

[0014] The antioxidant is not particularly limited and can be used alone or in combination, and is preferably 1-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0015] Furthermore, in terms of mass fraction, the toughening rubber accounts for 10%-30% of the total amount of the mixed glue including styrene, acrylate monomers, initiators, chain transfer agents and solvents, the amount of styrene accounts for 30%-50% of the total amount of the mixed glue, the amount of solvent accounts for 10%-20% of the total amount of the mixed glue, the acrylate monomers account for 20%-30% of the total amount of the mixed glue, the amount of initiator is 0.05-0.2% of the total mass of the monomers; the amount of chain transfer agent is 0.10%-0.40% of the sum of the mass of the acrylate monomers and styrene; the amount of antioxidant is 0.10%-0.30% of the total mass of the acrylate monomers and styrene.

[0016] Furthermore, the acrylic acid ester monomer used for polymerization is selected from methyl methacrylate, ethyl methacrylate, and butyl methacrylate, preferably methyl methacrylate.

[0017] Furthermore, in the step S1, before the mixed materials are sequentially placed in the three-stage static mixer for prepolymerization, they are first filtered through a filter to remove undissolved rubber particles.

[0018] Furthermore, the post-treatment method in step S4 is that after the material reaches the conversion rate, a secondary deashing treatment is first performed, and the volatile matter content at the outlet is controlled to be less than 300 ppm or below.

[0019] Beneficial effects:

[0020] The present invention adopts a continuous bulk method to prepare MBS resin. Compared with the traditional emulsion polymerization method, the process flow is shortened, the operation stability is good, the investment and production costs are reduced, and environmental protection is taken into consideration, so that the MBS resin product prepared by the present invention is pure, has low product odor, high grafting rate, good transparency, low haze, and good impact resistance. DETAILED DESCRIPTION

[0021] In order to more clearly understand the above-mentioned objectives, features and advantages of the present invention, the scheme of the present invention will be further described below. It should be noted that the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

[0022] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein; it is obvious that the embodiments in the specification are only part of the embodiments of the present invention, rather than all of the embodiments.

[0023] The preferred embodiments of the present invention will be described in detail below in conjunction with examples. It should be understood that the following examples are provided only for the purpose of illustration and are not intended to limit the scope of the present invention. Those skilled in the art may make various modifications and substitutions to the present invention without departing from the purpose and spirit of the present invention.

[0024] Test instrument model:

[0025] The rubber content was measured by nuclear magnetic resonance spectroscopy (NMR);

[0026] The grafting rate was measured by differential weight method: about 0.15g MBS sample (W 样 ) was dissolved in 30 mL of acetone solvent, refluxed for 8 h, centrifuged at 6000 rpm on an ultracentrifuge for 30 min, the supernatant was transferred to a watch glass, condensed with ethanol, and reserved for molecular weight and distribution measurement. The lower precipitate was repeatedly washed with solvent, and this was repeated, centrifuged 3 times, and dried at 50 ° C under vacuum to constant weight (W 沉淀 ).

[0027] Grafting rate = (W 沉淀 -W 橡胶 ) / W 橡胶 ×100%

[0028] Transparency and haze were measured using a photometric haze meter;

[0029] Impact resistance is measured using an impact tester.

[0030] Example 1

[0031] S1. Preparation of reaction materials: prepare a mixed solution of styrene, methyl methacrylate, toughened rubber, ethylbenzene and antioxidant in proportion, stir thoroughly to ensure that the toughened rubber particles are completely dissolved, and add an initiator and a chain transfer agent to the mixed solution; place the reaction materials in a three-stage static mixer in sequence for prepolymerization, with a reaction temperature of 100° C., a stirring speed of 25 r / min, a prepolymerization residence time of 1.5 hours, and a solid content at the outlet controlled at 12%-15%;

[0032] S2, pump the prepolymerized material from the inner circulation reactor into the primary plug flow reactor, control the reaction temperature at 100°C, the stirring speed at 30r / min, the residence time at 2 hours, and the solid content of the material at the outlet at 40%-45%;

[0033] S3, the material is pumped from the primary plug flow reactor to the secondary plug flow reactor, the reaction temperature is controlled at 110°C, the stirring speed is 12r / min; the material residence time is 2.0 hours, and the solid content of the material at the outlet is 55%-60%;

[0034] S4, the material is pumped from the secondary plug flow reactor to the static mixing reactor, the temperature of the upper and middle zones of the static mixing reactor is controlled to be 90°C, and the reaction temperature of the lower zone is controlled to be 130°C; the material residence time is 2.0 hours, and the solid content of the material at the outlet is 80%-85%; after the material reaches the conversion rate, it is subjected to secondary deashing treatment, and the volatile content at the outlet is controlled to be less than 300ppm, and granulation is performed to obtain the MBS resin product.

[0035] The toughening rubber is selected from styrene-butadiene copolymer rubber; the initiator is 2,2'-azobisisobutyronitrile; the chain transfer agent is n-butyl mercaptan; and the antioxidant is selected from 1-octadecyl-3-(3.5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0036] The toughened rubber accounts for 20% of the weight ratio of the mixed glue liquid including styrene, methyl methacrylate, initiator, chain transfer agent and solvent, styrene accounts for 40% of the total amount of the glue liquid, the solvent accounts for 15% of the total amount of the glue liquid, and methyl methacrylate accounts for 25% of the total amount of the glue liquid; the amount of initiator used is 0.1% of the total weight of the monomers; the amount of chain transfer agent used is 0.1% of the sum of the weights of methyl methacrylate, styrene and acrylonitrile; the amount of antioxidant used is 0.3% of the total weight of methyl methacrylate and styrene.

[0037] The prepared MBS resin product is pure and has low odor; the rubber grafting rate is 244%, the light transmittance is 91%, the haze is 7%, and the cantilever beam impact strength is 158 J / m.

[0038] Example 2

[0039] S1. Preparation of reaction materials: prepare a mixed solution of styrene, methyl methacrylate, toughened rubber, ethylbenzene and antioxidant in proportion, stir thoroughly to ensure that the toughened rubber particles are completely dissolved, and add an initiator and a chain transfer agent to the mixed solution; place the reaction materials in a three-stage static mixer in sequence for prepolymerization, with a reaction temperature of 110° C., a stirring speed of 20 r / min, a prepolymerization residence time of 0.5 hour, and a solid content at the outlet controlled at 12%-15%;

[0040] S2, pump the prepolymerized material in the inner circulation reactor to the primary plug flow reactor, control the reaction temperature to 110°C, the stirring speed to 15r / min, the residence time to 0.5 hours, and the solid content of the material at the outlet to 40%-45%;

[0041] S3, the material is pumped from the primary plug flow reactor to the secondary plug flow reactor, the reaction temperature is controlled at 120°C, the stirring speed is 5r / min; the material residence time is 1.5 hours, and the solid content of the material at the outlet is 55%-60%;

[0042] S4, the material is pumped from the secondary plug flow reactor to the static mixing reactor, the temperature of the upper and middle zones of the static mixing reactor is controlled to be 100°C, and the reaction temperature of the lower zone is controlled to be 120°C; the material residence time is 1.0 hour, and the solid content of the material at the outlet is 80%-85%; after the material reaches the conversion rate, it is subjected to secondary deashing treatment, and the volatile content at the outlet is controlled to be less than 300ppm, and granulation is performed to obtain the MBS resin product.

[0043] The toughening rubber is selected from styrene-isoprene-butadiene ternary integrated rubber; the initiator is dilauroyl peroxide; the chain transfer agent is isobutyl mercaptan, and the antioxidant is selected from 1-octadecyl-3-(3.5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0044] The toughened rubber accounts for 10% of the weight ratio of the mixed glue liquid including styrene, methyl methacrylate, initiator, chain transfer agent and solvent, styrene accounts for 50% of the total amount of the glue liquid, the solvent accounts for 10% of the total amount of the glue liquid, and methyl methacrylate accounts for 30% of the total amount of the glue liquid; the amount of initiator used is 0.2% of the total weight of the monomers; the amount of chain transfer agent used is 0.4% of the sum of the weights of methyl methacrylate, styrene and acrylonitrile; the amount of antioxidant used is 0.2% of the total weight of methyl methacrylate and styrene.

[0045] The prepared MBS resin product is pure and has low odor; wherein, the rubber grafting rate is 230%, the light transmittance is 90%, the haze is 8%, and the cantilever beam impact strength is 124 J / m.

[0046] Example 3

[0047] S1. Preparation of reaction materials: prepare a mixed solution of styrene, methyl methacrylate, toughened rubber, toluene and antioxidant in proportion, stir thoroughly to ensure that the toughened rubber particles are completely dissolved, and add an initiator and a chain transfer agent to the mixed solution; place the reaction materials in a three-stage static mixer in sequence for prepolymerization, with a reaction temperature of 100° C., a stirring speed of 25 r / min, a prepolymerization residence time of 1.0 hour, and a solid content at the outlet controlled at 12%-15%;

[0048] S2, pump the prepolymerized material from the inner circulation reactor into the primary plug flow reactor, control the reaction temperature at 100°C, the stirring speed at 30r / min, the residence time at 1.5 hours, and the solid content of the material at the outlet at 40%-45%;

[0049] S3, the material is pumped from the primary plug flow reactor to the secondary plug flow reactor, the reaction temperature is controlled at 110°C, the stirring speed is 12r / min; the material residence time is 2.0 hours, and the solid content of the material at the outlet is 55%-60%;

[0050] S4, the material is pumped from the secondary plug flow reactor to the static mixing reactor, the temperature of the upper and middle zones of the static mixing reactor is controlled to be 90°C, and the reaction temperature of the lower zone is controlled to be 130°C; the material residence time is 2.0 hours, and the solid content of the material at the outlet is 80%-85%; after the material reaches the conversion rate, it is subjected to secondary deashing treatment, and the volatile content at the outlet is controlled to be less than 300ppm, and granulation is performed to obtain the MBS resin product.

[0051] The toughening rubber is selected from styrene-isoprene-butadiene ternary integrated rubber; the initiator is dibenzoyl peroxide; the chain transfer agent is n-dodecyl mercaptan, and the antioxidant is selected from 1-octadecyl-3-(3.5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0052] The toughened rubber accounts for 30% of the weight ratio of the mixed glue liquid including styrene, methyl methacrylate, initiator, chain transfer agent and solvent, styrene accounts for 30% of the total amount of the glue liquid, the solvent accounts for 20% of the total amount of the glue liquid, and methyl methacrylate accounts for 20% of the total amount of the glue liquid; the amount of initiator used is 0.05% of the total weight of the monomers; the amount of chain transfer agent used is 0.3% of the sum of the weights of methyl methacrylate, styrene and acrylonitrile; the amount of antioxidant used is 0.1% of the total weight of methyl methacrylate and styrene.

[0053] The prepared MBS resin product is pure and has low odor; the rubber grafting rate is 230%, the light transmittance is 88%, the haze is 8%, and the cantilever beam impact strength is 197 J / m.

[0054] Example 4

[0055] S1. Preparation of reaction materials: prepare a mixed solution of styrene, methyl methacrylate, toughened rubber, ethylbenzene and antioxidant in proportion, stir thoroughly to ensure that the toughened rubber particles are completely dissolved, and add an initiator and a chain transfer agent to the mixed solution; place the reaction materials in a three-stage static mixer in sequence for prepolymerization, with a reaction temperature of 100° C., a stirring speed of 25 r / min, a prepolymerization residence time of 1.0 hour, and a solid content at the outlet controlled at 12%-15%;

[0056] S2, pump the prepolymerized material from the inner circulation reactor into the primary plug flow reactor, control the reaction temperature at 100°C, the stirring speed at 30r / min, the residence time at 1.5 hours, and the solid content of the material at the outlet at 40%-45%;

[0057] S3, the material is pumped from the primary plug flow reactor to the secondary plug flow reactor, the reaction temperature is controlled at 110°C, the stirring speed is 12r / min; the material residence time is 2.0 hours, and the solid content of the material at the outlet is 55%-60%;

[0058] S4, the material is pumped from the secondary plug flow reactor to a static mixing reactor, the temperature of the upper and middle zones of the static mixing reactor is controlled to be 90°C, and the reaction temperature of the lower zone is controlled to be 120°C; the material residence time is 2.0 hours, and the solid content of the material at the outlet is 80%-85%; after the material reaches the conversion rate, it is subjected to secondary deashing treatment, and the volatile matter content at the outlet is controlled to be less than 300ppm, and granulation is performed to obtain the MBS resin product.

[0059] The toughening rubber is selected from terminal amine functionalized styrene-butadiene copolymer rubber; the initiator is dibenzoyl peroxide; the chain transfer agent is n-dodecyl mercaptan, and the antioxidant is selected from 1-octadecyl-3-(3.5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0060] The toughened rubber accounts for 30% of the weight ratio of the mixed glue liquid including styrene, methyl methacrylate, initiator, chain transfer agent and solvent, styrene accounts for 30% of the total amount of the glue liquid, the solvent accounts for 20% of the total amount of the glue liquid, and methyl methacrylate accounts for 20% of the total amount of the glue liquid; the amount of initiator used is 0.1% of the total weight of the monomers; the amount of chain transfer agent used is 0.3% of the sum of the weights of methyl methacrylate, styrene and acrylonitrile; the amount of antioxidant used is 0.1% of the total weight of methyl methacrylate and styrene.

[0061] The prepared MBS resin product is pure and has low odor; the rubber grafting rate is 230%, the light transmittance is 86%, the haze is 10%, and the cantilever beam impact strength is 193 J / m.

[0062] Comparative Example 1

[0063] S1. Preparation of reaction materials: prepare a mixed solution of styrene, methyl methacrylate, toughened rubber, ethylbenzene and antioxidant in proportion, stir thoroughly to ensure that the toughened rubber particles are completely dissolved, and add an initiator and a chain transfer agent to the mixed solution; place the reaction materials in a three-stage static mixer in sequence for prepolymerization, with a reaction temperature of 100° C., a stirring speed of 25 r / min, a prepolymerization residence time of 1.5 hours, and a solid content at the outlet controlled at 12%-15%;

[0064] S2, pump the prepolymerized material from the inner circulation reactor into the primary plug flow reactor, control the reaction temperature at 100°C, the stirring speed at 30r / min, the residence time at 2 hours, and the solid content of the material at the outlet at 40%-45%;

[0065] S3, the material is pumped from the primary plug flow reactor to the secondary plug flow reactor, the reaction temperature is controlled at 110°C, the stirring speed is 12r / min; the material residence time is 2.0 hours, and the solid content of the material at the outlet is 55%-60%;

[0066] S4, the material is pumped from the secondary plug flow reactor to the static mixing reactor, the temperature of the upper and middle zones of the static mixing reactor is controlled to be 90°C, and the reaction temperature of the lower zone is controlled to be 130°C; the material residence time is 2.0 hours, and the solid content of the material at the outlet is 80%-85%; after the material reaches the conversion rate, it is subjected to secondary deashing treatment, and the volatile content at the outlet is controlled to be less than 300ppm, and granulation is performed to obtain the MBS resin product.

[0067] The toughening rubber is selected from styrene-butadiene copolymer rubber; the initiator is 2,2'-azobisisobutyronitrile; the chain transfer agent is n-butyl mercaptan; and the antioxidant is selected from 1-octadecyl-3-(3.5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0068] The toughened rubber accounts for 7% of the weight ratio of the mixed glue liquid including styrene, methyl methacrylate, initiator, chain transfer agent and solvent, styrene accounts for 52% of the total amount of the glue liquid, the solvent accounts for 15% of the total amount of the glue liquid, and methyl methacrylate accounts for 25% of the total amount of the glue liquid; the initiator amount is 0.3% of the total weight of the monomers; the chain transfer agent amount is 0.1% of the sum of the weights of methyl methacrylate, styrene and acrylonitrile; and the antioxidant amount is 0.3% of the total weight of methyl methacrylate and styrene.

[0069] The prepared MBS resin product is pure and has low odor; the rubber grafting rate is 214%, the light transmittance is 85%, the haze is 7%, and the cantilever beam impact strength is 58 J / m.

[0070] Comparative Example 2

[0071] S1. Preparation of reaction materials: prepare a mixed solution of styrene, methyl methacrylate, toughened rubber, ethylbenzene and antioxidant in proportion, stir thoroughly to ensure that the toughened rubber particles are completely dissolved, and add an initiator and a chain transfer agent to the mixed solution; place the reaction materials in a three-stage static mixer in sequence for prepolymerization, with a reaction temperature of 100° C., a stirring speed of 25 r / min, a prepolymerization residence time of 1.0 hour, and a solid content at the outlet controlled at 12%-15%;

[0072] S2, pump the prepolymerized material in the inner circulation reactor to the primary plug flow reactor, control the reaction temperature to 110°C, the stirring speed to 30r / min; the residence time to 1.5 hours, and the solid content of the material at the outlet to 40%-45%;

[0073] S3, the material is pumped from the primary plug flow reactor to the secondary plug flow reactor, the reaction temperature is controlled at 120°C, the stirring speed is 12r / min; the material residence time is 2.0 hours, and the solid content of the material at the outlet is 55%-60%;

[0074] S4, the material is pumped from the secondary plug flow reactor to the static mixing reactor, the temperature of the upper and middle zones of the static mixing reactor is controlled to be 90°C, and the reaction temperature of the lower zone is controlled to be 140°C; the material residence time is 2.0 hours, and the solid content of the material at the outlet is 80%-85%; after the material reaches the conversion rate, it is subjected to secondary deashing treatment, and the volatile content at the outlet is controlled to be less than 300ppm, and granulation is performed to obtain the MBS resin product.

[0075] The toughening rubber is selected from terminal siloxy styrene-isoprene-butadiene ternary integrated rubber; the initiator is dilauroyl peroxide; the chain transfer agent is isobutyl mercaptan, and the antioxidant is selected from 1-octadecyl-3-(3.5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0076] The toughened rubber accounts for 10% of the weight ratio of the mixed glue liquid including styrene, methyl methacrylate, initiator, chain transfer agent and solvent, styrene accounts for 50% of the total amount of the glue liquid, the solvent accounts for 10% of the total amount of the glue liquid, and methyl methacrylate accounts for 30% of the total amount of the glue liquid; the amount of initiator is 0.1% of the total weight of the monomers; the amount of chain transfer agent is 0.1% of the sum of the weights of methyl methacrylate, styrene and acrylonitrile; the amount of antioxidant is 0.3% of the total weight of methyl methacrylate and styrene.

[0077] The prepared MBS resin product is pure and has low odor; the rubber grafting rate is 219%, the light transmittance is 80%, the haze is 15%, and the cantilever beam impact strength is 127 J / m.

[0078] The above are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereto. Any equivalent structure or equivalent process transformation made by using the specification of the present invention, or directly or indirectly applied in other related technical fields, are also included in the protection scope of the present invention.

Claims

1. A method for preparing MBS resin, characterized in that: The following steps are involved: S1. Preparation of reaction materials: prepare a mixed solution of styrene, acrylate monomer, toughened rubber particles and antioxidant in proportion, stir thoroughly to ensure that the toughened rubber particles are completely dissolved, and add an initiator and a chain transfer agent to the mixed solution; place the mixed materials in a three-stage static mixer in turn for prepolymerization, with a reaction temperature between 100-110° C., a stirring speed of 10-25 r / min, a prepolymerization residence time of 0.5-1.5 hours, and a solid content at the outlet controlled at 12-15%; S2, pumping the material after the prepolymerization reaction in step S1 into a primary plug flow reactor, controlling the reaction temperature to 100-110°C, the stirring speed to 15-30r / min, the residence time to 0.5-2.0 hours, and the solid content of the material at the outlet to 40%-45%; S3, pumping the material after the reaction in the first plug flow reactor into the second plug flow reactor, controlling the reaction temperature to 110-120°C, the stirring speed to 5-12r / min; the material residence time to 1.5-2.5 hours, and the solid content of the material at the outlet to 55%-60%; S4, pumping the material after the reaction in the secondary plug flow reactor to the static mixing reactor, controlling the temperature of the upper and middle zones of the static mixing reactor to 90-100°C, and the reaction temperature of the lower zone to 120-130°C; the material residence time is 1.0-2.0 hours, and the solid content of the material at the outlet is 80%-85%; after the material reaches the conversion rate, it is post-processed and granulated to obtain the MBS resin.

2. The preparation method according to claim 1, characterized in that: The toughening rubber is selected from at least one of styrene-butadiene binary copolymer rubber, styrene-isoprene-butadiene ternary integrated rubber, amine functionalized styrene-butadiene copolymer rubber, and amine functionalized styrene-isoprene-butadiene copolymer integrated rubber.

3. The preparation method according to claim 1, characterized in that: The acrylic acid ester monomer is selected from methyl methacrylate, ethyl methacrylate and butyl methacrylate.

4. The preparation method according to any one of claims 1 to 3, characterized in that: In terms of mass fraction, the toughened rubber particles account for 10%-30% of the total amount of the mixed glue including styrene, acrylate monomers, initiators, chain transfer agents and solvents, the amount of styrene accounts for 30%-50% of the total amount of the mixed glue, the amount of solvent accounts for 10%-20% of the total amount of the mixed glue, the amount of acrylate monomers accounts for 20%-30% of the total amount of the mixed glue, the amount of initiator is 0.05%-0.2% of the total mass of the monomers; the amount of chain transfer agent is 0.10%-0.40% of the total mass of the acrylate monomers and styrene; the amount of antioxidant is 0.10%-0.30% of the total mass of the acrylate monomers and styrene.

5. The preparation method according to claim 4, characterized in that: The initiator is selected from at least one of 2,2'-azobisisobutyronitrile, dilauroyl peroxide and dibenzoyl peroxide.

6. The preparation method according to claim 4, characterized in that: The chain transfer agent is selected from at least one of n-butyl mercaptan, isobutyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan.

7. The preparation method according to claim 4, characterized in that: The antioxidant is selected from 1-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

8. The preparation method according to claim 4, characterized in that: In the step S1, before the mixed materials are sequentially placed in the three-stage static mixer for prepolymerization, they are first filtered through a filter to remove undissolved rubber particles.

9. The preparation method according to claim 4, characterized in that: The post-treatment method in step S4 is that after the material reaches the conversion rate, it is first subjected to secondary deashing treatment, and the volatile matter content at the outlet is controlled to be less than 300 ppm or below.

10. The preparation method according to claim 4, characterized in that: The solvent is toluene or ethylbenzene.