JPH0328211A - Continuous production of rubber-modified high impact resin - Google Patents

Abstract

PURPOSE:To prepare a rubber-modified high impact resin contg. rubber particles having a desired particle diameter by polymerizing a raw material soln. comprising a mixture of an arom. vinyl monomer with a vinyl cyanide monomer and a rubbery polymer dissolved therein while passing the soln. through the first reactor, a particle-dispersing machine, and the second reactor in this order. CONSTITUTION:A raw material soln. comprising a mixture of an arom. vinyl monomer with a vinyl cyanide monomer and a rubbery polymer dissolved therein is fed continuously with a radical polymn. initiator to the first reactor, wherein the monomer mixture is copolymerized to a conversion needed to cause the dissolved rubbery polymer to change into dispersed particles. The reacted soln. is fed to a particle-dispersing machine which has at least three fast-rotating blades or rotors within it and in which the dispersed particles are treated with shear. The treated soln. is then fed continuously to the second reactor and then, if necessary, to the third and subsequent reactors to continue the polymn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for continuously producing rubber-modified impact-resistant resin. More specifically, a raw material solution in which a rubbery polymer is dissolved in a mixture of an aromatic vinyl monomer and a vinyl cyanide monomer is continuously subjected to bulk or solution polymerization to form a rubbery polymer with a desired particle size. This article relates to a method for producing a rubber-modified impact-resistant resin that has excellent chemical resistance, heat resistance, and rigidity, and has a good appearance by forming dispersed particles. [Prior art] High impact polystyrene resin (hereinafter abbreviated as HIPS resin) is a resin with improved impact resistance of polystyrene resin obtained by polymerizing styrene in the presence of rubber components, and is used in a wide range of fields. It has been done. This HI-PS resin is a block-? It is also produced by batch polymerization such as the A turbidity method, but as a recent trend, it is often produced by continuous bulk polymerization. On the other hand, ABS resin obtained by polymerizing styrene and acrylonitrile in the presence of rubber compounds has many uses due to its excellent impact resistance, chemical resistance, heat resistance, rigidity, and good surface gloss. ing. This ABS resin is generally manufactured by the so-called emulsion polymerization method, in which styrene and acrylonitrile monomers are added to latex containing rubber components and polymerized. In the emulsion polymerization method, the amount of latex that is several times the amount of polymer is used, so the polymerization equipment becomes large and various processes such as emulsification, coagulation, and drying are required, making process control complicated. Because additives such as emulsifiers and coagulants are used, there are problems such as impurities being mixed into the polymer. As a method for improving the emulsion polymerization method, as in Japanese Patent Publication No. 49-35354 and 35355,
A method has been proposed in which the rubber components in rubber latex are directly extracted with styrene and acrylonitrile monomers, and then transferred to continuous bulk polymerization to produce ABS taku resin. Although this method is simpler than the usual emulsion polymerization method, it still requires a complicated extraction step. Continuous bulk or solution polymerization methods have been proposed as other methods for producing ABS. This includes, for example,
20303, JP-A-47-9144, JP-A-55-3
There are methods such as 6201, which have advantages such as simple polymerization and post-treatment steps and fewer waste materials that cause pollution, but these methods do not necessarily produce resins with excellent physical properties. In particular, there were problems such as poor surface gloss, which is one of the characteristics of ABS resin, and the need for special equipment. When manufacturing ABS resin using continuous bulk or solution polymerization methods, the size of the rubbery polymer particles in the product is determined by impact strength,
Adjusting the particle size plays an extremely important role, as it has a significant impact on performance such as gloss. As an operation for converting a phase containing a rubbery polymer (rubber phase) into dispersed particles, a method of applying strong stirring at a stage when the conversion rate of monomers to polymer is relatively low is known. The present inventors have proposed a method using a stirred tank reactor in such a process as described in Japanese Patent Publication No. 63-22.
This is proposed in No. 84. In addition, a method for obtaining rubber particles of a desired particle size by shearing the produced rubber particles using a dispersing machine is also disclosed in Japanese Patent Publication No. 49-1.
8477. In this method, rubber particles are sheared using a dispersing machine, and then a crosslinking agent is added to simultaneously complete crosslinking and polymerization of the rubber at 150 to 200°C. [Problems to be solved by the invention] However, in recent years, in order to meet the market's demand for high-performance products and the growing trend towards low-cost production through more efficient manufacturing methods, as the use of ABS resin has expanded, continuous manufacturing has been developed. Regarding the dispersion of rubbery polymers into particles in the process, the following problems are required to be solved. (1) A single production device can freely produce brands with different average particle diameters, rubber contents, and/or rubber class Il depending on the balance of market-required performance such as impact resistance and surface gloss of imposing objects. What you can do. For example, the method of Japanese Patent Publication No. 63-2284 is a simple method, but it needs to be improved in that it requires a large amount of stirring power to reduce the particle size to 0.6μ or less. (2) Generation of giant particles (observed as fin shears or poor appearance of molded products) during the particleization process to improve impact properties, gloss performance, and other appearance performance of imposing objects. To prevent The purpose of the present invention is to meet the above-mentioned requirements and to produce rubber particles of a desired particle size in an extremely efficient manner without requiring a large amount of stirring power or complicated operations in order to control the particle size. The object of this invention is to provide a method for producing a rubber-modified impact-resistant resin with a good appearance. [Means for Solving the Problems] That is, the present invention provides a raw material solution in which a rubbery polymer is dissolved in a mixture of an aromatic vinyl monomer and a vinyl cyanide monomer and a radical polymerization initiator in a first reaction tank. to polymerize monomer at a monomer conversion rate higher than that required for converting the rubber-like polymer into dispersed particles, and the amount corresponds to the amount of raw material solution supplied from the first reaction tank. An amount of the reaction solution is continuously taken out, and the reaction solution is sent to a particle dispersion machine having at least three or more blades or rotors that rotate at high speed to shear the dispersed particles of the rubbery polymer. The reaction solution treated with the particle disperser is continuously supplied to the second reaction tank to continue polymerization, or if necessary, it is further supplied to the third reaction tank and subsequent reaction tanks to continue polymerization. In the continuous production method of rubber-modified impact-resistant resin, (A) the weight mixing ratio of aromatic vinyl monomer/cyanide vinyl monomer in the raw material solution is from 99/l to 50/50.
(B) When the volume of the reaction liquid in the first reaction tank is v1 and the volume of the particle disperser is v8, Vt/Vl < 0.2 is satisfied, (C) Inside the particle disperser The linear velocity of the outer circumference of each blade or rotor is 0.5 m/sec or more, and (D
) Continuous production of rubber-modified impact-resistant resin with good appearance, characterized in that the second reaction tank is a stirred tank type reaction tank, and the monomer conversion rate in the reaction tank is maintained at 25% by weight or more. This is the manufacturing method. Examples of the aromatic vinyl monomer used in the present invention include styrene, α-methylstyrene, styrene in which the benzene ring is substituted with alkyl, such as 〇-m- or P-methylstyrene, 0-, m- or ρ-tertyl styrene. One or more types of styrene such as liptylstyrene, styrene in which the benzene ring is halogenated, such as 0-, m- or p-chlor, or promstyrene can be used. As the vinyl cyanide monomer, one or more of acrylonitrile, methacrylonitrile, etc. can be used. Furthermore, copolymerizable monomers such as acrylic esters such as methyl methacrylate, maleic anhydride, and maleimide may be added to these monomers as necessary. The weight mixing ratio of aromatic vinyl monomer/vinyl cyanide monomer in the raw material solution is in the range of 99/1 to 50/50, preferably in the range of 95/5 to 50/50. If the mixing ratio of aromatic vinyl monomer/vinyl cyanide monomer is greater than 99/1, the resulting resin will have poor chemical resistance, rigidity and heat resistance, and if it is less than 50/50, the resulting resin will have poor chemical resistance, stiffness and heat resistance. This is undesirable because the surface gloss of the resin is poor and the fluidity is poor. The rubbery polymer may be any commonly used rubber as long as it can be dissolved in these monomers, such as butane diene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, chlorobrene, etc. Rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, etc. Appropriate rubber components are those whose 5% styrene solution has a viscosity of 100 centipoise or less at 25"C. As is well known, in bulk or solution polymerization, the rubber components that initially existed as a homogeneous solution are When the polymerization rate of the monomer exceeds a certain level, the phase separates and takes the form of dispersed particles.This is a phenomenon generally called phase transition, but if the above-mentioned solution viscosity of the rubber component in the raw material solution exceeds 100 centivoids, , the rubber particles produced in the first reaction tank are large, and even if the rubber particles are treated with a particle dispersion machine described later, the rubber particles cannot be made small enough, and the resulting resin has poor surface gloss, which is undesirable. The raw material solution used in the present invention may be only an aromatic vinyl monomer, vinyl cyanide, and a rubbery polymer, but aromatic hydrocarbons, aliphatic hydrocarbons,
A welding agent such as alicyclic hydrocarbons, halogenated hydrocarbons, and ketones may be added to a concentration of 40% by weight or less.
When the amount of the @ agent exceeds 40% by weight, the chain transfer effect increases, and the rubber particles produced in the first reaction tank become larger.
Even if the rubber particles are treated with a particle separator, the rubber particles cannot be made sufficiently small, and the production efficiency also decreases, which is undesirable. The raw material solution of the present invention also includes solutions to which such solvents are added. In the method of the present invention, when the raw #4 solution is continuously supplied to the first reaction tank for polymerization, it is preferable to simultaneously supply a radical polymerization initiator as a catalyst to the reaction tank for polymerization. ．． The radical polymerization initiators used include organic peroxides and azo compounds, but their 10-hour half-life decomposition temperature is 1.
00°C or lower, preferably 90°C or lower. Such radical polymerization initiators include lauroyl peroxide, tert-butyl peroxide (2-ethylhexanonate), penzoyl peroxide, 1.1-
Bis(tert-butylbaroxy) 3.3.5-
}Limethylcyclohexane, azobisisobutyronitrile, azobis-2methylbutyronitrile, etc., and 11 or more of these are used. When polymerization is started thermally in the first reaction tank without using a radical polymerization initiator,
The reason is unclear, but the rubber particles generated in the first reaction tank are large, and even if the rubber particles are treated with a particle dispersion machine, the rubber particles cannot be made small enough, making it impossible to control them to the desired value. I don't like it. Furthermore, even if polymerization is carried out using a radical polymerization initiator, the lo time half-life decomposition temperature of the radical polymerization initiator used is 10
When using a material with a temperature exceeding 0°C, it is necessary to raise the polymerization temperature, which increases the rate at which polymerization is initiated thermally.
This is not preferable as it reduces the effect of using a radical polymerization initiator. The amount of radical polymerization initiator supplied to the first reaction tank is 30 pp+s or more, preferably 5 pp+s based on the raw material solution.
0 pp or more is better. The amount of radical polymerization initiator is 30
If it is less than 9ρ1, the polymerization temperature needs to be raised, so the proportion of thermally initiated polymerization increases, and the effect of using the radical polymerization initiator decreases, which is not preferable.
The first reaction tank in the present invention is a complete mixing tank type PR.
Any type of reaction tank may be used, such as a tank type reaction tank or a plug-flow type column type reaction tank. When a stirred tank type reaction tank is used as the first reaction tank, the amount of monomer in the first reaction tank is higher than the monomer conversion rate necessary for converting the rubbery polymer into dispersed particles. The body conversion rate must be maintained. In addition, when a tower type reaction tank is used as the first reaction tank, the monomer in the polymerization liquid at the outlet of the first reaction tank is the monomer amount necessary for converting the rubbery polymer into dispersed particles. The monomer conversion must be maintained at a monomer conversion rate higher than the monomer conversion rate.

In the present invention, when the proportion of the rubbery polymer at the outlet of the first reaction tank is X, weight %, and the proportion of the polymerized monomer is x2 weight %, the values of X1 and x2 are 1 <X, ≦15
And 2. OXI-0.05X+"<X1< 4.0Xl-
It is preferable to satisfy 0.05X12.
When Xl≦1, the rubber content in the product becomes low under normal operating conditions, and the resulting rubber-modified resin cannot be put to practical use. On the other hand, when XI>15, the viscosity of the polymerization solution becomes very high, the required stirring power of the reaction tank becomes large, and the rubber-like polymer does not convert into dispersed particles in the first reaction tank, or becomes particulate. In some cases, giant particles are also generated. Usually, X1 is preferably selected in the range of 2<X, <12. Regarding the value of X2, x≦2.0X+-0.05X+
”, the monomer conversion rate is low and the rubber-like polymer cannot be made into particles in the first reaction tank, or even if it is made into particles, the particles are unstable and large.Polymerization at the outlet of the first reaction tank If the monomer conversion rate of the liquid is low and the rubber-like polymer has not turned into particles, or if the particles are unstable and large, the rubber particles cannot be controlled to the desired value even if treated with a particle disperser. X.≧4.OXI−0.05X,” the first
The viscosity of the polymerization liquid at the outlet of the reaction tank becomes extremely high, making it difficult to process it in the particle disperser that follows the first reaction tank, and the effect of processing the rubber particles in the particle disperser becomes noticeable. do not have. In the first reaction tank, a rubbery polymer is dissolved in an aromatic vinyl monomer and a vinyl cyanide monomer, and a raw material solution with a solvent added as needed and a radical polymerization initiator are continuously supplied. Polymerization is carried out at a polymerization rate higher than that required for converting the rubbery polymer into dispersed particles, and is usually carried out at a temperature of 50 to 150°C, preferably 60 to 130°C. Here, the conversion rate of monomer to polymer, and therefore the polymer concentration xi (ffil%), is determined by operating conditions such as polymerization temperature, composition of feedstock to the first reaction tank, feedrate of feedstock, and feed rate of polymerization initiator. It can be adjusted by In the first reaction tank, polymerization is carried out while stirring the polymerization liquid using a stirring blade. When a rubbery polymer is turned into particles, the particle size generally changes depending on the stirring intensity, but in the present invention, the rubber particle size is determined by the particle size wka following the first reaction tank.
The agitation in the first reaction tank is determined by the
Any material that can maintain a nearly uniform mixture in the reaction tank or maintain a state in which no stagnation occurs will suffice. In the present invention, a raw material solution and a radical polymerization initiator are supplied to a first reaction tank, and the monomers are polymerized to a polymerization rate higher than that required for converting the rubbery polymer into dispersed particles. A particle dispersion machine that continuously takes out a reaction liquid in an amount corresponding to the supply amount of the raw material solution and radical polymerization initiator from the first reaction tank, and that has at least three internal blades or rotors that rotate at high speed. The rubber particles produced in the first reaction tank are sheared so that they have a desired particle size. The particle dispersion machine referred to in the present invention has a short fluid residence time,
It is also a type of compact stirring mixer with internal blades or rotors that rotate at high speed and can apply a high shear rate to the reaction solution. In the present invention, at least three blades or rotors rotating at high speed in the particle dispersion machine are used.
It is necessary that there be at least three, more preferably four or more. At this time, the reaction liquid to be treated must pass through these blades or rotors in sequence, and it is not preferable to use a short bath. In order to prevent a short bath of the reaction liquid, it is preferable to provide a banflue or stator between each blade or rotor, or to provide multiple dispersion chambers in series. When the number of blades or rotors is three or less, the number of times the rubber particles produced in the first reaction tank are sheared is insufficient, making it difficult to obtain the desired particle size using a particle disperser. The particle disperser may be of any type as long as it satisfies the above conditions and provides a high shear rate, but for example, propeller blades, paddle blades, inclined paddle blades, turbine blades, etc. may be used as stirring blades. A stirring mixer is used in which three or more of these blades are mounted on the same axis and a baffle is provided between each blade. Also, for example, it is composed of a combination of a concentric ring-shaped rotor and a stator with comb-like gears, and two or more of these combinations are arranged in a multilayer concentric ring shape, or they are arranged on the same axis in separate rooms. Stirring mixers are used that are installed in multiple stages of two or more in series, or are combined in a concentric ring shape and then installed in multiple stages in series in a separate room. In this case, it is necessary that there be at least three combinations of rotors and stators in a multi-layer, multi-stage, or multi-layer/multi-stage combination. As examples of these! KA LILTRA
-TIII? RAX-INLIN[! , IKA [ll
SPAX-Rl! ACTOR (IKA Corporation), τK Highline Mill, Tκ Vibrine Homogenizer (Tokushu Kika Kogyo), Ebara Milder (Ebara Corporation), etc. can also be used. At this time, the outer diameter d of the stirring blade or rotor (
m), the rotation speed of the stirring blade or rotor is n (rps
), then the linear velocity V of the outer periphery of the stirring blade or rotor, expressed as V=π・d−n (s+/sec), is 0.5.
It is preferable that it is more than plow/second. If the linear velocity (■) is less than 0.5 m/sec, the shearing speed within the particle dispersion machine is insufficient, and it becomes difficult to make the rubber particles produced in the first reaction tank into the desired particle size using the particle dispersion machine. ．．
In the method of the present invention, the dispersed particles of the rubbery polymer can be adjusted to a desired particle size using a particle disperser. For example, the rubber particle diameter can be adjusted by appropriately selecting the rotation speed n of the stirring blade or rotor of the particle disperser. In addition, when using a particle dispersion machine that has a combination of a rotor and a stator, the gap between each rotor and stator is h (m), and the linear velocity v (m/sec) of the outer circumference of the rotor is It is preferable that the relationship between v/h≧200 and preferably v/h≧300 be satisfied. However, if ν/h is less than 200, the shearing force is insufficient and it becomes difficult to make the rubber particles grown in the first reaction tank a desired particle size using a particle disperser.In the present invention, When the volume of the reaction liquid in the first reaction tank is V and the volume of the particle disperser is V, Vz/Vt
<0.2 Preferably v, /v, <0.15t'. ! If h/V+ is not smaller than 0.2, the volume of the particle disperser becomes large relative to the flow rate of the reaction liquid, and the average residence time in the particle disperser increases, during which time the monomer conversion rate decreases. This is undesirable because the particle size of the reaction solution also increases, requiring excessive power from the high-speed rotation of the stirring blade or rotor of the particle disperser. In the present invention, the reaction liquid continuously extracted from the first reaction tank is treated with a particle disperser, and the treated reaction liquid is then continuously supplied to the second reaction tank to continue polymerization. However, it is necessary that the second reaction tank is a stirred tank type reaction tank, and that the monomer conversion rate of the reaction liquid in the second reaction tank is maintained at 25% by weight or more. ．． At this time, when the second reaction tank is a reaction tank other than a stirred tank type reaction tank, for example, a column type reaction tank in which the monomer conversion rate of the reaction liquid at the inlet and outlet of the reaction tank is different,
Alternatively, even if the second reaction tank is a stirred tank type reaction tank, if the monomer conversion rate of the reaction liquid in the reaction tank is 25% by weight, the rubber particle size distribution in the resulting resin will be wide. , undesirable. It is necessary to stabilize the rubber particles produced in the Wi ring line by feeding them into a reaction solution with a high polymerization rate. The stirred tank type reaction tank used as the second reaction tank may be any reaction tank in which the reaction liquid in the reaction tank is mixed with a stirring blade so that the composition and temperature are almost uniform, and is well known in the art. For example, there are reaction vessels equipped with a screw type stirring blade with a draft or a double helical type stirring blade. The reaction liquid subjected to polymerization in the second reaction tank is continuously extracted from the reaction tank, and if necessary, the polymerization is continued in one or more stirred tank type reaction tanks or tower type reaction tanks, and then, for example, 18
Unreacted monomers and solvent are evaporated under vacuum at a temperature range of 0 to 260°C to obtain a rubber-modified impact-resistant resin. In the present invention, chain transfer agents such as mercabutanes may be used to adjust the molecular weight of the produced polymer. When using a chain transfer agent, the entire amount may be added to the raw material solution supplied to the first reaction tank, or a portion of the chain transfer agent may be added to the second reaction tank. Furthermore, if necessary, antioxidants such as alwylated phenol, plasticizers or lubricants such as butyl stearate, zinc stearate, and mineral oil may be added to the raw material solution, during polymerization, or at the end of polymerization. good. [Example] Next, an example of the present invention will be shown. Example 1 6.0 parts by weight of polybutadiene (manufactured by Asahi Kasei, trade name Asabrene 7000) and 55.5 parts by weight of styrene, 18.5 parts by weight
A raw material solution was prepared by dissolving 20.0 parts by weight of acrylonitrile (styrene/acrylonitrile weight ratio 75/25) in 20.0 parts by weight of ethylbenzene. The solution viscosity of a 5% styrene solution of Asaprene 700A at 25°C is 45 centipoise. To this raw material solution, 0.2 parts by weight of tertiary dodecyl butane was added as a molecular weight regulator, and penzoyl peroxide (BPO) was added as a radical polymerization initiator.
: After adding 0.02 parts by weight of 10-hour half-life temperature 74°C) and 0.2 parts by weight of 2,6-ditertiarybutylphenol as an antioxidant, the mixture was prepared using a liquid-filled, draft-equipped screw type stirring blade. Volume (V+)18. Continuously 15. It was supplied at a speed of /hour. In the first reaction tank, polymerization was carried out at a reaction temperature of 110° C. and a stirring blade rotation speed of 1.5 rρS to cause phase transition of the rubbery polymer and produce rubber particles. The reaction liquid at the outlet of the first reaction tank contains a rubbery polymer L=6. omt%, weight part produced from monomer κ. =
It was 16.4% by weight (monomer conversion 122.2% by weight). The reaction solution from the first reaction tank was continuously taken out and sent to a particle disperser for treatment. The particle disperser has an inner volume (V) of 0.481, and an outer diameter (d) as a 13l stirring blade.
) 6 sets of 0.05-4 paddle blades are attached to one shaft, and a disc that rotates at the same time as the shaft is installed between each paddle blade as a baffle. was used. The rotation speed (n) of the stirring blade in the particle disperser is 16.7 rps (1000 rpm
). Volume ratio V of the first reaction tank and particle disperser
Z/Vl is 0.027, and the velocity of the outer periphery of each stirring blade in the particle disperser is 2.6 m/sec. The reaction liquid treated with the particle disperser was then transferred to a 10.2f volume tank equipped with a liquid-filled screw-type stirring blade with a draft.
Polymerization was continued by continuously feeding fi to the second reactor.
In the second reaction tank, the reaction temperature was 110℃, and the rotation speed of the stirring blade was l.
．． Polymerization was carried out using Orps. Monomer conversion rate is 33.2
%Met. Furthermore, the reaction liquid polymerized in the second reaction tank is continuously taken out and supplied to third, fourth, and fifth reaction tanks equipped with the same draft screw type stirring blades as the first and second reaction tanks. The outlet temperature of each tank is 120℃ and 130℃, respectively.
Polymerization was continued at The reaction liquid continuously taken out from the fifth reaction tank is used to remove unreacted monomers and solvent under high temperature and high vacuum using a conventionally known devolatilization device, and then pelletized using an extruder. and obtained an ABS resin product. The volume average diameter of the rubber particles in the obtained product was measured based on electron micrographs. Also, the product is 0
．． The number of finshuai having an area of 2 ml+" or more after extruding to a thickness of 1-1 was measured.Furthermore, 4
The test piece was molded using a JIS Z
-8741 was used to measure the surface gloss of the precept at an incident angle of 60°. The operating conditions and evaluation results are shown in Table 1. Similar evaluations were conducted for the following Examples and Comparative Examples, and are shown in Tables 1 and 2, respectively. Examples 2 and 3 Same as Example 1 except that the rotation speed of the stirring blade in the particle dispersion machine was changed.
I drove it exactly the same way. Example 4 The operation was carried out in the same manner as in Example 1 except that the reaction temperature of the first reaction tank was changed to 107°C. Example 5 In Example 1, 1 of the polybutadiene in the raw material solution was changed to 8
．． The operation was carried out by changing the amount of styrene/acrylonitrile used and the temperature of the first reaction tank as shown in Table 1. Example 6 Styrene-butadiene copolymer (manufactured by Asahi Kasei, trade name: Tuffden 2000^) was used as the rubbery polymer in the raw material solution.
The operation was carried out in the same manner as in Example 1, except that a 5% styrene solution (solution viscosity at 25°C: 50 centivoise) was used. Example 7 10 hour half-life decomposition temperature 62 as a radical polymerization initiator
℃ lauroyl peroxide (LPO) 0.04
The operation was carried out in the same manner as in Example 1, except that parts by weight were used and the polymerization temperature in the first reaction tank was 105°C. Example 8 In Example 1, a combination of a rotor and a stator with comb teeth was used as a particle dispersion machine,
These 2 meters are arranged in two layers in a concentric ring shape, and the combination of the rotor and stator in the two-layer ring shape is arranged in three stages in series on the same axis in a separate room. Using. In this device, there are six combinations of rotor and stator. The internal volume (v2) of the particle disperser is 0.24 ffi, and the outer diameter (do) of the outer rotor of the two layers of rotors at each stage is 0.0.
55m, inner rotor outer displacement (di) is 0.04m
, and the clearance (h) between the rotor and stator is 0.001. The rotation speed (n) of the rotor in the particle disperser was 8.3 rps (500 prs). Volume of the first reaction tank and particle disperser (cV1/V+ is 0.
013, the linear velocity of the outer circumference of each rotor in the particle disperser is 1.44 s/sec for the outer rotor (v.), 1.05 m/sec for the inner rotor (νi), and the gap between the rotor and stator and the linear velocity of the rotor periphery v
/h is V@ /h-1440 on the outside, vi on the inside
/h -1050. Example 9, lO Example 8 except that the rotation speed of the stirring blade in the particle dispersion machine was changed.
I drove it exactly the same way. Comparative Example 1 Except that there is no particle disperser between the first reaction tank and the second reaction tank,
It was operated in the same manner as in Example 1. The average particle size of the rubber particles was large, and some giant particles were observed. Comparative Example 2 In Comparative Example 1, the rotation speed of the first reaction tank stirring blade was set to 6, Orp.
s (360 rpm). Although no giant particles were observed, the average particle size was larger than in Example 1. Comparative Example 3 In Example 1, the rotation speed of the stirring blade in the particle disperser was set to 2.
．． Orps (120 rpm). Comparative Example 4 In Example 1, as a particle disperser, the internal volume (V.)
0.961 fi Outer diameter (d) as stirring blade 0.08 m (7
) A stirrer with one 4-piece inclined pattle blade was used, and the stirring rotation speed was 16.7 rps (1000 rpm). Comparative Example 5 In implementation g#l, the internal volume was 7.62 as a particle disperser.
As stirring blades, six sets of four battle blades with an outer diameter (d) of 0.14 m were used, and the stirring rotation speed was set to 3.
．． It was operated at 33 rps (20 rpm). Comparative Example 6 In Example 1, the temperature of the first reaction tank and the second reaction tank were changed to such conditions (Table 2) that the monomer conversion rate of the second reaction tank was 25% by weight or less. Comparative Example 7 In Comparative Example 6, when the first reaction tank was operated at 95°C, the rubbery polymer did not undergo phase transition and remained in a continuous phase in the first reaction tank. Comparative Example 8 In which rubber particles were not generated even when treated with a particle disperser, and rubber particles were generated only after the temperature was raised to 120°C in the second reaction tank.In Example 1, the temperature of the first reaction tank was raised to 123°C. During operation, the rubber particles that had grown in the first reaction tank were large, and giant particles were observed in some parts. This reaction solution was treated in a circulation line and a line mixer in the middle of the circulation line, but the average particle size was larger than in Example 1, and a few large particles were observed. Comparative Example 9 The weight ratio of the monomers styrene/acrylonitrile in the raw material solution was set to 40/60 (29.6 parts by weight of styrene, 44.4 parts by weight of acrylonitrile), and the amount of tert-dodecyl mercabutane was set to 0.3 parts by weight. Example 1 except that
When tested in the same way as ABS resin, the gloss was slightly reduced and the fluidity deteriorated. Comparative Example 10 Same as Example 1 except that high viscosity polybutadiene (Diene 55^ manufactured by Asahi Kakai Co., Ltd., solution viscosity of 5% styrene melt at 25°C: 160 centiboise) was used as the rubbery polymer in the raw material solution. I did it. I! ! Comparative Example 11 in which the rubber particle size in the product was large and the gloss was poor In Example 1, ditertiarybutyl peroxide (10 hour half-life decomposition temperature 12
4°C) was used, and the temperature of the first reaction tank was set to 1.
The operation was carried out at 26°C. The obtained product had a large rubber particle size and low gloss. Comparative Example 12 In Example 1, the temperature of the first reaction tank was set to 130° C. without using a radical polymerization initiator, and thermal polymerization was started and operated. The resulting product had a large rubber particle size and low gloss. Comparative Example 13 In Example 1, the rubbery polymer in the raw material solution was
Parts by weight, 48.0 parts by weight of styrene, 1 part by weight of acrylonitrile
6.0 parts by weight and 20.0 parts by weight of ethylbenzene. The rubber concentration in the first reaction tank was too high, and the viscosity of the reaction solution increased and became gel-like, making it impossible to obtain a normal product. Comparative Example 14 The same operation as in Example 1 was carried out using 1.0 parts by weight of the rubbery polymer in the raw material solution, 59.3 parts by weight of styrene, 19.7 parts by weight of acrylonitrile, and 20.0 parts by weight of ethylbenzene. Rubber particles with a small average particle size and no giant particles were observed, but the rubber content in the product was low and ABS
Impact strength etc. were too low for a resin. Comparative Example 15 In Example 8, the opening in the particle disperser. The motor was operated at a rotation speed of 1.67 rpi (100 rpm). Comparative Example 16 In Example 8, a particle dispersion machine having only one stage of a two-layer concentric ring-shaped rotor and stator combination was used.
．． It was operated at 3rps (500prs+). Comparison box 17 On the day of the example, the gap between the rotor and stator (
h) using a particle disperser with a diameter of 0.01 m, 8.3r9s
(50 rpm). [Effects of the Invention] According to the present invention, under specific conditions, a reaction liquid containing a rubber component that has been granulated in a first reaction tank is dispersed into a particle dispersion having at least three or more blades or rotors that rotate at high speed inside. Rubber particles are processed in a machine to obtain rubber particles with a desired particle size, and then polymerized in a second reaction tank to stabilize the rubber particles. Excellent chemical resistance, heat resistance, and rigidity. Outside li5!
Good so-called ABS resin can be produced extremely efficiently. The present invention thus provides a method that meets the demands for manufacturing high-quality products accompanying the expansion of uses for rubber-modified impact-resistant resins, as well as the demand for low-cost production through more efficient manufacturing methods. is extremely large.

Claims (1)

[Claims] (1) A raw material solution in which a rubbery polymer is dissolved in a mixture of an aromatic vinyl monomer and a vinyl cyanide monomer and a radical polymerization initiator are continuously fed into a first reaction tank. Supplying a raw material solution and a radical polymerization initiator from the first reaction tank while polymerizing the monomer at a monomer conversion rate higher than that required for converting the rubbery polymer into dispersed particles. A corresponding amount of the reaction liquid is continuously taken out, and the reaction liquid is sent to a particle dispersion machine that has at least three or more blades or rotors that rotate at high speed to shear the dispersed particles of the rubbery polymer. Then, the reaction liquid treated with the particle disperser is continuously supplied to the second reaction tank to continue polymerization, or if necessary, it is further supplied to the third reaction tank and subsequent reaction tanks for polymerization. (A) The weight mixing ratio of aromatic vinyl monomer/vinyl cyanide monomer in the raw material solution is from 99/1 to 50/50. (B) When the volume occupied by the reaction liquid in the first reaction tank is V_1 and the volume of the particle disperser is V_2, V_2/V_1<0.
(C) The linear velocity v (m/sec) of the outer periphery of each blade or rotor in the particle disperser is 0.5 m/sec or more, and (D) The second reaction tank is a stirring tank. 1. A method for continuously producing a rubber-modified impact-resistant resin with a good appearance, characterized in that a monomer conversion rate in a molded reaction tank is maintained at 25% by weight or more. (2) The viscosity of the 5% styrene solution of the rubbery polymer in the raw material solution is 100 centipoise or less at 25°C, and the radical polymerization initiator supplied to the first reaction tank decomposes within its 10-hour half-life. 2. The method for continuously producing a rubber-modified impact-resistant resin according to claim 1, wherein the temperature is 100° C. or lower, and the amount of the radical polymerization initiator supplied is 30 ppm or more based on the raw material solution. (3) When the proportion of the rubbery polymer in the reaction liquid at the outlet of the first reaction tank is X_1% by weight, and the proportion of the polymer produced by polymerization of monomers is X_2% by weight, the values of X_1 and X_2 1
<X_1≦15 and 2.0X_1-0.05X_1^2<X_2<4.0X
3. The method for continuously producing a rubber-modified impact-resistant resin according to claim 1 or 2, wherein the rubber-modified impact-resistant resin is maintained to satisfy _1-0.05X_1^2. (4) The particle disperser is composed of a concentric ring-shaped rotor and a stator, and the number of combinations of the rotor and stator is at least three, and the gap between each rotor and stator is h (m). The method for continuously producing a rubber-modified impact-resistant resin according to claim 1, 2 or 3, which satisfies the relationship v/h≧200 with the linear velocity v (m/sec) of the outer periphery of the rotor.