JPH07173231A - Method and apparatus for producing high-impact styrenic resin - Google Patents

Abstract

PURPOSE:To obtain a styrenic resin which gives a molded article excellent in gloss and impact resistance by adopting a specific production process to control the rubber content and the particle size and distribution of a rubber phase. CONSTITUTION:A mixture contg. a styrenic monomer (e.g. styrene) and a rubber component (e.g. polybutadiene) is polymerized in a prepolymerizer 2. The resulting polymer soln. is polymerized in the first polymerizer 4 connected to the prepolymerizer 2, while a polymerizable soln. at least contg. a styrenic monomer (e. g. styrene) is polymerized in the second polymerizer 7. Polymer solns. from the first and second polymerizers 4 and 7 are combined together and polymerized in postpolymerizers 9 and 11.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an impact resistant styrene resin useful for obtaining various molded articles.

[0002]

2. Description of the Related Art A continuous bulk polymerization method, which is economically advantageous, has become the mainstream process at present as a process for producing an impact-resistant styrene resin. In addition, as for the continuous bulk polymerization method process mainly composed of a complete mixing type reactor or a plug flow type reactor, many processes have been proposed from the viewpoints of quality design and productivity. Of these, in many cases, a complete mixing type reactor capable of uniform stirring in a region where the conversion rate to a polymer is low is adopted as a reactor for inversion as rubber particles.

On the other hand, as for the impact resistant styrene resin, grades having various characteristic values with respect to the characteristics such as impact resistance, molding processability and rigidity are manufactured according to the use. Impact-resistant styrenic resin according to the above required characteristics,
Polymerization is often performed by adjusting the rubber content. That is, once the impact-resistant styrene-based resin has been produced, the same apparatus is used to supply a mixed solution having different rubber component contents to the styrene-based monomer to the reactor, whereby grades having different rubber contents are obtained. Are manufactured. Therefore, in one manufacturing process in which multiple reactors are connected in series, in order to manufacture impact-resistant styrene-based resins having different rubber contents, rubber components and molecular weights, the previous brands (previous It is necessary to replace the (grade) polymerization liquid with a new grade (new grade) polymerization liquid.

However, the polymerization liquid containing the rubber component has a high viscosity. Therefore, it takes a long time to replace or replace the polymerization liquid, and the rubber content of the styrene resin cannot be adjusted efficiently. In addition, since the replacement liquid mixes the polymerization liquid of the previous brand with the polymerization liquid of the new brand, a large amount of off-grade having intermediate properties is generated. Further, the dissolution tank of the mixed liquid containing the styrene-based monomer and the rubber component also requires concentration adjustment or washing and replacement operations each time the brand is changed. This is a particularly serious problem in a continuous bulk polymerization process in which a highly viscous polymer is engineered.

On the other hand, when an impact-resistant styrene-based resin is produced by grafting a styrene-based monomer onto the rubber component in the presence of the rubber component, the rubber particle size has a great influence on the gloss and impact strength of the product. It is technically important how to uniformly and finely disperse the rubber component into fine particles.

However, when the rubber content or the type of the rubber component is changed by changing the brand, the polymerization conversion rate of the styrene-based monomer at the time of phase inversion is also changed, which makes it very difficult to control the rubber particle size. In particular, when producing an impact resistant styrene-based resin having a low rubber content, it is necessary to lower the stirring rotation speed, but in this case, uniform stirring becomes difficult, and polymer scale is formed in the reactor. It adheres and it becomes impossible to operate continuously. Further, the phase inversion phenomenon becomes unstable, and it becomes more difficult to control the rubber particle size.

In the styrene-based resin containing the rubber particles, a contradictory relationship between the gloss and the impact strength is recognized, and the gloss is improved when the diameter of the rubber particles is reduced,
Impact strength decreases. Further, since it is more difficult to make fine particles of butadiene rubber than styrene-butadiene rubber, impact-resistant styrene-based resin containing butadiene rubber generally has low gloss.

In order to achieve both gloss and impact resistance, an impact resistant styrene resin having a bimodal particle size distribution composed of rubber having a small particle size and a large particle size has been proposed. For example, JP-A-59-1519 and JP-A-63-241.
No. 053, JP-A-1-261444, JP-A-4-25518, and JP-A-4-88006 disclose an impact-resistant styrene resin containing a rubber phase having a small particle diameter and a rubber having a large particle diameter. Disclosed is a method for producing an impact-resistant styrenic resin in which a rubber phase has a bimodal particle size distribution by mixing with an impact-resistant styrenic resin containing a phase. In Japanese Patent Laid-Open No. 4-80203, a polymerization liquid containing phase-inverted rubber particles is supplied to a particle disperser equipped with blades and rotors, and the disperser is alternately operated at high speed and low speed at predetermined intervals. , A method for producing an impact-resistant styrenic resin containing a rubber phase having a bimodal particle size distribution is disclosed.

In Japanese Patent Laid-Open No. 3-199212, a raw material solution containing a rubber component is supplied to a first reactor to granulate the rubber component, and the polymerization liquid is connected in series with the first reactor. A method for producing an impact-resistant styrene-based resin having a bimodal particle size distribution by supplying a styrene-butadiene block rubber to the second reactor and granulating the same while supplying the styrene-butadiene block rubber to the second reactor is disclosed. . Furthermore, Japanese Patent Laid-Open No. 3-1
In JP 03414, a plug flow type reactor connected in parallel is used to prepare rubber particles having a small particle size and a rubber particle having a large particle size, respectively, to produce an impact resistant styrene resin having a bimodal particle size distribution. A method is disclosed.

However, it is more difficult to reduce the particle size of the rubber particles when using a non-styrene rubber component such as butadiene rubber than when using a rubber component containing a styrene unit such as styrene-butadiene rubber. is there.

[0011]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a method and an apparatus for producing an impact-resistant styrene resin whose rubber content can be easily adjusted.

Another object of the present invention is to produce impact-resistant styrenic resins having different kinds of rubber components and different rubber contents.
An object of the present invention is to provide an impact-resistant styrene-based resin production method and production apparatus capable of controlling the rubber particle size.

Still another object of the present invention is to provide a method and a method for producing an impact resistant styrene resin which can control the rubber particle size with higher accuracy.

Another object of the present invention is to use a non-styrene type rubber component to reduce the particle size of the rubber particles to obtain a molded article which is excellent in both gloss and impact resistance. An object of the present invention is to provide a method and an apparatus for producing a high impact styrene resin.

[0015]

Means for Solving the Problems The inventors of the present invention have earnestly studied the production of impact-resistant styrene-based resin in order to achieve the above-mentioned object, and have completed the present invention by obtaining the following findings.

(1) When the polymerization liquid after the rubber component undergoes phase inversion and the polymerization liquid of the styrene-based monomer are combined and supplied to the post-polymerization reactor, the rubber component and the styrene-based monomer are contained. By adjusting the supply ratio of the mixture and the styrene-based monomer without changing the composition of the mixed solution, the rubber content of the styrene-based resin can be easily and efficiently adjusted,
(2) The rubber particle size can be controlled by polymerizing through a prepolymerization process and inverting the rubber component into rubber particles. (3) In the reactor for polymerizing by inverting the prepolymerization liquid, the non-styrene rubber component is used. By co-existing with and polymerizing by supplying a mixed solution of a styrene-based monomer and a rubber component containing a styrene unit, the phase inversion particle diameter of the non-styrene-based rubber component can be reduced,
In addition, the rubber particle size can be controlled, and (4) the polymerizability of a polymerization liquid obtained by polymerizing a mixed liquid of a styrene-based monomer and a non-styrene-based rubber component with a rubber component containing a styrene-based monomer and a styrene unit. When a polymerization liquid obtained by polymerizing a liquid is combined and polymerized, an impact-resistant styrene resin containing rubber particles having a bimodal particle size distribution with controlled particle size can be obtained.

That is, in the method of the present invention, a mixed solution containing a styrene monomer and a rubber component is polymerized in a pre-reactor, and the pre-reactor is pre-reacted in a first reactor connected in series with the pre-reactor. The polymerization liquid from the reactor is polymerized, the polymerizable liquid containing at least a styrene monomer is polymerized in the second reactor, and the polymerization liquid from the first reactor and the second reactor is post-polymerized. Impact-resistant styrenic resin is produced by polymerizing in a reactor.

In the above production method, the styrene resin may be continuously produced by continuously subjecting the polymerization component such as the styrene monomer to the polymerization reaction. Further, the pre-reactor and the first reactor may be composed of complete mixing type reactors, and the post-polymerization reactor may be composed of a plurality of perfect mixing type reactors or a plurality of plug flow type reactors. Good.

In the first reactor, a mixed liquid containing a styrene-based monomer and a rubber component different from the rubber component supplied to the pre-reactor is supplied, whereby the pre-reactor is discharged. The polymerization may be carried out in the presence of a polymerization liquid. By this method, a styrene resin having a bimodal particle size distribution can be obtained.

In another method of the present invention, a mixed solution containing a styrene monomer and a non-styrene rubber component is polymerized in the pre-reactor and the first reactor in order, and the styrene monomer and The impact-resistant styrene-based resin may be produced by polymerizing a polymerizable liquid containing a rubber component having a styrene unit (styrene-based rubber component) in the second reactor. Also in this method, a mixed solution containing a styrene-based monomer and a rubber component having a styrene unit may be polymerized in the first reactor in the presence of the polymerization liquid from the preliminary reactor.
By such a method, it is possible to obtain a styrene resin having a bimodal particle size distribution in which rubber particles have different particle sizes. The difference between the particle size of the large particle rubber and the particle size of the small particle rubber may be 0.5 μm or less. The non-styrene rubber component includes butadiene rubber and the like, and the rubber component having a styrene unit includes styrene-butadiene rubber and the like. In these processes, the pre-reactor, the first reactor and the second reactor may consist of a fully mixed reactor.

Further, the production apparatus of the present invention comprises a pre-reactor for pre-polymerizing a mixed solution containing a styrene monomer and a rubber component, and a pre-reactor connected in series to the pre-reactor. A first reactor for polymerizing a polymerization liquid from the reactor, a second reactor for polymerizing a polymerizable liquid containing at least a styrenic monomer, the first reactor and the second reactor. And a post-polymerization reactor for increasing the polymerization conversion rate of the polymerization liquid from the reactor.

The present invention will be described in more detail below with reference to the accompanying drawings as needed.

FIG. 1 is a schematic block diagram showing an example of the apparatus and process of the present invention.

This manufacturing process constitutes a continuous bulk polymerization process, in which a mixed solution containing a styrene monomer and a rubber component is continuously supplied to a preliminary reactor 2 through a supply line 1 to carry out preliminary polymerization. The preliminary polymerization liquid from the preliminary reactor 2 is continuously supplied to the first reactor 4 through the connection line 3 for polymerization. The preliminary reactor 2 and the first reactor 4 are connected in series and are configured as a complete mixing type reactor. Further, in the first reactor 2, the polymerization conversion rate of the prepolymerization liquid is increased, and the rubber component is phase-inverted and polymerized.

Further, the styrene-based monomer is continuously supplied through the supply line 6 to the second reactor 7, which may be a complete mixing type reactor, for prepolymerization.
The polymerization liquids from the first reactor 4 and the second reactor 7 are continuously supplied to the post-polymerization reactor 9 composed of a complete mixing type reactor through connection lines 5 and 8, respectively. . The combined polymerization liquid is polymerized in the post-polymerization reactor 9 and is also supplied to the subsequent post-polymerization reactor 11 through the connection line 10 to be polymerized while increasing the polymerization conversion rate.
The highly polymerized polymerization liquid is subjected to a post-treatment step such as purification from the post-polymerization reactor 11 through the supply line 12.

In such a method, the polymerization conversion rate in the pre-reactor 2 and the first reactor 4 is increased successively,
Polymerization can be performed while phase inversion of the rubber component and conversion into dispersed particles, and the particle size of the rubber phase can be controlled because the pre-reactor 2 and the first reactor 4 are constituted by a complete mixing type reactor. In addition, the styrene-based monomer can be prepolymerized in the second reactor 7 which is independent of the preliminary reactor 2 and the first reactor 4 and is provided in parallel.

Therefore, the polymerization liquid from the first reactor 4 and the styrene-based monomer from the second reactor 7 are adjusted without adjusting the content of the rubber component in the mixed liquid supplied to the preliminary reactor 2. Of the post-polymerization reactors 9 and 11 while adjusting the ratio with the polymerization liquid of
Styrene-based resins having different rubber contents can be produced by supplying them to and joining them. The degree of polymerization of the styrene-based monomer containing the rubber component is often smaller than that of the styrene-based monomer alone. Therefore, the preliminary reactor 2
The molecular weight distribution and average degree of polymerization of the impact resistant styrene resin can be easily controlled by simply adjusting the ratio of the mixed liquid supplied to the second reactor 7 and the styrene monomer supplied to the second reactor 7. The processability such as moldability of the obtained styrene resin can be improved.

Further, by supplying the polymerization liquid of the styrenic monomer from the second reactor 7 to the post-polymerization reactors 9 and 11, the polymerization liquid remaining in the post-polymerization reactors 9 and 11 can be efficiently treated. It can be replaced well and the rubber content of styrene resin can be adjusted within a short time. That is, even if styrene-based resins having different rubber contents are continuously produced after the impact-resistant styrene-based resin is produced, the polymerization liquid from the first reactor 4 and the second
Of the high-viscosity polymerization liquid remaining in the post-polymerization reactors 9 and 11 and the connection line 10 by merging with the polymerization liquid from the reactor 7 of FIG. , And can be efficiently replaced by a new grade of confluent, and the amount of off-grade styrene resin produced can be reduced.

When a new brand of styrene-based resin is produced after the styrene-based resin is produced, the rubber content in the mixed liquid is often changed.

FIG. 2 is a schematic block diagram showing another example of the apparatus and process of the present invention. It should be noted that the same elements as those of the manufacturing apparatus of FIG.

In this example, a plurality of post-polymerization reactors are composed of a tower type reactor 21 equipped with a stirrer and a static mixer type reactor 22 connected in series to the reactor. Except for the above, the process is basically the same as that shown in FIG.

In such a method, a rubber phase having an average particle diameter of 0.1 to 5 μm, preferably about 0.3 to 3 μm is used depending on the stirring efficiency and shear rate of the pre-reactor, the first reactor and the like. It is possible to produce a styrene resin containing In addition,
The average particle size of the rubber phase can be measured as a volume average particle size by a light scattering method using a mixed solution of a resin and an organic solvent.

In the second reactor, if the amount is small,
A styrenic monomer containing a rubber component may be supplied. In this case, the content of the rubber component supplied to the second reactor can be selected within a range that does not impair the substitution efficiency of the polymerization liquid in the post-polymerization reactor in the subsequent stage, and for example, the rubber supplied to the preliminary reactor can be selected. 0 to 1/2 of the content of the component, preferably 0 to 1
4, more preferably about 0 to 1/10. In addition,
When the polymerizable liquid containing the rubber component is supplied to the second reactor, the second reactor is preferably a complete mixing type reactor.

In order to efficiently adjust the rubber content, the degree of polymerization, the molecular weight distribution and the like, in a preferred method, a styrene-based monomer containing no rubber component is supplied to the second reactor. In such a method, at the same polymerization conversion rate, the viscosity of the polymerization liquid from the second reactor is small, so that the polymerization liquid in the subsequent post-polymerization reactor can be efficiently replaced within a short time, and the styrene resin The rubber content of the can be easily adjusted.

The rubber component in the liquid mixture supplied to the preliminary reactor and the first reactor may be either a non-styrene rubber component or a styrene rubber component containing a styrene unit. The non-styrene rubber component such as polybutadiene tends to have a large phase-inverted rubber particle size, and the styrene-rubber component such as styrene-butadiene rubber has a phase-inverted rubber particle size larger than that of the non-styrene rubber component. Is easy to become small. On the other hand, when the prepolymerization and the phase inversion polymerization into the rubber phase are combined, the rubber particle size becomes smaller than that in the case where the polymerization is carried out in a single polymerization system. Therefore, it is preferable that the styrene-based monomer containing the non-styrene-based rubber component is prepolymerized in the pre-reactor and the rubber component is phase-inverted in the first reactor.

Further, the first reactor may be supplied with a styrene monomer, or a mixed liquid containing a styrene monomer and a rubber component. FIG. 3 is a schematic configuration diagram showing still another example of the apparatus and process of the present invention.

In this example, in the first reactor 32, in addition to the preliminary polymerization liquid supplied from the preliminary reactor 2 through the connection line 3, the polymerization liquid supplied to the preliminary reactor 2 through the supply line 31. The process is basically the same as the process shown in FIG. 1, except that a mixed liquid containing a rubber component different in type from the rubber component and the styrene-based monomer is supplied.

FIG. 4 is a schematic block diagram showing another example of the apparatus and process of the present invention.

In this example, in the first reactor 42, in addition to the preliminary polymerization liquid from the preliminary reactor 2, the rubber component of the mixed liquid supplied to the preliminary reactor 2 through the supply line 41 is different. The process is basically the same as that shown in FIG. 2, except that a mixed liquid containing different rubber components and a styrenic monomer is supplied.

In the process of FIGS. 3 and 4, in the presence of the prepolymerization liquid from the prereactor 2, the first reactor 32, 42
In the above, it is possible to polymerize a mixed liquid containing a rubber component of a different type from the rubber component of the prepolymerization liquid and a styrene-based monomer.

A method of supplying a mixed solution containing different rubber components to the pre-reactor and the first reactor and polymerizing the mixture.
That is, in the method of supplying a mixed liquid containing a rubber component different from the rubber component supplied to the pre-reactor and a styrene-based monomer to the first reactor for polymerization, the pre-polymerization from the pre-reactor is performed. In the presence of a liquid, a mixed liquid containing different rubber components can be polymerized, bimodal rubber particles having two peaks in the particle size distribution can be efficiently generated, and the gloss and impact resistance of molded products are improved. it can. Further, since the polymerization can be performed in the presence of the prepolymerization liquid before the phase inversion of the rubber component, it is possible to prevent the particles phase-inverted to the rubber phase, particularly the phase-inverted rubber particles of the non-styrene rubber component from becoming coarse. Moreover, the rubber content of the styrene resin can be efficiently adjusted by utilizing the polymerization liquid from the second reactor.

In a preferred method, a mixed solution containing a styrene-based monomer and a non-styrene-based rubber component or a styrene-based rubber component is sequentially polymerized in the pre-reactor and the first reactor, and the first reaction is performed. A mixed liquid containing a styrene-based monomer and a styrene-based rubber component or a non-styrene-based rubber component is supplied to a vessel and polymerized.

In this method, the styrene rubber component or the non-styrene rubber component is added to the first reactor in the presence of the non-styrene rubber component or the prepolymerization liquid containing the styrene rubber component from the pre-reactor. Since a mixed liquid containing the same can be polymerized, a rubber component containing a unit which is the same as or similar to the unit of the non-styrene rubber component as the styrene rubber component (for example, when a butadiene-rubber is used as the non-styrene rubber component, styrene-butadiene It is possible to prevent the coarsening of the rubber phase particles, especially the phase-inverted rubber particles of the non-styrene-based rubber component, probably because of the affinity of each rubber component, and to use the styrene-based rubber that has been phase-inverted to the rubber phase. The particle size of each rubber phase can be made small, and the particle size distribution of each rubber phase is sharp, and the particle sizes of the large particle rubber phase and the small particle rubber phase are close to each other, resulting in a difference in particle size. It can be reduced. Therefore, a styrene-based resin useful for obtaining a molded article having excellent gloss and impact resistance can be produced.

The styrene resin obtained by such a method has (A) an average particle diameter of 0.1 to 1 μm, preferably 0.1.
2 to 0.8 μm (for example, 0.3 to 0.7 μm) small particle rubber phase, and (B) average rubber particle diameter 0.5 to 5 μm
m, preferably 0.7-2.5 μm (eg 0.8-
It often contains a large particle rubber phase of about 1.5 μm).

Further, in the method of the present invention, a second reactor which is independent of the pre-reactor and the first reactor connected in series with each other and which is connected in parallel is used, It is possible to obtain a styrene-based resin containing rubber particles having a controlled particle size and having a plurality of peaks in the particle size distribution.

For example, in the process shown in FIG. 1 or 2, a mixed solution containing a styrene-based monomer and a non-styrene-based rubber component is sequentially polymerized in the pre-reactor 2 and the first reactor 4, and styrene When a polymerizable liquid containing a system monomer and a styrene-based rubber component is polymerized in the second reactor 7 and the degree of polymerization of the combined polymerization liquid in the post-polymerization reactors 9, 11, 12, 22 is increased, It is possible to obtain a styrene resin containing rubber particles having a peak-shaped particle size distribution.

That is, the non-styrene rubber component such as polybutadiene has a tendency that the particle diameter of the rubber phase tends to increase due to phase inversion, as compared with the styrene rubber component such as styrene-butadiene rubber, and the styrene content in the styrene rubber component is large. As the amount increases, the particle size of the rubber phase tends to decrease. Utilizing this fact, it is possible to produce a styrene resin containing a large particle diameter rubber phase composed of a non-styrene rubber component and a small particle diameter rubber phase composed of a styrene rubber component. At that time, if the pre-reactor, the first reactor and the second reactor are constituted by a complete mixing type reactor, the particle diameter of each rubber phase can be controlled more accurately.

Further, in the process shown in FIG. 3 or 4, a mixed liquid containing a styrene monomer and a non-styrene rubber component is supplied to the pre-reactor 2 to prepare the pre-reactor 2 and the first reactor. Polymerization is sequentially carried out in 32, 42, and a mixed solution containing a styrene-based monomer and a styrene-based rubber component is supplied to the first reactors 32, 42 for polymerization, and then the second reactors 7, 42 are polymerized. A styrene resin containing rubber particles having a bimodal particle size distribution can also be obtained by a method of supplying and polymerizing a polymerizable liquid containing a styrene monomer and a styrene rubber component.

In these methods, in addition to the methods shown in FIGS. 3 and 4, the polymerization liquid from the first reactor (non-styrene rubber component, styrene rubber component and styrene monomer polymerization) is used. Liquid) and the polymerization liquid from the second reactor (polymerization liquid of the non-styrene rubber component and the styrene monomer) are merged and polymerized in the post-polymerization reactor to increase the polymerization conversion rate. . Therefore, similarly to the above, if a rubber component containing the same or similar units as the units of the non-styrene rubber component is used as the styrene rubber component, it may be due to the affinity of each rubber component, or with the large particle rubber phase. The difference in particle size from the small particle rubber phase can be further reduced, and a styrene resin useful for obtaining a molded article excellent in gloss and impact resistance can be produced.

In such a method, the difference between the particle diameter of the large particle rubber composed of the non-styrene rubber component and the particle diameter of the small particle rubber composed of the styrene rubber component is 0.5 μm.
m or less, preferably 0.05 to 0.5 μm, more preferably about 0.1 to 0.4 μm, and a molded product excellent in both properties of gloss and impact strength can be produced. There is a feature that it can be obtained.

In the styrene resin obtained by the method of supplying the mixture of the styrene rubber component and the styrene monomer to the second reactor, the rubber component is (A) an average particle diameter of 0.1 to 0.1. 0.8 μm, preferably 0.2 to 0.7
Small particles of about μm, and (B) average particle diameter 0.5 to 2.0
In many cases, they are dispersed in large particles having a size of μm, preferably about 0.6 to 1.8 μm. The average particle size of the small particles is 0.
If it is less than 1 μm, the impact strength is reduced, and if it exceeds 0.8 μm, the gloss is reduced. If the average particle size of the large particles is less than 0.5 μm, the impact strength is reduced, and if it exceeds 2.0 μm, the gloss and the impact strength are poor. Debris or one of the characteristics deteriorates. When the particle size distribution of the dispersed particles of the rubber component has a single peak, any one of the impact resistance, the rigidity, and the gloss tends to be deteriorated.

In the process of the present invention, the pre-reactor and / or the first reactor are not limited to one reactor and may be composed of a plurality of reactors. The type of the reactor is not particularly limited, but the particle size of the phase-inverted rubber phase is controlled while completely mixing the mixed liquid containing the rubber component and the styrene-based monomer. The reactor of (1) is preferably composed of a complete mixing type reactor.

The complete mixing type reactor is only required to be able to stir the mixed liquid containing the styrene-based monomer and the rubber component while maintaining a substantially uniform mixed state. Examples of the stirring blades include anchor blades and double helical type Wings, screw type wings, etc. can be used. In order to efficiently disperse the rubber component, the first reactor is preferably equipped with a double helical blade (for example, double helical ribbon stirring blade) or a screw stirring blade.

Further, the second reactor is not limited to one and may be composed of a plurality of reactors. When the rubber component is not supplied, the type of the second reactor is not particularly limited, and the second reactor can be composed of a complete mixing type reactor or a plug flow type reactor. The plug flow type reactor can be selected from a static mixer type in which a plurality of static mixing elements are fixed and built in without having any moving parts, a tower type reactor with a stirrer that allows gentle stirring, etc. . When the rubber component is supplied, the second reactor is preferably composed of a complete mixing type reactor for the same reason as above.

The mixture liquid of the rubber component and the styrene-based monomer is supplied to the first reactor to polymerize, and the polymerizable liquid of the rubber component and the styrene-based monomer is supplied to the second reactor. When supplying and polymerizing, a styrene resin containing phase-inverted rubber particles having a plurality of peaks in the particle size distribution can be obtained according to the number of the first reactors and / or the second reactors.

Further, the type of the subsequent post-polymerization reactor is not particularly limited, but it is often a complete mixing type reactor or a plug flow type reactor. The post-polymerization reactor is preferably composed of a plurality of perfect mixing type reactors or a plurality of plug flow type reactors in order to sequentially increase the polymerization conversion rate. The number of post-polymerization reactors is not particularly limited as long as the polymerization conversion rate can be sequentially increased, and can be appropriately selected from the range of usually about 1 to 10 groups depending on the type of reactor and the like. For example, the number of complete mixing type reactors is about 1 to 5, and when the plug flow type reactor is a static mixer type reactor, it is often about 2 to 7 units.
The number of other plug flow type reactors is often about 2 to 5.

Examples of the styrene-based monomer include styrene, alkyl-substituted styrene (for example, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,
4-dimethylstyrene, p-ethylstyrene, pt-
Butyl styrene, etc.), α-alkyl substituted styrene (eg, α-methyl styrene, α-methyl-p-methyl styrene, etc.), halogenated styrene (eg, o-chlorostyrene, p-chlorostyrene, etc.) and the like. . Preferred styrenic monomers include, for example, styrene, p-methylstyrene, α-methylstyrene, especially styrene. These styrene-based monomers may be used alone or in combination of two or more.

The styrene-based monomer may be, for example, (meth) acrylic acid ester such as methyl methacrylate, ethyl acrylate, butyl acrylate, (meth) acrylic acid, maleic anhydride, acrylonitrile, etc., if necessary. The copolymerizable monomer of may be added.

The rubber component does not contain styrene units such as polybutadiene rubber, butadiene-isoprene rubber, butadiene-acrylonitrile copolymer, ethylene-propylene rubber, isoprene rubber, acrylic rubber and ethylene-vinyl acetate copolymer. Styrene-based rubber component: A styrene-based rubber component containing a styrene unit such as a styrene-butadiene copolymer or a styrene-butadiene block copolymer is included. These rubber components may be used alone or in combination of two or more depending on the type of polymerization process.

The rubber component can be selected according to the desired characteristics of the styrene resin, and for example, a polymer containing a butadiene unit (for example, polybutadiene) is often used. The rubber component containing a butadiene unit is cis-
It may be a polymer containing a high cis butadiene unit having a high 1,4 structure content, or a polymer containing a low cis butadiene unit having a low cis-1,4 structure content.
The molecular weight of the rubber component can be selected according to the characteristics of the impact-resistant styrene resin, for example, 1 × in terms of polystyrene.
About 10 ^{4 to} 100 × 10 ⁴ , 5 of rubber component at 25 ° C.
The weight% styrene solution viscosity is, for example, 15 to 2000 c.
It is often about ps.

The preferred non-styrene type rubber component includes butadiene rubber and the like, and the rubber component having a styrene unit includes styrene-butadiene rubber and the like.

The content of the rubber component in the raw materials such as the mixed liquid or the polymerizable liquid charged into the reactor can be selected within a wide range depending on the characteristics of the impact-resistant styrene resin, for example, 1 to
It is about 25% by weight, preferably about 2 to 20% by weight, and more preferably about 3 to 15% by weight.

When the styrene monomer is supplied to the second reactor and the polymerization liquids from the first reactor and the second reactor are combined to efficiently adjust the rubber content, the preliminary reaction is performed. The content of the rubber component in the mixed liquid supplied to the container is, for example, 5
It is often about 25 to 25% by weight, preferably about 7 to 15% by weight. When efficiently adjusting the rubber content of the styrene resin, the flow rate ratio of the polymerization liquid from the first reactor to the polymerization liquid from the second reactor depends on the rubber content and characteristics of the styrene resin. You can choose from a wide range. For example, when polymerizing while continuously supplying a mixed liquid or a styrene-based monomer, the flow rate of the polymerization liquid from the first reactor is 1 kg / hr, and the flow rate of the polymerization liquid from the second reactor is 1 kg / hr. Is 0.1-5
kg / hr, preferably 0.25 to 3 kg / hr, preferably 0.3 to 2 kg / hr. Further, in order to enhance the gloss and impact resistance of the molded product, the content of the non-styrene rubber component and the styrene rubber component in the mixed liquid is often about 5 to 15% by weight.

When the rubber component is contained, the mixed liquid or the polymerizable liquid is often supplied to the reactor as a uniform solution containing the styrene monomer and the rubber component.

The liquid mixture or the polymerizable liquid containing the styrene-based monomer is a polymerization initiator such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, dicumyl peroxide, methyl ethyl ketone peroxide, and azobisisooxide. Although it often contains butyronitrile or the like, it is not always necessary in the case of thermal polymerization.

If necessary, a solvent such as benzene, ethylbenzene, toluene or xylene, or a solvent inert to the reaction such as mineral oil may be added to each of the mixed liquids and the polymerizable liquid. When a solvent is added, the viscosity of the mixed liquid or the polymerizable liquid can be adjusted, and it may be easier to control the particle diameter of the rubber component. The amount of the solvent added is, for example, 30 parts by weight or less, preferably about 1 to 20 parts by weight, based on 100 parts by weight of the styrene-based monomer. If necessary, a molecular weight modifier, an antioxidant, a lubricant, a plasticizer, etc. may be added to the mixed liquid or the polymerizable liquid.

When the styrene resin is produced by the continuous process shown in FIGS. 3 and 4, the mixing liquid and the polymerizable liquid are fed to the reactor at a rate of non-styrene rubber component and styrene rubber component. Can be appropriately selected depending on the ratio, the ratio of the rubber component to the styrene-based monomer, the rubber phase inversion particle size, and the like.

In the polymerization process of the mixed liquid containing the rubber component or the polymerizable liquid, the rubber component is converted into dispersed particles, that is, the phase is converted into the rubber phase, as the polymerization reaction proceeds. The polymerization conversion rate of the styrene-based monomer in the polymerization step is not particularly limited, and for example, in the preliminary reactor, a range in which the phase conversion of the rubber component can be suppressed by the preliminary polymerization, for example, 5 to 30.
%, Preferably about 7 to 20%, and in the first reactor, the rubber component can undergo phase inversion, for example, 10 to 50%, preferably about 15 to 30%. When the styrene-based monomer is supplied to the second reactor for polymerization, the polymerization conversion rate in the second reactor is, for example, 7 to 40%, preferably about 10 to 30%. Further, even when the polymerizable liquid containing the styrene-based monomer and the rubber component is supplied to the second reactor for polymerization, the polymerization conversion rate in the second reactor may be the same as above. Many. Then, the subsequent post-polymerization reactor is polymerized to a high polymerization conversion rate to produce an impact-resistant styrene resin.

Polymerization is carried out in an inert gas atmosphere such as nitrogen, helium or argon while stirring, for example, 50 to 2
It can be carried out at about 00 ° C., and in the case of thermal polymerization, it is usually carried out at a temperature of 100 ° C. or higher.

In the bulk polymerization, after the completion of the polymerization reaction, the unreacted monomer and, if necessary, the solvent are recovered by a known method, for example, a method such as stripping in which degassing treatment is performed under heating. An impact resistant styrene resin can be obtained. The styrene-based resin may be cut into pellet size by a pelletizer while cooling and solidifying the molten and fluid resin by a conventional method.

These production processes may be carried out in a semi-batch system, but in order to improve the production efficiency, the mixed solution or the polymerizable liquid is continuously fed to the preliminary reactor, the first reactor and the second reactor. Continuously, the polymerization liquid from the first reactor and the polymerization liquid from the second reactor are continuously supplied to the subsequent post-polymerization reactor to successively increase the polymerization conversion rate. It is preferred to polymerize by the formula, especially the continuous bulk polymerization method.

In the rubber-modified styrenic resin obtained by the above-mentioned polymerization, the content of the rubber component substantially corresponds to the total content of the rubber component in the mixed liquid or the polymerizable liquid.
The amount is 1 to 25% by weight, preferably 2 to 20% by weight, more preferably 3 to 15% by weight.

The impact-resistant styrene-based resin may include a stabilizer against heat, light and oxygen (for example, an antioxidant, an ultraviolet absorber, etc.), a flame retardant, a plasticizer, a lubricant, a release agent, if necessary. You may add additives, such as an antistatic agent, a coloring agent, and a filler.

The impact-resistant styrenic resin obtained by the method of the present invention is used in various molded products such as household appliances such as daily necessities, vacuum cleaners, refrigerators, washing machines, fans, radios, televisions, and electronic devices. It can be used for a wide range of applications such as housings and interior / exterior parts for vehicles.

[0075]

In the method and apparatus of the present invention, the pre-reactor and the first reactor, which are connected in series with each other, successively polymerize, and the polymerization liquid from the first reactor and the second reaction are polymerized. The rubber content of the styrene-based resin can be adjusted easily and efficiently by joining the polymerization liquid from the vessel. Further, by confluence of the polymerization solution, the polymerization solution in the previous stage can be efficiently replaced with a new polymerization solution, and various brands of impact-resistant styrene resins having different rubber contents and types of rubber components can be efficiently produced. The rubber particle size can be controlled by sequentially polymerizing the pre-reactor and the first reactor.

When a mixed solution containing a rubber component and a styrene-based monomer is supplied to the first reactor and polymerized, the rubber particle size of the impact-resistant styrene-based resin can be controlled with high accuracy and the bimodal A styrenic resin containing rubber phase particles having a characteristic particle size distribution can be produced. Furthermore, by polymerizing in a polymerization system containing a styrene-based rubber component in the coexistence of a non-styrene-based rubber component, the particle size of the rubber particles can be reduced, and a molded product excellent in both gloss and impact resistance can be obtained. The above-mentioned useful impact resistant styrene resin can be produced.

[0077]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. The rubber particle size and the replacement time were examined as follows.

(1) Rubber particle diameter 0.2 g of a resin sample was added to methyl ethyl ketone / acetone = 1
The mixture was mixed with 10 ml of a mixed solvent of 1/1 (v / v), and the volume average particle size was measured by a light scattering method using a particle size analyzer.

(2) Substitution time In the case of producing a new brand of impact-resistant styrene resin by producing impact-resistant styrene-based resin having a specific rubber content and then supplying and mixing a mixed solution having a different rubber content. The time until the rubber content in the new brand styrene-based resin reaches the control range of the target rubber content ± 0.2% by weight was defined as the replacement time.

Example 1 Using the apparatus composed of the reactor shown in FIG. 1, 9% by weight of polybutadiene, 88% by weight of styrene and 3% of ethylbenzene were used.
The mixed liquid consisting of wt% was fed at a feed rate of 10 Kg / hr to a complete mixing type pre-reactor equipped with a double helical blade, and polymerized at 130 ° C to a conversion of 15 wt%.
The polymerization liquid from the preliminary reactor was sent to the first reactor,
The conversion was increased to 22% by weight at 0 ° C. to invert the rubber component.

On the other hand, 14 kg of styrene was added to the second reactor.
The solution was fed at a feed rate of / hr and polymerized at 135 ° C to a conversion of 25% by weight. The conversion liquid in the final reactor was increased to 90% by weight by feeding the polymerization liquids from the first reactor and the second reactor to the post-polymerization reactor in the latter stage for polymerization.

After the styrene resin was produced as described above, 9K of styrene was added to the second reactor of the apparatus shown in FIG.
Polymerization was carried out in the same manner as above except that the solution was fed at a feeding rate of g / hr. As a result, the substitution time until the resin produced by the first polymerization and remaining in the apparatus was replaced with a new resin was 8 hours, and the rubber content could be adjusted within a short time.

Example 2 Polymerization was carried out by the method of Example 1 to produce a new brand of styrene-based resin, and then styrene was fed to the second reactor of the apparatus shown in FIG. 1 at a feed rate of 4 kg / hr. When the polymerization was carried out in the same manner as in Example 1, the replacement time until the resin remaining in the apparatus was replaced with a new resin was 8 hours, and the rubber content was kept within a short time even if the supply amount of styrene was small. I was able to adjust efficiently.

Example 3 A styrene-containing resin was prepared by using the apparatus composed of the reactor shown in FIG.
A mixed solution of 9% by weight of butadiene rubber, 88% by weight of styrene and 3% by weight of ethylbenzene was supplied at a feed rate of 10 kg.
/ Hr to a complete mixing type pre-reactor equipped with a double helical blade and polymerized at 125 ° C. to a conversion of 10% by weight. The polymerization liquid from the pre-reactor was fed to the first reactor, the conversion rate was increased to 24% by weight at 135 ° C., and the rubber component was phase-inverted. Meanwhile, 14 kg of styrene was added to the second reactor.
The solution was fed at a feed rate of / hr and polymerized at 135 ° C to a conversion of 25% by weight.

The polymerization liquids from the first reactor and the second reactor were fed to the post-polymerization reactor at the latter stage, and the conversion rate in the final reactor was increased to 90% by weight.

After the styrene resin was produced, styrene was polymerized in the same manner as above except that styrene was fed to the second reactor of the apparatus shown in FIG. 1 at a feed rate of 4 kg / hr. The time required for replacement with a new resin was 8 hours, and the rubber content could be adjusted within a short time.

Example 4 Polymerization was carried out in the same manner as in Example 1 except that the apparatus composed of the reactor shown in FIG. 2 was used. After the styrene-based resin was produced, styrene was polymerized in the same manner as above except that styrene was fed to the second reactor of the apparatus shown in FIG. 2 at a feed rate of 4 kg / hr. The time required for replacement with a new resin was 5 hours, and the rubber content could be adjusted within a short time.

Example 5 Using the apparatus composed of the reactor shown in FIG. 3, 9% by weight of polybutadiene, 88% by weight of styrene and 3% of ethylbenzene were used.
The mixed liquid consisting of wt% was supplied at a feed rate of 8 kg / hr.
The mixture was fed to a complete mixing type pre-reactor equipped with a double helical blade and polymerized at 130 ° C. to a conversion of 15% by weight. While feeding the polymerization liquid from the preliminary reactor to the first reactor, 9% by weight of styrene-butadiene rubber and 88% of styrene
2 wt% and 3 wt% ethylbenzene mixed solution
At a feed rate of kg / hr, liquid was sent to the first reactor,
The conversion was increased to 25% by weight at 0 ° C. to invert the rubber component. On the other hand, styrene was fed to the second reactor at a feed rate of 14 kg / hr to carry out polymerization at a conversion rate of 25% by weight at 135 ° C. The polymerization liquids from the first reactor and the second reactor were fed to the post-polymerization reactor in the latter stage, and the conversion rate in the final reactor was increased to 90% by weight.

After the styrene resin was produced, styrene was polymerized in the same manner as above except that styrene was fed to the second reactor of the apparatus shown in FIG. 3 at a feed rate of 4 kg / hr, and remained in the apparatus. The substitution time until the resin was replaced with a new resin was 8 hours, and the rubber content could be adjusted within a short time.

Example 6 Styrene-containing resin was prepared by using the apparatus composed of the reactor shown in FIG.
A mixed liquid composed of 9% by weight of polybutadiene rubber, 88% by weight of styrene and 3% by weight of ethylbenzene was supplied at a feed rate of 8 k.
The mixture was fed at a rate of g / hr to a complete mixing type pre-reactor equipped with a double helical blade and polymerized at 125 ° C. to a conversion of 10% by weight. The polymerization liquid from the pre-reactor was sent to the first reactor, and polybutadiene 9% by weight and styrene 88
A mixed liquid consisting of 3 wt% of ethylbenzene and 3 wt% of ethylbenzene was sent to the first reactor at a feed rate of 2 kg / hr, and was heated at 130 ° C.
The conversion rate was increased to 25% by weight to invert the rubber component.

On the other hand, 14 kg of styrene was added to the second reactor.
The liquid was sent at a flow rate of / hr, and polymerization was performed at 135 ° C with a conversion of 25% by weight. The polymerization liquids from the first reactor and the second reactor were fed to the post-polymerization reactor at the latter stage, and the conversion rate in the final reactor was increased to 90% by weight.

After the styrene resin was produced, styrene was polymerized in the same manner as above except that styrene was fed to the second reactor of the apparatus shown in FIG. 4 at a feed rate of 4 kg / hr.
The replacement time until the resin remaining in the apparatus was replaced with a new resin was 5 hours, and the rubber content could be adjusted within a short time.

Comparative Example 1 An apparatus constituted by the reactor shown in FIG. 5, that is, an apparatus in which four completely mixed reactors 51, 52, 53 and 54 were connected in series was used. A mixed solution of 3.7% by weight of polybutadiene, 94.3% by weight of styrene, and 2% by weight of ethylbenzene was supplied at a supply rate of 10 kg / hr to a complete mixing type pre-reactor 51 equipped with a double helical blade, and 1
Polymerization was carried out at 25 ° C to a conversion of 10% by weight.

The polymerization liquid from the pre-reactor 51 was fed to the first reactor 52 and the conversion rate was increased to 17% by weight at 125 ° C. to invert the rubber component. The polymerization liquid from the first reactor 52 was sent to the post-polymerization reactors 53 and 54 in the subsequent stage, and the conversion rate in the final reactor was increased to 90% by weight.

After the styrene resin was produced, a mixed solution of 4.7% by weight of polybutadiene, 93.3% by weight of styrene and 2% by weight of ethylbenzene was fed to the preliminary reactor of the apparatus shown in FIG. 5 at a feed rate of 10 kg / hr. Supplied at 125 ° C
Was polymerized to a conversion of 10% by weight. The polymerization solution from the prognosis reactor was sent to the first reactor, and the conversion was 19 at 127 ° C.
The rubber component was phase-inverted by increasing it to the weight percent.

The polymerization liquid from the first reactor was fed to the post-polymerization reactor at the latter stage, and the conversion rate in the final reactor was increased to 90% by weight. Then, when the substitution time until the resin remaining in the apparatus was replaced with a new resin was examined, it was 12 hours, and it took a long time to adjust the rubber content.

Comparative Example 2 After polymerizing by the method of Comparative Example 1 to produce a new brand of styrene resin, 6.4% by weight of polybutadiene and 91 of styrene were placed in the complete mixing type pre-reactor 51 of the apparatus shown in FIG. ．
A mixed solution of 6% by weight and 2% by weight of ethylbenzene,
Supply at a supply rate of 10 kg / hr and a conversion rate of 1 at 125 ° C.
It was polymerized to 0% by weight.

The polymerization liquid from the pre-reactor 51 was fed to the first reactor 52, the conversion rate was increased to 21% by weight at 128 ° C., and the rubber component was phase-inverted. The polymerization liquid from the first reactor 52 was sent to the post-polymerization reactors 53 and 54 in the subsequent stage, and the conversion rate in the final reactor was increased to 90% by weight. Then, when the substitution time until the resin remaining in the apparatus was replaced with a new resin was examined, it was 13 hours, and it took a long time to adjust the rubber content.

Comparative Example 3 An apparatus constituted by the reactors shown in FIG. 6, that is, two complete mixing type reactors 61 and 62, a tower type reactor 63 with a stirrer, and a static mixer type reactor 64. Was used in series.

Polybutadiene 3.7% by weight, styrene 9
A mixed solution consisting of 4.3% by weight and 2% by weight of ethylbenzene was supplied at a supply rate of 10 kg / hr to a complete mixing type pre-reactor 61 equipped with a double helical blade and polymerized at 125 ° C. to a conversion of 10% by weight. Let The polymerization liquid from the pre-reactor 61 was sent to the first reactor 62, the conversion rate was increased to 17% by weight at 125 ° C., and the rubber component was phase-inverted. The polymerization liquid from the first reactor 62 was sent to the reactors 63 and 64 in the subsequent stage, and the conversion rate in the final reactor was increased to 90% by weight.

After the impact resistant styrene resin was produced as described above, 6.4% by weight of polybutadiene and 91.6% by weight of styrene were added to the pre-reactor 61 of the apparatus shown in FIG.
A mixed solution consisting of 2% by weight of ethylbenzene was fed at a feed rate of 1
It was fed at 0 kg / hr and polymerized at 125 ° C. to a conversion of 10% by weight. The polymerization liquid from the pre-reactor 61 was fed to the first reactor 62, the conversion rate was increased to 21% by weight at 128 ° C., and the rubber component was phase-inverted. The polymerization liquid from the first reactor 62 was sent to the reactors 63 and 64 in the subsequent stage, and the conversion rate in the final reactor was increased to 90% by weight. Then, when the substitution time until the resin remaining in the apparatus was replaced with a new resin was examined, it was 11 hours, and it took a long time to adjust the rubber content.

Tables 1 and 2 show the polymerization conditions in Examples 1 to 6 and Comparative Examples 1 to 3 and the characteristics of the obtained styrene resins.

[0103]

[Table 1]

[0104]

[Table 2] As is clear from Table 1 and Table 2, in the methods of Examples 1 to 7, even if the rubber content of the styrene resin is high, the replacement time until the resin remaining in the apparatus is replaced with a new resin is shortened. Therefore, the rubber content of the styrene resin can be efficiently adjusted. Further, a styrene resin having a bimodal rubber phase particle diameter can be produced by supplying a mixed liquid containing a rubber component and a styrene monomer to the first reactor.

Example 7 Using the apparatus composed of the reactor shown in FIG. 1, 8% by weight of polybutadiene, 90% by weight of styrene and 2% of ethylbenzene were used.
A mixed liquid consisting of wt% was supplied at a supply rate of 10 kg / hr,
It is supplied to a complete mixing type pre-reactor equipped with a double helical blade and polymerized at 130 ° C, and the polymerization liquid from the pre-reactor is fed to the first reactor and polymerized at 130 ° C to obtain a conversion of 20% by weight. And the rubber component was phase-inverted.

On the other hand, a mixed solution of 8% by weight of styrene-butadiene rubber, 90% by weight of styrene and 2% by weight of ethylbenzene was fed to the second reactor at a feeding rate of 8 kg / hr and polymerized at 135 ° C. First reactor and second
The polymerization liquid from the reactor of (1) was sent to the subsequent post-polymerization reactor to increase the polymerization conversion rate in the final reactor to 90%.

Example 8 Polymerization was carried out in the same manner as in Example 1 except that the feed rates of the raw material solutions to the pre-reactor and the second reactor were 4 kg / hr and 6 kg / hr, respectively, and the impact resistance was measured. A styrene resin was produced.

Example 9 Using the apparatus composed of the reactor shown in FIG. 1, 6% by weight of polybutadiene, 92% by weight of styrene and 2% of ethylbenzene were used.
The mixed liquid consisting of wt% was supplied at a supply rate of 3 kg / hr to a complete mixing type pre-reactor equipped with a double-helical blade and was polymerized at 130 ° C.
Sent to the reactor, polymerized at 130 ° C, conversion rate 20% by weight
And the rubber component was phase-inverted.

On the other hand, a mixed solution of 6% by weight of styrene-butadiene rubber, 92% by weight of styrene and 2% by weight of ethylbenzene was fed to the second reactor at a feeding rate of 7 kg / hr and polymerized at 135 ° C. First reactor and second
The polymerization liquid from the reactor of (1) was sent to the subsequent post-polymerization reactor to increase the polymerization conversion rate in the final reactor to 90%.

Example 10 Using the apparatus composed of the reactor shown in FIG. 2, 8% by weight of polybutadiene, 90% by weight of styrene, and 2% of ethylbenzene were used.
The mixed liquid consisting of wt% was supplied at a supply rate of 2 kg / hr to a complete mixing type pre-reactor equipped with a double helical blade, and polymerized at 130 ° C. While feeding the polymerization liquid from the preliminary reactor to the first reactor, 8% by weight of styrene-butadiene rubber and 90% by weight of styrene were fed to the first reactor.
A mixed solution consisting of 2% by weight of ethylbenzene was fed at a feed rate of 1
It was supplied at kg / hr, polymerized at 130 ° C., the conversion rate was increased to 20% by weight, and the rubber component was phase-inverted.

On the other hand, a mixed solution of 8% by weight of styrene-butadiene rubber, 90% by weight of styrene and 2% by weight of ethylbenzene was fed to the second reactor at a feeding rate of 7 kg / hr and polymerized at 135 ° C. First reactor and second
The polymerization liquid from the reactor of (1) was sent to the subsequent post-polymerization reactor to increase the polymerization conversion rate in the final reactor to 90%.

Example 11 Polymerization was performed in the same manner as in Example 10 except that the feed rates of the raw material solutions to the pre-reactor and the second reactor were 3 kg / hr and 6 kg / hr, respectively, and impact resistance was measured. A styrene resin was produced.

Example 12 Polymerization was carried out in the same manner as in Example 10 except that the feed rates of the raw material solutions to the pre-reactor and the second reactor were 2 kg / hr and 6 kg / hr, respectively, and impact resistance was measured. A styrene resin was produced.

Example 13 The feed rates of the raw material solutions to the pre-reactor, the first reactor and the second reactor were 3 kg / hr and 2 kg / hr, respectively.
Polymerization was carried out in the same manner as in Example 10 except that the amount was 5 kg / hr and an impact resistant styrene resin was produced.

Example 14 Polymerization was performed in the same manner as in Example 13 except that the feed rates of the raw material solutions to the first reactor and the second reactor were 3 kg / hr and 4 kg / hr, respectively. An impact styrenic resin was produced.

Example 15 Using the apparatus composed of the reactor shown in FIG. 2, 6% by weight of polybutadiene, 92% by weight of styrene, and 2% of ethylbenzene were used.
The mixed liquid consisting of wt% was supplied at a supply rate of 3 kg / hr to a complete mixing type pre-reactor equipped with a double helical blade, and polymerized at 130 ° C. While feeding the polymerization liquid from the preliminary reactor to the first reactor, 6% by weight of styrene-butadiene rubber and 92% by weight of styrene were fed to the first reactor.
A mixed solution consisting of 2% by weight of ethylbenzene was supplied at a feed rate of 4
It was supplied at kg / hr, polymerized at 130 ° C., the conversion rate was increased to 20% by weight, and the rubber component was phase-inverted.

On the other hand, a mixed solution of 6% by weight of styrene-butadiene rubber, 92% by weight of styrene and 2% by weight of ethylbenzene was fed to the second reactor at a feeding rate of 3 kg / hr and polymerized at 135 ° C. First reactor and second
The polymerization liquid from the reactor of (1) was sent to the subsequent post-polymerization reactor to increase the polymerization conversion rate in the final reactor to 90%.

Comparative Example 4 An apparatus constituted by the reactor shown in FIG. 5, that is, an apparatus in which four completely mixed reactors 51, 52, 53 and 54 were connected in series was used. The preliminary reactor was used as the first reactor 51. A mixed liquid consisting of 8% by weight of polybutadiene, 90% by weight of styrene and 2% by weight of ethylbenzene was supplied at a supply rate of 2 kg / hr to a complete mixing type first reactor 51 equipped with a double helical blade, at 130 ° C.
Was polymerized to a conversion of 20% by weight, and the rubber component was phase-inverted.

On the other hand, while feeding the polymerization liquid from the first reactor 51 to the second reactor 52, 8% by weight of styrene-butadiene rubber, 90% by weight of styrene, and 2% of ethylbenzene were fed to the second reactor 52. A mixed solution of wt% was fed at a feed rate of 8 kg / hr and polymerized at 135 ° C.

The polymerization liquid from the first reactor 51 and the second reactor 52 was fed to the post-polymerization reactors 53 and 54 in the subsequent stage, and the conversion rate in the final reactor was increased to 90% by weight.

Comparative Example 5 A mixed solution of 6% by weight of polybutadiene, 92% by weight of styrene and 2% by weight of ethylbenzene was supplied to the first reactor 51 of the apparatus shown in FIG. 5 at a supply rate of 4 kg / hr.
Same as Comparative Example 4 except that a mixed solution of 6% by weight of styrene-butadiene rubber, 92% by weight of styrene and 2% by weight of ethylbenzene was fed to the second reactor 52 at a feed rate of 6 kg / hr for polymerization. Then, a styrene resin was produced.

Comparative Example 6 Device constituted by the reactor shown in FIG. 6, that is, two completely mixed reactors (first reactor and second reactor) 6
A styrene-based resin was produced in the same manner as in Comparative Example 4 except that an apparatus in which 1, 62, a tower reactor 63 with a stirrer, and a static mixer reactor 64 were connected in series.

Comparative Example 7 A styrenic resin was produced in the same manner as in Comparative Example 6 except that the mixed liquid supply rates to the first reactor and the second reactor were 4 kg / hr and 6 kg / hr, respectively. did.

Comparative Example 8 The apparatus shown in FIG. 7, that is, the apparatus shown in FIG. 1 without the preliminary reactor was used. In this apparatus, a first reactor 71 and a second reactor 72 are provided in parallel, and two post-polymerization reactors 73 and 74 are connected in series to the first reactor 71. . Then, a styrene resin was produced in the same manner as in Comparative Example 5 except that the apparatus shown in FIG. 7 was used.

Polymerization conditions and properties of the resulting styrene resin are shown in Tables 3 and 4.

[0126]

[Table 3]

[0127]

[Table 4] As is clear from Tables 3 and 4, according to the methods of Examples 7 to 15, the rubber particle size of the impact resistant styrene resin can be controlled with high accuracy. Furthermore, by polymerizing in a polymerization system containing a styrene-based rubber component in the coexistence of a non-styrene-based rubber component, the particle size of rubber particles can be reduced.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing an example of an apparatus of the present invention.

FIG. 2 is a schematic configuration diagram showing another example of the apparatus of the present invention.

FIG. 3 is a schematic configuration diagram showing still another example of the apparatus of the present invention.

FIG. 4 is a schematic configuration diagram showing another example of the apparatus of the present invention.

FIG. 5 is a schematic configuration diagram showing an apparatus used in Comparative Examples 1, 2, 4 and 5.

FIG. 6 is a schematic configuration diagram showing an apparatus used in Comparative Examples 3, 6 and 7.

FIG. 7 is a schematic configuration diagram showing an apparatus used in Comparative Example 8.

[Explanation of symbols]

 2 ... Pre-reactor 4, 32, 42 ... First reactor 7 ... Second reactor 9, 11, 12, 22 ... Post-polymerization reactor

Claims (12)

[Claims] 1. A mixed solution containing a styrene-based monomer and a rubber component is polymerized in a pre-reactor, and a polymerization liquid from the pre-reactor is polymerized in a first reactor connected in series with the pre-reactor. Polymerization and polymerization of a polymerizable liquid containing at least a styrene monomer in the second reactor, and polymerization of the polymerization liquid from the first reactor and the second reactor in a post-polymerization reactor. A method for producing an impact-resistant styrene resin. 2. A mixed liquid containing a styrene-based monomer and a rubber component is continuously supplied to a pre-reactor and a first reactor for polymerization, and a polymerizable liquid containing at least a styrene-based monomer is added. Polymerization by continuously feeding to the second reactor,
The method for producing an impact-resistant styrene-based resin according to claim 1, wherein the polymerization liquids from the first reactor and the second reactor are continuously supplied to the post-polymerization reactor to perform polymerization. 3. The pre-reactor and the first reactor are constituted by perfect mixing type reactors, and the post-polymerization reactor is constituted by a plurality of perfect mixing type reactors or a plurality of plug flow type reactors. Item 2. A method for producing an impact resistant styrene resin according to Item 1. 4. A mixed solution containing a styrene-based monomer and a rubber component different from the rubber component supplied to the preliminary reactor in the presence of the polymerization liquid from the preliminary reactor is fed to the first reactor. The method for producing an impact-resistant styrenic resin according to claim 1, wherein the method comprises supplying and polymerizing. 5. A solution containing a styrene-based monomer and a non-styrene-based rubber component or a rubber component having a styrene unit is continuously supplied to a fully mixed pre-reactor and a completely mixed first reactor. The rubber component was sequentially polymerized to invert the rubber phase, and the styrene-based monomer was continuously supplied to the second reactor to polymerize, and the styrene-based monomer was fed from the first reactor and the second reactor. The method according to claim 1, wherein the impact-resistant styrenic resin is produced by a bulk continuous polymerization method in which the polymerization liquid is continuously supplied to a post-polymerization reactor to perform polymerization. 6. A rubber composition having a styrene monomer and a styrene unit while polymerizing a mixed solution containing a styrene monomer and a non-styrene rubber component in a pre-reactor and a first reactor in order. The method for producing an impact-resistant styrenic resin according to claim 1, wherein a polymerizable liquid containing a is polymerized in the second reactor. 7. A mixture of a styrene monomer and a non-styrene rubber component is polymerized in a pre-reactor, and the styrene monomer and styrene unit are present in the presence of the pre-polymerization liquid from the pre-reactor. A polymerization solution containing a styrene-based monomer and a rubber component having a styrene unit is polymerized in a second reactor while a mixed solution containing a rubber component having a styrene unit is polymerized in the first reactor. The method for producing an impact-resistant styrene-based resin according to 1 or 6. 8. The difference between the particle size of a large particle rubber composed of a non-styrene rubber component and the particle size of a small particle rubber composed of a rubber component having a styrene unit is 0.5 μm or less. Item 7. A method for producing an impact resistant styrene-based resin according to Item 6. 9. A rubber component is obtained by continuously supplying a solution containing a styrene-based monomer and a non-styrene-based rubber component to a completely mixed pre-reactor and a completely mixed first reactor to sequentially polymerize them. While inverting the rubber phase, styrene-based monomer,
A solution containing a rubber component having a styrene unit is polymerized in the second reactor, and the polymerization liquids from the first reactor and the second reactor are continuously supplied to the post-polymerization reactor for polymerization. By the block continuous polymerization method, the difference between the particle size of the large particle rubber composed of the non-styrene-based rubber component and the particle size of the small particle rubber composed of the rubber component having a styrene unit is 0.1.
The method according to claim 1, wherein an impact-resistant styrenic resin having a particle size of 0.5 μm is produced. 10. The non-styrene rubber component is butadiene rubber, and the rubber component having a styrene unit is styrene-
A method for producing an impact-resistant styrene resin according to any one of claims 6 to 9, which is a butadiene rubber. 11. A pre-reactor, a first reactor and a second reactor.
7. The impact-resistant styrenic resin according to claim 6, wherein said reactor is a completely mixed reactor, and said post-polymerization reactor is composed of a plurality of completely mixed reactors or a plurality of plug flow reactors. Production method. 12. A pre-reactor for pre-polymerizing a mixed solution containing a styrenic monomer and a rubber component, and a polymerization solution connected from the pre-reactor in series with the pre-reactor. Of the polymerization liquid from the first reactor and the second reactor, and a second reactor for polymerizing a polymerizable liquid containing at least a styrenic monomer. An apparatus for producing an impact-resistant styrene-based resin, comprising a post-polymerization reactor for increasing a polymerization conversion rate.