JPS60233117A - Continuous preparation of rubber-modified aromatic monovinyl resin - Google Patents

Abstract

PURPOSE:To obtain continuously the titled resin having improved coloring properties and mechanical properties, by blending the first flow prepared by a solution of a rubber-like substance and an aromatic vinyl monomer in a solvent with the second flow prepared by polymerizing a solution of the monomer in a solvent in a specific device with stirring. CONSTITUTION:(A) The first flow prepared by polymerizing a solution consisting of (i) 6-13wt% rubber-like substance, (ii) 62-94wt% aromatic monovinyl monomer, and (iii) 0-25wt% solvent, in which polymerization is stopped so that the polymer has <= polymerization conversion ratio to granulate the component i is blended with stirring with (B) the second flow prepared by polymerizing a solution consisting of 75-100wt% component ii and 0-25wt% component iii, containing 30-70wt% solid substance in a ratio of 7/3-3/7 while maintaining the distance d between the tip of agitating blade and a device wall of 1-20mm., and a ratio r/d of the peripheral speed r (mm./sec) of at the tip of the agitating blade to d of >=50. After the blending, the polymerization is further advanced, unpolymerized component ii and the solvent are recovered to give continuously the desired resin containing 3-15wt% component i.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a continuous process for producing a rubber-modified aromatic monovinyl resin having excellent colorability and good mechanical properties.

[Problem that the invention seeks to solve]

In the production of rubber-modified aromatic monovinyl resins, such as rubber-modified polystyrene, continuous bulk polymerization or continuous solvent bulk polymerization using a solvent is carried out in bulk-part 2 using water as a medium.
Compared to stage polymerization, it is less sloppy during water contamination, uses less energy, and is generally better than bulk-suspension polymerization, which is a batch process.
It is advantageous in terms of uniformity of quality and productivity, and is highly economical. However, on the other hand, polymers obtained by continuous bulk polymerization or continuous solvent bulk polymerization have poorer coloring properties than those obtained by batch-type bulk-suspension polymerization. In recent years, in order to rationalize coloring, it has become important to adjust the color of natural-colored pellets with a small amount of dye and pigment, and excellent coloring properties are required. Furthermore, in order to make products thinner, there is a demand in the market for rubber-modified polystyrene having better impact strength and rigidity.

[Conventional technology]

Conventionally, a styrene monomer solution containing a rubbery substance is polymerized,
A method is known in which a rubber-like substance is made into particles, bulk polymerization is carried out until a stable particle size is maintained, and then transferred to suspension polymerization in the middle of polymerization.
Tokuko Sho'l/-/93! ; Ko Publication, U.S. Patent No. 3 Dag
g7da No. 3 specification, etc.), a method in which polystyrene is added during polymerization and then polymerization is continued to form particles of a rubber-like substance (
Special Public Sho 4 (J-/39t3 Publication, Special Public Sho 3 Co/
74!4, etc.), a method in which a part of the rubbery substance is polymerized, and then the rubbery substance and, if necessary, a styrene polymer are added to make the rubbery substance into particles (Japanese Patent Publication No. 1I9-3!f
07'1 Publication). However, both of these techniques involve a suspension polymerization step. Also, bulk-suspension polymerization,
It is known to add polystyrene before the start of polymerization in any bulk polymerization process (US Pat. No. 3/1).
I41IIaO specification etc.). In bulk polymerization, a styrene solution of a rubber-like substance is polymerized17, the rubber-like substance is made into particles and the polymerization is allowed to progress (such as U.S. Pat. No. 249116-j), or after particle formation, a separately prepared polystyrene solution is used. It has been proposed to mix and further carry out continuous polymerization without a catalyst (US Pat. No. 3,471,127).

The present inventors have intensively studied a method for producing a rubber-modified aromatic monovinyl resin that takes advantage of the above-mentioned continuous bulk polymerization (including solvent bulk polymerization) and has excellent coloring properties and mechanical properties, and as a result, has developed a new method. We have arrived at the present invention as a manufacturing method.

[Means for solving problems]

That is, in the present invention, a solution of an aromatic monovinyl monomer of a rubber-like substance is polymerized, and a first stream is maintained within a range that does not exceed the polymerization conversion rate at which the rubber-like substance becomes particles, and an independent first stream is In producing a polymerization product from an aromatic monovinyl monomer as the second stream, continuously mixing the first stream and the second stream in the middle of polymerization, and forcibly turning the rubbery substance into particles, The λ liquid in the middle of polymerization is mixed and stirred under a controlled device and conditions.
Furthermore, the present invention relates to a method characterized in that after the rubber-like substance is made into particles, polymerization is continued.

The present inventors have previously proposed a novel method for producing a continuous rubber-modified aromatic monovinyl resin in Japanese Patent Application No. Sho Sku 2/'IA3/. The present invention relates to a production method that specifies polymerization conditions and further improves resin properties. More specifically, (a) Rubber-like substance 6-
Polymerizing a solution (1) consisting of 73% by weight, aromatic monovinyl monomer t2 to 91% by weight, and 0 to 25% by weight of solvent,
(b) aromatic monovinyl monomer; (b) aromatic monovinyl monol;
Polymerize solution (II) containing 75 to 10 θ weight % of isomer and 0 to 23 weight % of solvent to obtain 30 to 70 weight % of isomer
A production method characterized by continuously mixing and stirring the second stream containing □ under specific equipment and conditions, and further polymerizing the rubber-like substance by continuously mixing and stirring the second stream containing □. It is related to. Here, the specific equipment and conditions are such that the mixing agitator is placed between the tip of the stirring blade and its side wall so that the two solutions can be mixed and stirred in an extremely short time.
This means that d is /~, 2011BIl, and the ratio r/d between the interval @d and the circumferential speed r (m/sec) of the tip of the stirring blade is 501, preferably 70 or more. Further, the mixing ratio of the solution (1) and the solution (1) is adjusted to be in the range of 7:3 to 3 degrees, and the solid substance of the solution (n) is adjusted to be in the range of 3θ to 70 degrees.
% by weight.

〔Effect of the invention〕

According to the method of the present invention, a rubber-modified aromatic monovinyl resin with an excellent balance of colorability, impact resistance, and rigidity can be produced by continuous bulk polymerization (including solvent bulk polymerization). In general, impact resistance and colorability, and impact resistance and rigidity are contradictory properties, and it is of great value to be able to obtain a resin that is excellent in all three properties by a highly economical continuous polymerization method.

In the present invention, the rubber-like substance refers to a homopolymer of a conjugated 3-diene having a carbon number of d to 6, such as a homopolymer of 3-butadiene,
, 3-butadiene and isopre/copolymer, /, 3-
Copolymerization of isoprene with phtadiene or/or 3-butadiene and other copolymerizable compounds, such as styrene, methylstyrene of nuclear alkyl-substituted styrenes, dimethylstyrene, acrylonitrile, methacrylonitrile, alkyl esters of acrylic acid and methacrylic acid. It is a combination. These may be used alone or as a mixture of two or more. Particularly preferred are polybutadiene rubber and butadiene-styrene random copolymer rubber.

In the present invention, the aromatic monovinyl monomers include styrene and nuclear alkyl-substituted styrenes such as 0-methylstyrene, -methylstyrene, m-methylstyrene, co-, tert-methylstyrene, ethylstyrene, and p-tert-butylstyrene, α - methylstyrene, α-furkyl substituted styrene such as α-methyl-p-methylstyrene, 0-chlorostyrene, m-chlorostyrene, p-chlorostyrene,
Nuclear halokenated styrenes such as p-bromostyrene, comethyl-/, lI-chlorostyrene, co- and terdipromostyrene, and vinylnaphthalene can be used alone or as a mixture of two or more of them.

Solvents used in the present invention include aromatic hydrocarbons (a) such as toluene, peroxylene, and ethylbenzene alone or in mixtures of two or more. Furthermore, within the range not impairing the dissolution of the rubbery substance and the polymerization product from the aromatic monovinyl monomer,
Other solvents, such as aliphatic hydrocarbons, dialkyl ketones, can be used in combination with aromatic hydrocarbons. The rubbery material is dissolved in a mixture with aromatic monovinyl monomer or solvent to a concentration of 6 to 3% by weight. Outside this range, the resin obtained by mixing and stirring with the solution (n) containing 30 to 70% by weight of solid substances and polymerizing the resin will have poor impact strength, rigidity, and colorability. The solvent is O-
It is used in a range of 25% by weight. If it exceeds 25% by weight, the polymerization rate will drop significantly and the impact strength of the resulting resin will drop significantly.

Moreover, the energy required to recover the solvent is large, resulting in poor economic efficiency. The solvent may be added after the polymerization conversion reaches a relatively high viscosity, or may be added before the polymerization. It is preferable to add 5 to 75% by weight before polymerization in terms of quality uniformity and polymerization temperature control.

The present invention is characterized in that the first flow is kept within a range that does not exceed the polymerization conversion rate at which the rubber-like material becomes particles, and the solid material content is within a range that does not cause a so-called phase transition phenomenon;
In the second stream, the first stream and the second stream are mixed at a mixing ratio of 7:1 while producing a polymerization product from the aromatic monovinyl monomer with a solids content in the range of 30-70% by weight. 3～
3: Continuously mix and stir to bring the rubbery substance to about 10%. − It consists in forcibly turning into particles. When the mixing ratio is greater than 7=3, it becomes difficult to forcibly form the rubbery substance into particles. Moreover, if it is outside the 3-nea range, it is difficult to obtain a resin that satisfies the impact strength. The mixing ratio is preferably in the range of 7:3 to 7:6.

The mixing agitator of the present invention has a space between the tip of the agitating blade and the 1000 lateral wall so that the two flows can be mixed and agitated instantly.
d should be 7 to 20 m, and any material that can maintain the ratio r/d between the distance 1 it Ld and the circumferential speed r (w/sec) of the tip of the stirring blade to SO, preferably 70 or more is sufficient. For example, it is a mixing agitator having a stirring blade that imparts dynamic shear or a stirring rotor blade. In the present invention, the gap between the rotor and the side wall, and the gap between the tip of the protrusion on the side wall when a protrusion such as a bottle, a heat transfer tube, or a baffle plate is protruding, and the stirring blade or the stirring rotor are generally the same as the tip of the stirring blade. It shall be called the gap between it and the side wall. The stirring blades in the present invention are multi-stage rod-shaped, seed-shaped, turbine-shaped, propeller-shaped, etc., which can apply shear force to stir the mixed solution in the circumferential direction at least three times when the mixed solution is extruded in the axial direction. 10- It is a stirring rotor blade that can apply shear force in the la-type or gap. After particle formation under such conditions, polymerization is continued. The solid substance referred to herein is composed of a polymerization product from an aromatic monovinyl monomer or a rubber-like substance together with the polymerization product.

The first stream is a polymerization product of aromatic monovinyl monomer/
The weight ratio of the rubbery substance is /,j is the upper limit, and O7~/,2
A range of 03 to /, θ is preferable in order to particularly improve the rigidity among the coloring properties and mechanical properties of the resulting resin. If the polymerization conversion rate is increased to the point where the rubber-like substance becomes particulate, the colorability of the final resin will be significantly reduced, making it impossible to achieve the object of the present invention. The first stream can be polymerized in the temperature range of 100 to 10° C. in the absence of a polymerization initiator, but a polymerization initiator is used to increase colorability and improve impact strength. Organic peroxides that generate radicals can be used as polymerization initiators in the present invention. Temperature Sθ~/'10°C, preferably 70-/
Polymerization is carried out in the temperature range of -0 DEG C., either at a constant temperature or by gradually increasing the temperature, in the non-particulate range μ of the rubbery substance.

The organic peroxide may be added to the first stream only;
, and the second. Further, it may be added during or immediately after the rubber-like substance is made into particles. In order to obtain a resin with excellent colorability and impact strength, it is preferable to polymerize the rubber-like substance in the presence of an organic peroxide.

The organic peroxide used in the present invention is j,,2-bis(
1-butylperoxy)butane, Co, Corbis(t-butylperoxy)octane, /, /-bis(t-butylperoxy) 3. J,! -)limethylcyclohexane, /,/-bis(-t-butylperoxy)cyclohexane, peroxyketals such as n-butyluda, Dervis(t-butylperoxy)valate, di-t-butylperoxide, t -butylcumyl peroxide, dicumyl peroxide, α,α'-bis(t-butylperoxyisopropyl)benzene, 2. Dialkyl peroxides such as S-dimethyl-J, S-di(t-)ethylperoxy)hexane, co,5-dimethylco, and S-di(1-butylperoxy)hexyne-3, acetyl peroxide, Imptyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide 5,? .

5, t-trimethylhexanoyl peroxide,
Diacyl peroxides such as benzoyl peroxide, J,lI-dichlorobenzoyl peroxide, m-)luoyl peroxide, di-inopropyl peroxydicarbonate, di-1-ethylhexyl oxydicarbonate, and di-diacyl peroxide.

-Propyl peroxydicarbonate, di-myristyl peroxydicarbonate, dicoethoxyethyl peroxydicarbonate, di-7toxyisopropyl peroxydicarbonate, di, (3-methyl-3-methoxybutyl) peroxydicarbonate Peroxydicarbonates such as carbonate, t-butyl peroxyacetate,
t-Butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxycoethylhexanoate, t73-monobutyl Peroxy3. ! ,! -trimethylhexanoate, t-butylperoxylaurate, -butylperoxybenzoate, di-t-butylciba-oxyisophthalate, co-,t-terdimethyl-x, t-(benzoylperoxy)hexane, -butylbar Peroxy esters such as oxyisoglobil carbonate, acetylacetone peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3
．． ! f-) Ketone peroxides such as limethyl cyclohexanone peroxide and methyl cyclohexanone peroxide, t-butylnohydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, p-mentha hydroperoxide , J! -Dimethyl bexanoco. 5-Gino・
Hydroperoxides such as hydroperoxide, /, /, 3-tetramethylbutyl hydroperoxide, polyacyl peroxides of cobasic acids, and polyperoxy esters of dibasic acids and polyols are included.

-/4'- In the second stream, 7S to ioo weight percent of aromatic monovinyl monomer and 0 to 25 weight percent of solvent are polymerized in the temperature range of 110 to 7 g in the absence of a polymerization initiator, or Using the organic peroxide, 50-7g0℃, preferably 70-760℃
°C, more preferably? polymerize at a temperature range of θ to /lIO°C to produce a polymerization product of aromatic monovinyl monomer sufficient to particulate the rubbery material when continuously mixed with the first stream; .

In the first stream and the second stream, chain transfer agents such as mercaptans, α-methylstyrene linear dimer, terpinolene, and antioxidants such as hindered phenols, hindered bisphenols, and hindered trisphenols are added. etc., e.g.
-butyl-guhydroxyphenyl) propionate can be added. By adding one chain transfer agent and an antioxidant to the first stream, a resin with better coloring properties can be obtained.

After mixing, the system has a ratio of the amount of polymerization product of aromatic monovinyl monomer/the amount of rubbery substance of 2 or more. Furthermore, the polymerization conversion rate of the aromatic monovinyl monomer is increased in at least one polymerization machine, and the average particle diameter of the rubbery substance is 0.7 to 0.7.
Make it S micron.

The amount of the organic peroxide added is 0.007 to 0.007 to 700 parts by weight of the rubbery material, aromatic monovinyl monomer, and solvent in the first stream and the second stream combined. 2 parts by weight, preferably 0.02 to θ parts by weight. The organic peroxide is preferably decomposed while the solvent and unpolymerized monomer are recovered.

Next, volatile components such as the solvent and unpolymerized monomers are removed from the solid substance in vacuum in a short time in a temperature range of 7tθ to 260°C by a conventional method.

Furthermore, additives such as antioxidants, dyes and pigments, lubricants, fillers, mold release agents, plasticizers, and antistatic agents can be added as necessary.

At the stage of removing volatile components, the rubber-modified aromatic monovinyl resin of the present invention contains a rubber-like substance in an amount of 3~/j% by weight, has an average particle size of 07~S microns, and has a gel content of 6~/j% by weight.
lIθ weight %, swelling index 7 to /lI, and in addition to excellent colorability, it has good mechanical properties with excellent impact strength and rigidity.

〔Example〕

Examples are shown below. The characteristic values in the examples were measured based on the following method.

Mechanical properties: Tensile strength: Measured in accordance with JISK RI//3. Izotsu impact strength: JIS K? // According to θ. Flexural modulus: According to ASTM D 790. The three above pellets were wrapped around an injection molded specimen. Gel content and swelling index: Toluene of λθ- is added to a resin of /f, and the resin is vigorously mixed for 7 hours to dissolve or swell. Next, the gel is sedimented using a centrifuge, and the supernatant liquid is discarded by decantation, and the sedimented gel is weighed. The toluene-swollen gel thus obtained is dried at /Aθ° C. and normal pressure for 4 Ij minutes, then for 1S min under reduced pressure on a 3-liquid fin mass, cooled in a desiccator, and then weighed. Gel content is expressed in weight percent by dividing the weight of dry gel by the weight of resin. The swelling index is expressed as the quotient obtained by dividing the weight of the toluene-swollen gel by the weight of the dry gel.

Particle size of rubbery substance in resin: Coulter counter (
Using a mixed electrolyte of dibutylformamide and ammonium thiocyanate, 2 to 7 resin pellets are placed in about 50% dimethylporamide using a Coulter Counter (type TA-it) and left for about 1 to 3 minutes. Next, the dimethylformamide dissolved content is adjusted to an appropriate particle concentration and measured using a 30 micron aperture tube. The median diameter of Sθ is defined as the average particle diameter.

EXAMPLE/ The following mixture (a) was prepared in 2.5 hours at a feed rate of 2117 hours as the first stream. It is continuously fed into the first polymerizer of Ql.

Mixture (a) Polybutadiene rubber 2 parts by weight Styrene 25 parts by weight Ethylbenzene io, o by weight Total 190 parts by weight i, 1-bis(t-butylperoxy)cyclohexane aots parts by weight - di-t-butyl-goo Methylphenol Q10 Part by weight α-methylstyrene linear dimer 007! ; Parts by weight The temperature of the seventh polymerizer was 96° C., and the solid material concentration at the outlet was 15% by weight. Phase contrast microscopy showed black polystyrene particles in the white rubber continuous phase, and the rubber phase had not yet turned into particles.

As a second stream, the following mixture (b) is continuously fed into the second polymerizer A, jJ at a feed rate of /l/h.

Mixture (b) 100 parts by weight The temperature of the second polymerizer was /3θ~/Da3°C, and the solid material concentration at the outlet was 36% by weight.

These first and second flows have a capacity of azl, the gap between the tip of the stirring blade and the mixer wall is 5 m, and /j stages of stirring rods are installed in the axial direction, and bottles are installed on the side wall. is introduced into a mixing agitator protruding between stirring rods and mixed at a rotation speed of 150 rpm. Furthermore, the pellets were fed into a third polymerization machine at 6.21°C, where they were polymerized at a temperature of 1/1 to 100°C, and stirred so that the average particle diameter of the rubbery material in the pellets was a, SZ chron. The solid material concentration at the outlet was 37% by weight. This material is further sent to the second polymerization machine at 6.2 mm, and the temperature/
One in three/! ; Polymerized at °C. The solids concentration at the outlet was go% by weight.

The obtained polymer was fed to an extruder with a covent and heated to 230°C.
,-? 3! Volatile components were removed under a reduced pressure of rIIIHg, and the molten strand was drawn out from the die, cooled with water, and cut with a cutter to continuously obtain cylindrical pellets. Various physical properties of the obtained pellets were measured, and the results are shown in Table 1.

Example 2 As the first stream, the following mixture (&) was added at a feed rate of 21/hour: 2.4! 1 of the first polymerizer.

Mixture (a) Polybutadiene rubber 703% by weight Styrene 3% by weight Ethylbenzene /Y01ifL% Total 100 parts by weight 27- Bis(t-butylperoxy) 3, J,! ;-Human methylcyclohexane 0071
Parts by weight Stearyl-β-(3,5-di-t-buty/L-4-hydroxyphenyl)propionate 6, is Parts by weight α-methylstyrene linear dimer 0073 parts by weight The temperature of the first polymerization machine was 96°C, and the outlet The solid material concentration was 76% by weight. Phase contrast microscopy showed black polystyrene particles in the white rubber continuous phase, and the rubber phase had not yet turned into particles.

As a second stream, the following mixture (b) is fed continuously into a 6.2 mm second polymerizer at a feed rate of /11/100.

Mixture (b) 3.7 parts by weight of mineral oil The temperature of the copolymerizer was 13θ to 3°C, and the solids concentration at the outlet was sII% by weight.

-11 These first flow and second flow have a capacity of 051, the gap between the tip of the stirring blade and the mixer wall is 2.5 fins, and six stages of stirring rods are installed in the axial direction. A heat transfer tube is inserted into the side wall of a mixing stirrer protruding between stirring rods, and the mixture is mixed at a rotation speed of 100 rpm. The pellets were then fed into a third polymerization machine, where they were polymerized at a temperature of 77° C. and stirred so that the average particle diameter of the rubbery material in the pellets was 2.S microns. The solid material concentration at the outlet was 52% by weight. This material is further sent to the second polymerization machine in 6.21, and the temperature/
Polymerization was carried out at 4I~iss°C. The solid substance concentration at the outlet is 1
It was 0% by weight.

The obtained polymer was fed to an extruder with copent and heated to 30°C.
Volatile components were removed under reduced pressure of 735 wIIHg, and the molten strand was drawn out from the die, cooled with water, and cut with a cutter to continuously obtain cylindrical pellets. Various physical properties of the obtained pellets were measured, and the results are shown in Table 1.

Example 3 The following mixture (a) is fed continuously as a first stream into a 2.1110 first polymerizer at a feed rate of 21/h.

Mixture (a) Butadiene-styrene random copolymer rubber/Co, 0 weight 1% Styrene Rigo weight % Ethylbenzene 100 weight % Total 700 parts by weight /, /-bis(t-butylperoxy) 3, ? ,
&-) Limethylcyclohexane 0θls parts by weight Stearyl β-(3,3-di-t-butyl-y-hydroxyphenyl)gropionate 0. /! Part by weight α-methylstyrene linear dimer ooqsMk part The temperature of the first polymerizer was 97°C, and the solid material concentration at the outlet was 18% by weight.
Met. Phase contrast microscopy showed black polystyrene particles in the white rubber continuous phase, indicating that the rubber phase had not yet turned into particles. 6. As a second stream, the following mixture (b) is added at a feed rate of t, tl/h. The polymer is continuously fed into the second polymerizer.

Mixture (b) Mineral oil 522 parts by weight tert-butylperoxybenzony QO' 1 part by weight The temperature of the second polymerizer was 1-137 DEG C. and the solids concentration at the outlet was 4% by weight. These first and second streams have a capacity of aSl, the gap between the tip of the stirring blade and the mixer wall is km, and /j stages of stirring rods are installed in the axial direction, and bottles are installed on the side wall. The mixture is introduced into a mixing agitator protruding between stirring rods, and mixed at a rotation of 2Q Orp. Further 6.
The pellets are fed into the third polymerization machine of No. 21 and polymerized at a temperature of 10°C to 10°C until the average particle size of the rubbery material in the pellets reaches 3.5°C.
The mixture was stirred to a thickness of 3 microns. The solid material concentration at the outlet was S% by weight. This material was further fed into the second polymerization machine of No. 21 and polymerized at a temperature of /30 to /kO°C. The solids concentration at the outlet was to 100 ml by weight.

-,2! r - The obtained polymer was fed to an extruder with two vents and heated to 230°C.
, 7351m) (Volatile components were removed under reduced pressure of g, the molten strand was pulled out from the die, cooled with water, and cut with a cutter to continuously obtain cylindrical pellets. Various physical properties of the obtained pellets were measured. The results are shown in Table 1.

COMPARATIVE EXAMPLE/The following mixture (a) was mixed at a feed rate of 21/hour as the first stream in 2. 1ll is continuously fed into the first polymerizer.

Mixture (a) Polybutadiene rubber 7 parts] it% Styrene Zayu g weight% Ethylbenzene /aθ weight - [it% total /Qθ weight part / -bis(t-butylperoxy) cyclohexane 0.0 ? 3 parts by weight, 6-Gt
-Butyluda-methylphenol a/θ Part by weight α-
Methylstyrene linear dimer aθ75 heavy ship part 1
The temperature of the polymerization machine was 97°C, and the solid material at the outlet was
/A weight %. Phase contrast microscopy showed black polystyrene particles in the white rubber continuous phase, confirming that the rubber phase had not yet turned into particles. 4.2 of the following mixture (b) at a feed rate of 117 hours as a second stream.
1 and continuously into the second polymerizer.

Mixture (b) The second polymerizer was at a temperature of /30°C and a solids concentration of &&% by weight at the outlet. These first flow and second flow are mixed in a static mixer (number of elements: 3).
After mixing in step 0), 6. The pellets are fed into the third polymerization machine of 10-10 and polymerized at a temperature of lθ7 to ii'y°C, so that the average particle diameter of the rubber-like substance in the pellet is 3. The mixture was stirred to achieve gs chron. The solids concentration at the outlet was % SII by weight. Next is 6. Introduced into the first polymerization machine of 1, and brought the temperature to /3~/j-
Polymerization occurred at j°C. The solids concentration at the outlet was go% by weight. Next, the obtained polymer was fed into an extruder with two vents at 230°C. j j; lllllff) (Volatile components were removed under reduced pressure of Table 1
Shown below.

Comparative Example 2 The following mixture (IL) is continuously fed as a first stream into a first polymerizer at a feed rate of All/hour.

Mixture (a) Polyptadier/Rubber IQ! Weight% Styrene Kudako Weight% Ethylbenzene iho Weight% Total 100 parts by weight /, /-Bis(t-butylperoxy)J, 3.j
-) Limethylcyclohexane aoqs parts by weight Stearyl-β-(3,5-di-t-butyl-terhydroxyphenyl)propionate θ/k parts by weight α-methylstyrene linear dimer Qoqsl parts by weight 1st type part 1st
The temperature of the polymerizer was 6°C, and the original solids concentration was 16% by weight. Phase contrast microscopy showed black polystyrene particles in the white rubber continuous phase, indicating that the rubber phase had not yet turned into particles.

6. The following mixture (b) at a feed rate of 117 hours as the first stream. -7 continuously into the second polymerizer.

Mixture (b) Mineral oil, 2 parts by weight The temperature of the second polymerization machine was 1g -770°C, and the outlet ports 1 and 2 were at a temperature of -770°C. The solid material concentration was 57% by weight. These first and second streams are fed into a third polymerizer at a temperature of t,,al and polymerized at a temperature of //λ~//1°C to reduce the average particles of rubbery material in the pellets. It was stirred so that the diameter was 2.7 microns. The solid material concentration at the outlet was 31% by weight.

This one also has 6. The polymer was sent to a second polymerization machine in a factory and polymerized at a temperature of 0-1ss°C. The solids concentration at the outlet was go% by weight.

The obtained polymer was fed to an extruder equipped with a copent, and 23
Volatile components were removed under reduced pressure at 0°C and 7315 aaT (H), the molten strand was pulled out from the die, cooled with water, and cut with a cutter to continuously obtain cylindrical pellets. Physical properties of the obtained pellets. was measured, and the results are shown in Table 1.

Comparative Example 3 As a first stream, the following mixture (a) was continuously fed into the first polymerizer of 1 and 1 at a feed rate of 137 hours.

Mixture (a) Butadiene-styrene random rubber 40% by weight] (
Same as the rubber used in Example 3) Total 700 parts by weight/,/-bis(t-butylperoxy)3,j,!
r-trimethylcyclohexane 001,2! ; parts by weight stearyl-β-(3,5-di-t-butyl→-hydroxyphenyl)gropionate 0725 parts by weight α-methylstyrene linear dimer 0075 parts by weight The temperature of the first polymerization machine was 9 g°C, and the solid substance concentration at the outlet was 12% by weight. Phase contrast microscopy and mirror observation revealed black polystyrene particles in the white rubber continuous phase, and the rubber phase had not yet turned into particles.

As a second stream, the following mixture (b) is continuously fed into the second polymerizer of A, 211 at a feed rate of o, bl/h.

Mixture (b) Mineral oil 5.2 parts by weight The temperature of the second polymerizer was l-0~/30°C, and the solid material concentration at the outlet was 57% by weight. The first flow and the second flow have a capacity of θ, 5/, the gap between the tip of the stirring blade and the mixer wall is 25 m, and six stages of stirring rods are installed in the axial direction. The mixture is introduced into a stirrer and mixed at a rotation angle of 20θ. Furthermore, the pellets were sent to the third polymerization machine of 6.1 and polymerized at a temperature of 11.2 to 7 degrees Celsius, and stirred so that the average particle size of the rubbery material in the pellets was 4.4 microns. Ta. The solid substance concentration at the outlet was H,tλ% by weight. This material is further sent to No. 21 polymerization machine A, and the temperature is /lθ~/! Polymerized at j℃. The solid material concentration at the outlet was 30% by weight.

The obtained polymer was fed to an extruder with copent and heated to 3θ℃.
Volatile components were removed under reduced pressure of , 733 wnHg, and the molten strand was drawn out from the die, cooled with water, and cut with a cutter to continuously obtain cylindrical pellets. Various physical properties of the obtained pellets were measured, and the results are shown in Table 1.

COMPARATIVE EXAMPLE As a first stream, the following mixture (a) is continuously fed into the first polymerizer in U.S. at a feed rate of /Sl/hr.

Mixture (a) Polybutadiene rubber 10. gM amount% Styrene 7'A2% by weight Ethylbenzene /0% by weight Total ioo parts by weight /, /-Bis(t-butylperoxy) J, j, j
-) Limethylcyclohexane θθ7! r parts by weight stearyl β-(,?, S-di-t-butyl-hydroxyphenyl)globionate ais ii: parts α-
Methylstyrene linear dimer 007! Parts by weight The first polymerizer was at a temperature of 9.3 DEG C. and the solids concentration at the outlet was 16% by weight. Observation using a phase contrast microscope revealed black polystyrene particles 33- in the continuous white rubber phase, indicating that the rubber phase had not yet become particles.

As a second stream, the following mixture (b) is continuously fed into the second polymerizer of A, 21j at a feed rate of 1117 hours.

Mixture (b) 31 parts by weight of mineral oil The temperature of the second polymerizer was between /20 and /3'C, and the solid matter concentration at the outlet was lI! r% by weight. These first flow and second flow have a capacity of θ, sll, a gap between the tip of the stirring blade and the mixer wall is ko, ri, and 6 in the axial direction.
The mixer is equipped with stage stirring rods, and heat transfer tubes are introduced into the mixing stirrer that protrudes between the stirring rods, and the mixture is mixed at a rotational speed of 20 θ rpm. Furthermore, it is sent to the third polymerizer of /,,,ll, and the temperature is //3;-/,l! Polymerization was carried out at i.degree. C. and stirred so that the average particle size of the rubbery material in the pellets became more microns. The solid material concentration at the outlet was 53% by weight. In addition to this one 6. ．． It was sent to the second polymerization machine of 2JI and polymerized at a temperature of /4'j -/Si°C. The solids concentration at the outlet was 0 wt.

The obtained polymer was fed to an extruder with copento and heated to 230°C.
, -73,! Volatile components were removed under reduced pressure of r wmHg, and the molten strand was drawn out from the die, cooled with water, and cut with a cutter to continuously obtain cylindrical pellets. Various physical properties of the obtained pellet were measured, and the results are shown in Table 1.
Shown below.

(Margin below)

Claims (1)

[Scope of Claims] , a first flow that is kept within a range that does not exceed the polymerization conversion rate at which the rubbery substance becomes particles, and (b) an aromatic monovinyl monomer of 75 to θθ weight % and a solvent of 0 to .25 weight %. The solution (I) and the solution (II) are continuously mixed and stirred with a second stream containing 30 to 70% by weight of a solid substance to form particles of the rubbery substance. (It) The mixing agitator mixes and stirs these two solutions so that the mixing ratio with (It) is in the range of 7:3 to 3. and
The ratio r between the distance 111d and the stirring blade tip circumferential speed r (m/sec)
/dtso or more, and furthermore, after mixing, the polymerization is allowed to proceed, and the unpolymerized aromatic monovinyl monomer and solvent are recovered, so that the rubber-like substance is contained in an amount of 3 to 1/S by weight. Continuous manufacturing method for rubber-modified aromatic monovinyl resin. (2) "The mucous substance is polybutadiene, butadiene-
7 types or 2 selected from styrene random copolymer rubber
The manufacturing method according to claim 1, which is a mixture of s or more. (8) The manufacturing method according to claim 1, wherein the aromatic monovinyl monomer is styrene. (4) Organic peroxide is added at 0.0/~ to 700 parts by weight of the rubbery substance, aromatic monovinyl monomer, and solvent.
2. The production method according to claim 1, wherein a certain amount of Oal is used and the polymerization is allowed to proceed so that it remains even after the first stream and the second stream are mixed and stirred.