KR20130076615A - Continuous process for preparing thermoplastic resin from conjugated diene and thermoplastic resin prepared therefrom - Google Patents

Abstract

PURPOSE: A continuous process for preparing a thermoplastic resin from a conjugated diene is provided to reduce energy and CO2 by omitting a veil-forming process after demolding, washing, and coagulation processes. CONSTITUTION: A continuous process for preparing a thermoplastic resin from a conjugated diene comprises a step of manufacturing a rubber solution by primarily polymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer in a first reactor (10), under the presence of an organic metal-based catalyst and a first solvent, to manufacture a rubber solution; and a step of putting an aromatic vinyl-based monomer and a copolymerizable monomer therewith into the rubber solution and conducting a second polymerization in a second reactor (20), under the presence of a second solvent. The first solvent and the second solvent are the same. The amount of the organic metal-based catalyst is 0.005-1.0 wt%.

Description

FIELD OF THE INVENTION A process for continuously preparing a thermoplastic resin from a conjugated diene and a thermoplastic resin produced therefrom {CONTINUOUS PROCESS FOR PREPARING THERMOPLASTIC RESIN FROM CONJUGATED DIENE AND THERMOPLASTIC RESIN PREPARED THEREFROM}

The present invention relates to a process for continuously producing thermoplastic resins from conjugated dienes and to thermoplastic resins produced therefrom. More specifically, the present invention relates to a thermoplastic resin produced from a method having high impact and low light properties, saving energy and CO ₂ , and having excellent productivity.

In general, ABS (acrylonitrile-butadiene-styrene) resin has excellent impact resistance and processability, and is widely used in various applications such as automobiles, electrical and electronic equipment, office equipment, home appliances, toys, stationery, etc. due to its mechanical strength and beautiful appearance characteristics. There are three general methods for manufacturing the ABS resin. Emulsion polymerization of butadiene, which is a raw material, and the addition of styrene and acrylonitrile to form grafted ABS. Bulk-suspension preparation method (Bulk-Sus Prosess) to prepare ABS by polymerizing styrene and acrylonitrile and changing to suspension polymerization form after the phase inversion step. There is a continuous manufacturing process (Mass / continuous process) using ABS kneading extrusion manufacturing method is a high gloss ABS production by using a relatively simple graft ABS particles produced in the batch polymerization method and relatively simple manufacturing equipment. It is possible to easily change the mixing ratio of raw materials in the kneading extrusion step, which is advantageous for controlling physical properties There is an advantage but not through the many processes difficult to manufacture the final product doeeojim stable ABS manage properties due to additives such as emulsifiers and dispersants are added to the Batch polymerization process has the disadvantage that occurs incidental issues.

The ABS bulk-suspension manufacturing method is a manufacturing method that is frequently used in the early stages of ABS development.As the ABS product is manufactured using only one reactor, physical properties are relatively stable, operation cost and energy consumption are low, and inefficient for mass production of one product. Due to the many aspects, new investments are currently hardly made as mass production facilities.

On the other hand, the ABS manufacturing method using the continuous polymerization process has a big advantage that it can stably manufacture a large quantity at a time, whereas the limitation of the type of rubber that can be used and the control of the physical properties of the rubber itself are achieved by using the rubber manufactured in another process. The disadvantage is that it is not easy to produce and develop various products. In addition, the conventional ABS manufacturing method using a continuous polymerization process is a step of removing the solvent and water through a stripping process after the polymerization of the conjugated diene-based monomer and preparing a rubber in the form of a bale. Two steps of dissolving the rubber bale in the polymerized monomer after grinding it for use in the ABS resin manufacturing process. The rubber solution and the solvent dissolved in the polymerization monomer are mixed and continuously added to the reactor to carry out the polymerization, followed by three steps to prepare the final ABS pellets. In the first step, the rubber removal process includes removing the solvent and water and manufacturing the rubber in the form of a bale, and thus, a large amount of energy is consumed by using a large amount of steam, and at the same time, a large amount of waste water is generated. In addition, there is a disadvantage in that the energy consumption is much during the grinding and melting of the rubber in the second step.

The rubber used in the thermoplastic resin can be produced by various polymerization methods, but in general, the solution polymerization or emulsion polymerization method is generally used because the bulk polymerization is difficult to control the polymerization in the mass production process. However, in the case of the rubber produced by the polymerization method, it is necessary to remove the water and the solvent. US 6,143,833 discloses a process for preparing rubber using n-buthyllithuim as a catalyst and n-hexane as a solvent for separating the rubber from the rubber solution. The method removes the solvent through a direct devolatilization process after the rubber polymerization, and after the rubber is separated from the solvent to prepare a rubber bale, there is a problem that a lot of energy is consumed in the post-treatment process such as solvent removal, ABS polymerization In case of producing rubber with low viscosity, it is difficult to post-treatment and commercialization due to problems such as cold flow. In US Pat. No. 6,951,901, a rubber is polymerized using n-buthyllithuim catalyst, n-hexane as solvent, stripping with water and resolving of rubber bale. However, this also has the disadvantage that the post-treatment process is complicated and consumes a lot of energy. In addition, when the rubber produced through the patents is applied to a continuous process for producing a thermoplastic resin, the solvent must be removed during rubber production, and the rubber is separated, the bale forming process and the veil are dissolved in the solvent again. Through the crushing process, a lot of energy is consumed, and the labor cost of equipment operation costs are all increased.

Therefore, it is necessary to develop a method capable of directly injecting a rubber solution into a thermoplastic resin polymerization process without forming a rubber bale.

SUMMARY OF THE INVENTION An object of the present invention is a method of continuously preparing a thermoplastic resin from a conjugated diene, wherein the rubber is prepared by solution polymerization, and then a stripping process using steam and water, and washing and flocculation processes are not required for solvent removal. To provide.

Another object of the present invention is to provide a method that can reduce the energy and CO ₂ because there is no baling process for the production of the product after the stripping process using water and steam, water washing, flocculation process.

It is still another object of the present invention to provide a thermoplastic resin manufacturing method which can improve production efficiency since the same solvent is used in all stages in continuously preparing the thermoplastic resin from the conjugated diene.

Another object of the present invention is to provide a method for minimizing energy consumption, generating no waste water, and lowering manufacturing costs.

Another object of the present invention is to provide a method of maximizing the properties of the final product with low light properties by controlling the physical properties of the rubber from the initial polymerization stage.

The technical objects to be achieved by the present invention are not limited to the above-mentioned technical problems, and other technical subjects which are not mentioned can be understood by those skilled in the art from the following description.

One aspect of the present invention relates to a method for continuously preparing thermoplastic resins from conjugated dienes. The method comprises first polymerizing a conjugated diene monomer and an aromatic vinyl monomer in a first reactor in the presence of an organometallic catalyst and a first solvent to prepare a rubber solution; And incorporating the aromatic vinyl monomer and the monomer copolymerizable with the rubber solution into the rubber solution in the second reactor in the presence of the second solvent, wherein the first solvent and the second solvent are the same.

The secondary polymerization is characterized in that the polymerization using a radical polymerization initiator.

The organometallic catalyst is characterized in that 0.005 to 1.0% by weight of the monomer mixture.

In embodiments, the conjugated diene monomer may be butadiene, isoprene or a combination thereof.

In embodiments, the organometallic catalyst may be selected from the group consisting of linear or branched alkyl lithium of 1 to 6 carbon atoms, cycloalkyl lithium of 5 to 10 carbon atoms, aromatic lithium of 6 to 12 carbon atoms.

In an embodiment, the rubber solution polymerized in the first reactor may be injected into the second reactor after removing the solvent by extrusion.

In embodiments, the first and second solvents may be aromatic for daily use.

After the primary polymerization, a rubber solution may be prepared by adding a hydroxyl group-containing polymerization inhibitor.

In embodiments, the hydroxyl group-containing polymerization inhibitor may be selected from the group consisting of water, methanol, ethanol, monovalent, divalent low molecular alcohols.

In an embodiment, the aromatic vinyl monomer introduced into the second reactor may be selected from styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, and the like.

In an embodiment, the copolymerizable monomer introduced into the second reactor may be selected from vinyl cyanide monomers, (meth) acrylate monomers, unsaturated carboxylic acids, anhydrides thereof, and the like.

In embodiments, the radical polymerization initiator introduced into the second reactor may be selected from organic peroxides, hydroperoxides or azo compounds and the like.

The method does not form a rubber bale.

Another aspect of the invention relates to a thermoplastic produced by the above method. The thermoplastic resin has a YI (Yellow Index) of 5 or less according to ASTM E313, 75 to 30 to 60 GU using a Gardner glossmeter, and a 1/8 "notch impact strength of 10 to 60 kgf · cm / according to ASTM D256. It is characterized by being cm.

The present invention relates to a method for continuously producing a thermoplastic resin from a conjugated diene, and a method for continuously producing a thermoplastic resin from a conjugated diene, wherein the rubber is prepared by solution polymerization and then stripped using steam and water for solvent removal. Because it does not require stripping process, water washing and flocculation process, energy and CO ₂ can be saved, productivity is excellent, energy consumption is minimized, waste water is not generated, manufacturing costs can be reduced, and rubber properties are controlled from the initial polymerization stage. This has the effect of the invention to provide a method of maximizing the properties of the final product.

1 schematically shows a continuous polymerization apparatus for continuously producing a thermoplastic resin from a conjugated diene according to one embodiment of the present invention.

The method of the present invention is to prepare a rubber solution by first polymerizing a conjugated diene monomer and an aromatic vinyl monomer in a first reactor in the presence of an organometallic catalyst and a first solvent; And incorporating the aromatic vinyl monomer and the copolymerizable monomer into the rubber solution in the second reactor in the presence of a second solvent.

Rubber polymerization

The conjugated diene monomer may be butadiene, isoprene or a combination thereof.

The aromatic vinyl monomers include styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, and the like. Among these, preferably styrene.

The conjugated diene monomer may be polymerized to solution polymerization in the presence of a first solvent when preparing a rubber solution. As the first solvent, most of commonly used solvents capable of effective control of the heat of reaction generated during the polymerization process may be used, and there is no limitation on the use range. However, aromatic solvents such as ethylbenzene, benzene, xylene, toluene, methyl ethyl ketone, and the like, which are easy to obtain and can be used in the rubber polymerization process and subsequent thermoplastic resin polymerization processes, may be applied, and are preferably aromatic solvents. .

Conventionally, n-hexane was used as a solvent during rubber polymerization. However, in the continuous polymerization process of polymerizing the thermoplastic resin from the rubber polymerization, the n-hexane solvent must be removed, which requires a post-treatment process and consumes a lot of energy. In the present invention, the same solvent is applied in the continuous polymerization process for producing the rubber to the thermoplastic resin, but preferably the aromatic solvent applied during the polymerization of the thermoplastic resin.

When the rubber solution is prepared, the first reactor may be charged with 10 to 50 wt% of the conjugated diene monomer, 0 to 25 wt% of the aromatic vinyl monomer, and 50 to 90 wt% of the first solvent. There is an advantage that can be stable polymerization in the above range. Preferably 15 to 40% by weight of the conjugated diene monomer, 3 to 20% by weight of the aromatic vinyl monomer and 55 to 80% by weight of the first solvent may be added.

In an embodiment, the organometallic catalyst used in the first reactor is preferably selected from a metal catalyst system capable of living polymerization of a diene monomer, and in particular, using a lithium catalyst for controlling Cis-Trans-Vinyl content of the prepared polymer. More preferred. In specific embodiments, linear or branched alkyl lithium having 1 to 6 carbon atoms, cycloalkyl lithium having 5 to 10 carbon atoms, aromatic lithium having 6 to 12 carbon atoms, and the like may be used. For example, methyllithium, ethyllithium, n- or sec-butyllithium, isopropyllithium, cyclohexyllithium orphenyllithium, n-Butyllithium, sec-butyllithium and the like may be applied alone or in combination of two or more, but are not necessarily limited thereto. In embodiments, the catalyst may be added at 0.005 ~ 1.0% by weight of the monomer mixture. The rubber polymerization reaction is stable in the above range, and has excellent low light properties, impact strength and discoloration resistance in the production of thermoplastic resins. Preferably it may be added at 0.01 to 0.8% by weight of the monomer mixture. Low light characteristics can be realized in the above range and excellent impact strength can be obtained.

The reaction in the first reactor is polymerized at 30 to 100 ° C. for 40 to 150 minutes.

In a specific embodiment, when the conversion rate after polymerization in the first reactor is 95% or more, preferably 100%, additives such as a polymerization inhibitor and an antioxidant may be added.

As the polymerization inhibitor, it is preferable to use a hydroxyl group-containing polymerization inhibitor which can effectively stop the activity of lithium living ions and minimize the influence on the thermoplastic resin polymerization process continuously connected. Water, alcohols, etc. may be used as the hydroxyl group-containing polymerization inhibitor. In the specific example, it is preferable to use water or mono- and divalent low molecular weight alcohols such as methanol and ethanol, and most preferably, inexpensive water. The hydroxyl group-containing polymerization inhibitor is suitable to use 0.005 to 2.0% by weight relative to 100% by weight of the monomer mixture, preferably 0.01 to 1.0% by weight.

As the antioxidant, octadyl-3 (4-hydroxy-3,5-di-tert-butylphenyl) propionate may be used as the hindered phenol-based antioxidant. These can be applied individually or in mixture of 2 or more types. Among these are preferably octadil-3 (4-hydroxy-3,5-di-tert-butylphenyl) propionate. The antioxidant may be added at 0.2 ~ 0.8% by weight of the conjugated diene monomer.

The rubber solution prepared as described above is dissolved in a first solvent, and the rubber solution dissolved in the first solvent is removed using a twin screw extruder and then transferred to a subsequent process.

That is, in the present invention, unlike the prior art, the solvent used in the rubber polymerization and the solvent used in the subsequent thermoplastic resin polymerization process are the same, so that the solvent which cannot be used in the subsequent process after the rubber polymerization must be completely removed. In addition, the present invention includes a process of directly removing a part of a solvent without using an energy-consuming post-treatment process.

An extruder can be used to remove the first solvent used in the rubber polymerization. For example, using a twin screw extruder having a diameter of 30 Φ, L / D 45, four vent zones, and adjusting the vacuum degree of each vent zone to 10 torr to atmospheric pressure, solvent removal can be performed. At this time, it is preferable to adjust the concentration of the rubber solution so that the rubber component is 10 to 70% by weight. It is possible to remove and transport a stable solvent in the above range.

Thermoplastic resin polymerization using the rubber

The rubber solution in which the solvent is partially removed is dissolved in an aromatic vinyl monomer, and the thermoplastic resin is polymerized by adding an aromatic vinyl monomer, a copolymerizable monomer, and a radical polymerization initiator.

The aromatic vinyl monomers include styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, and the like. Among these, preferably styrene. These may be used alone or in combination of two or more.

The copolymerizable monomers include vinyl cyanide monomers, (meth) acrylate monomers, unsaturated carboxylic acids, and anhydrides thereof, but are not necessarily limited thereto. These may be used alone or in combination of two or more.

In the thermoplastic resin polymerization step of the present invention, an initiator different from the first polymerization that polymerizes the rubber is applied. That is, in the first polymerization that polymerizes rubber, an organometallic catalyst is applied as a polymerization initiator to form a block copolymer, and in the second polymerization that polymerizes a thermoplastic resin, a radical polymerization initiator is used, thereby yielding less yield using a solvent. To improve the performance and control the reaction.

The radical polymerization initiator may be used an organic peroxide, hydro peroxide or azo compound. Specifically, Benzoyl peroxide, t-Butyl peroxyisobutyrate, 1,1-Bis (t-butylperoxy) cyclohexane, 2,2-Bis (4,4-di-t-butylperoxy cyclohexane) propane, t-Hexyl peroxy isopropyl monocarbonate, t -Butyl peroxylaurate, t-Butyl peroxy isopropyl monocarbonate, t-Butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-Butyl peroxyacetate, 2,2-Bis (t-butyl peroxy) butane, t-Butyl peroxybenzoate, Dicumyl peroxide , 2,5-Dimethyl-2,5-bis (t-butyl peroxy) hexane, t-Butyl cumyl peroxide, Di-t-butyl peroxide, Di-t-amyl peroxide and the like can be used. These may be used alone or in combination of two or more.

Polymerization for the production of the thermoplastic resin may be applied to bulk polymerization, solution polymerization, bulk-suspension polymerization (Bulk-suspension polymerization), and the like. Preferably solution polymerization can be applied.

In an embodiment, an aromatic vinyl monomer, a monomer copolymerizable with the monomer, and a second solvent may be added together to the rubber solution from which the solvent is removed to polymerize. When the aromatic vinyl monomer and the second solvent are added together, the rubber component is added so as to be 6-10 wt%. For example, 40 to 70% by weight of aromatic vinyl monomer, 6 to 10% by weight of rubber component, 5 to 25% by weight of copolymerizable monomer and 2 to 20% by weight of second solvent are added.

The radical polymerization initiator is used 0.01 to 0.5% by weight of the monomer mixture copolymerizable with the aromatic vinyl monomer introduced into the second reactor, preferably 0.04 to 0.1% by weight. In the above range, the reaction temperature, residence time, and the like can be effectively controlled, and the impact strength of the low light thermoplastic resin, which is the final product, can be prevented from being lowered, and the conversion rate is excellent. The thermoplastic resin prepared in the above range has excellent low light characteristics, impact strength and fluidity.

As the second solvent, an aromatic solvent such as ethylbenzene, benzene, xylene, toluene, etc. may be used to be the same as the first solvent, but is not limited thereto.

In the second reactor, the solid phase content may be polymerized to 10-30% by reacting before the phase transition.

1 schematically shows a continuous polymerization apparatus for continuously producing a thermoplastic resin from a conjugated diene according to one embodiment of the present invention. A step is a rubber polymerization process, B is a thermoplastic resin polymerization process.

As shown, an organometallic catalyst and a first solvent are added to the first reactor 10 together with the conjugated diene monomer and the aromatic vinyl monomer to polymerize.

The first reactor 10 may be preferably a reactor having a stirrer of a double-helical-ribbon type. Reaction conditions of the first reactor is polymerized for 40 to 150 minutes at 30 ~ 100 ℃.

In the polymerization, when the conversion rate is 95% or more, preferably 100%, the polymerization inhibitor and the polar hydrocarbon are added, and the solvent is removed by moving to the twin screw extruder 12 for removing the solvent. The rubber solution in which the solvent is partially removed from the twin screw extruder 12 is transferred to the rubber solution reservoir 15 through the line 1. The rubber solution passing through the line is 75-92 wt% of the solvent and 10-70 wt% of the rubber component.

In the rubber solution reservoir 15, an aromatic vinyl monomer, a copolymerizable monomer, a radical polymerization initiator, and a second solvent are added to dissolve the rubber solution. The rubber solution is continuously introduced into the second reactor 20 for thermoplastic resin polymerization through the line (2). The rubber solution passing through the line 2 is in a state in which a rubber solution is dissolved in an aromatic vinyl monomer, a copolymerizable monomer, and a second solvent. Component of the rubber solution is 40 to 70% by weight aromatic vinyl monomer, 6 to 10% by weight rubber component, 5 to 25% by weight copolymerizable monomer, 0.01 to 0.5% by weight of radical polymerization initiator And 2-20 wt% of the second solvent.

The rubber solution is reacted in the second reactor 20 at a temperature of 100 to 135 ° C. for 0.5 to 1.5 hours to a point before the phase change, thereby producing a first polymer having a solid content of 20 to 30%. The second reactor 20 is a continuous flow stirred reactor (CSTR) is suitable and a full charge type (full charge type) in which the polymerization mixture is supplied to the bottom of the reactor and the reactant is directed upward to the reactor may be preferably applied.

The first polymer is continuously introduced into the third reactor 30 via the line 3. The third reactor 30 may be polymerized at 110 to 145 ° C. for 1.5 to 3.0 hours to produce a second polymer having a solid content of 30 to 50%. The third reactor 30 may be a continuous flow stirred reactor (CSTR) is applied. In embodiments, a continuous flow stirred reactor (CSTR) with an agitation device in the form of an anchor may be applied.

The second polymer is continuously introduced into the fourth reactor 40 through the line 4 again. The fourth reactor 40 may be reacted at 120 to 155 ° C. for 1.5 to 3.0 hours to produce a third polymer having a solid content of 60 to 90%. The fourth reactor 40 may also be applied to a double-helical-ribbon type stirrer.

The third polymer may be added to the devolatilization tank 50 through the line 5 to remove unreacted monomers and solvents. After that, it can be prepared in pellet form using a pelletizer.

As such, the method of the present invention eliminates the need for water removal by introducing a rubber manufacturing process in the first half of the thermoplastic resin polymerization process, and does not require a rubber bale manufacturing process and a crushing process. It is possible to produce a high impact thermoplastic resin.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Example

Example 1

18.25% by weight of butadiene monomer, 6.25% by weight of styrene and 75% by weight of toluene were added to the first reactor, and 0.12% by weight of a butadiene monomer and a styrene monomer mixture was added to the metal catalyst n-Buthyllithuim (NBL) at 50 ° C. Polymerization at 60 minutes. After confirming that 100% of the polymerization proceeded, the polymerization inhibitor was terminated by adding 0.2 wt% of polymerization inhibitor and 0.4 wt% of antioxidant. Thereafter, toluene was removed from the rubber polymerization solution using a twin screw extruder so that the rubber component was 50% by weight in the rubber solution.

After transferring the rubber solution dissolved in the aromatic monomer prepared in the rubber polymerization reaction to the rubber solution reservoir, the rubber content reservoir 8% by weight, styrene monomer 54%, acrylonitrile 18% by weight and 20% ethylbenzene After adding%, the reactant and the solvent were added to a rubber solution reservoir so that the radical polymerization initiator, t-Butyl peroxyacetate (TBPA), was added 0.06% by weight of the styrene monomer and acrylonitrile monomer mixture. The rubber solution thus prepared was continuously added to a second reactor in a series of reactors for making a thermoplastic resin to react the polymer until the phase transition point, thereby producing a first polymer such that the solid content was 25%. The resulting first polymer was continuously introduced into a third reactor to further react the polymer and produce a second polymer such that the solid content was 45%. Thereafter, the produced second polymer was continuously added to the fourth reactor to further react the polymer to obtain a target solid content of 63%, thereby preparing a third polymer. The third polymer prepared was subjected to a step of separating the unreacted material from the final polymerized product using a devolatilization tank at a high temperature and a vacuum state, and prepared in pellet form by using a pelletizer.

The prepared pellet was dried at 80 ° C. for 3 hours, and then injected into a 6 Oz injection machine under conditions of a molding temperature of 180 to 280 ° C. and a mold temperature of 40 to 80 ° C. to prepare a specimen.

Examples 2-5

The same process as in Example 1 was carried out except that the amounts of n-buthyllithuim catalyst, monomer and solvent of the first reactor were changed as shown in Table 1.

division Example One 2 3 4 5 First reactor

[Rubber polymerization
Reactor] toluene 75.5 80 NBL
(Content in monomer mixture) 0.12 0.10 0.08 0.15 0.11 butadiene 18.25 18.25 18.25 15 15 Styrene 6.25 6.25 6.25 5 5 Second reactor Solid content (%) 25 Reaction temperature (℃) 112 112 112 111 112 Retention time (hr) One Third reactor Solid content (%) 45 Reaction temperature (℃) 126 125 126 125 126 Retention time (hr) 2 Fourth reactor Solid content (%) 63 Reaction temperature (℃) 135 135 135 135 135 Retention time (hr) 2 Gloss 55 50 42 57 55 rps (μm) 0.88 1.02 1.23 0.90 0.91 Impact strength 22 20 19 24 22 Flow 20 19 22 18 19 Graft ratio (%) 75 77 79 75 73

As shown in Table 1, Examples 1 to 5 can be confirmed that the ABS resin having excellent low light properties while excellent impact properties and flow properties.

Examples 6-9

The same process as in Example 1 was performed except that the amounts of n-buthyllithuim catalyst, butadiene, styrene, and solvent of the first reactor were changed as shown in Table 2.

division Example 6 7 8 9 First reactor

[Rubber polymerization
Reactor] toluene 75.5 75.5 80 80 NBL
(Content in monomer mixture) 1.2 0.003 1.2 0.003 butadiene 18.25 18.25 15 15 Styrene 6.25 6.25 5 5 Second reactor Solid content (%) 25 25 25 25 Reaction temperature (℃) 118 113 112 109 Retention time (hr) One One One One Third reactor Solid content (%) 45 45 45 45 Reaction temperature (℃) 125 125 125 123 Retention time (hr) 2 2 2 2 Fourth reactor Solid content (%) 63 63 63 63 Reaction temperature (℃) 135 130 135 135 Retention time (hr) 2 2 2 2 Gloss 96 49 94 41 rps (μm) 0.16 2.10 0.16 2.50 Impact strength 3 9 4 11 Flow 21 16 26 13 Graft ratio 70 67 89 92

As shown in Table 2, Examples 6 and 8 are prepared with a rubber having a low viscosity, the rubber particle size is very small, Gloss and high fluidity, while Examples 7 and 9 it can be seen that the rubber particles are large. Therefore, it is easy to adjust the rubber particle diameter by the method of the present invention, it can be adjusted to the desired physical properties.

Resin characterization and physical property analysis of the injection molded product were performed on the prepared final polymer.

(1) Glossiness: 75 degree glossiness was measured using a BYK-Gardner Gloss Meter. (Unit: G.U.)

(2) Rubber particle size (rps): measured by Malvern's Mastersizer S Ver 2.14 (μm)

(3) Izod impact strength: measured in 1/8 "Notched condition by ASTM D256 (unit: kgfcm / cm).

(4) Fluidity: measured under the condition of 220 ° C / 10kg according to ASTM D1238 (g / 10min).

(5) Graft ratio: Take 10g of the prepared sample, put it into acetone, dissolve it sufficiently and leave it for 2 days at room temperature, then centrifuge it and separate it into a gel and a solution. Subsequently, the gel was taken, stored in a vacuum oven at 50 ° C. for one day, completely dried, and the Graft ratio (%) was calculated according to Equation 1 below.

[Equation 1]

In the above, the weight part of the dry gel means the weight% of the dry gel to the sample used in the analysis, the weight% of the rubber means the weight% of the rubber in the rubber solution added to the thermoplastic resin production.

Although the embodiments of the present invention have been described above with reference to the accompanying drawings and tables, the present invention is not limited to the above embodiments, but may be manufactured in various forms, and common knowledge in the art to which the present invention pertains. Those skilled in the art can understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features of the present invention. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

10: first reactor 12: extruder
15: rubber solution reservoir 20: second reactor
30: third reactor 40: fourth reactor
50: devolatilization

Claims (12)

Preparing a rubber solution by first polymerizing the conjugated diene monomer and the aromatic vinyl monomer in the first reactor in the presence of an organometallic catalyst and a first solvent; And
Including the aromatic vinyl monomer and the copolymerizable monomer in the rubber solution to the second polymerization in the second reactor in the presence of a second solvent,
The first solvent and the second solvent is the same method for continuously producing a thermoplastic resin from the conjugated diene.
The method of claim 1, wherein the secondary polymerization is polymerized using a radical polymerization initiator.
The method of claim 1, wherein the organometallic catalyst is 0.005 to 1.0% by weight of the monomer mixture.
The method of claim 1, wherein the conjugated diene monomer is butadiene, isoprene or a combination thereof.
The method of claim 1, wherein the organometallic catalyst is selected from the group consisting of linear or branched alkyl lithium of 1 to 6 carbon atoms, cycloalkyl lithium of 5 to 10 carbon atoms, and aromatic lithium of 6 to 12 carbon atoms. .
The method of claim 1, wherein the rubber solution polymerized in the first reactor is extruded to remove the solvent, and then introduced into the second reactor.
The method of claim 1 wherein the first and second solvents are aromatic solvents.
The method according to claim 1, wherein a rubber solution is prepared by adding a hydroxyl group-containing polymerization inhibitor after the first polymerization.
The method of claim 8, wherein the hydroxyl group-containing polymerization inhibitor is at least one selected from the group consisting of water, ethanol, methanol, 1,2-hydric alcohols.
The method according to claim 1, wherein the second reactor reacts to a point before the phase change and polymerizes the solid content to 20 to 30%.
The method of claim 1 wherein the method does not form a rubber bale.
Manufactured by the method of any one of claims 1 to 11, the 75 degree Gloss measurement using the Gardner glossmeter is 30 ~ 60 GU, 1/8 "Notch impact strength according to ASTM D256 10 ~ 60 kgf · cm / cm is a thermoplastic resin.

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