KR101672056B1 - - A Manufacturing method for Maleimide--alkyl styrene based heat-resistant ter-polymer with low oligomer content - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a method for producing a heat resistant mass copolymer, and more particularly, to a method for producing a maleimide- alpha -alkylstyrene heat resistant three-dimensional mass copolymer.
The maleimide-α-alkylstyrene heat resistant three-dimensional block copolymer according to the present invention is characterized in that it is prepared by dissolving an N-substituted maleimide monomer in an unsaturated nitrile monomer and charging it separately from other monomers.
The three-dimensional block copolymer according to the present invention is a heat-resistant three-dimensional block copolymer having a weight average molecular weight (Mw) of from 7 to 300,000 and a glass transition temperature of from 130 to 200 ° C, And has remarkably low melt viscosity. Therefore, it has excellent productivity, processability, moldability and kneadability when blended with other resins as well as self-processing.
Also, the continuous bulk polymerization process of the present invention is a continuous bulk polymerization process with a devolatilization apparatus, and it is possible to produce a trivalent block copolymer at low cost and high efficiency.
In the copolymer produced by the present invention, the content of oligomer due to side reaction is reduced in the final product and the heat resistance property is improved.

Description

Technical Field [0001] The present invention relates to a maleimide-alkylstyrene-based terpolymer having a low oligomer content,

The present invention relates to a process for producing a maleimide-? Alkylstyrene-based heat resistant three-dimensional block copolymer, and more particularly to a process for producing a maleimide-? The method comprising the steps of:

Conventional heat-resistant copolymers can be classified differently according to the constituent components and the polymerization process. First, based on the constituents, the copolymer is largely divided into a maleimide-based copolymer and an -alkylstyrene-based copolymer. It can be classified into emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization.

The maleimide-based copolymer generally adopts only the solution polymerization process due to the technical problems of the polymerization. It contains a large amount of maleimide and exhibits a high heat distortion temperature and a high thermal decomposition temperature. Thus, when mixed with various thermoplastic resins The heat resistance of the applied thermoplastic resin is greatly improved and the processability is excellent. On the other hand, since the maleimide content is high, the melt viscosity is considerably high, which not only requires a high processing temperature during processing, However, in the case of the maleimide-based heat-resistant copolymer, the heat resistance is so high that the impact resistance of the maleimide-based heat-resistant copolymer is drastically lowered as the application amount of the maleimide-based heat resistant copolymer is increased in the thermoplastic resin. And the polymerized heat-resistant copolymer Price competitiveness has drawbacks falling.

On the other hand, the α-alkylstyrene-based copolymer is mainly composed of a bulk polymerization and an emulsion polymerization process. In the case of an α-alkylstyrene-based copolymer which is polymerized in bulk, the product is a bulk polymerized product. It has excellent processability and has good color of thermoplastic resin applied to various thermoplastic resins, excellent impact resistance, and relatively low cost. However, most importantly, it has a high heat resistance (high heat resistance) Is difficult to be expressed. In addition, the α-alkylstyrene-based copolymer emulsion polymerized has a high α-alkylstyrene content and thus can exhibit a heat resistance (heat resistance) level at 135 ° C. However, since the melt viscosity is higher than that of heat resistance, The emulsifier and various additives of low molecular weight applied to the final product are remained so that the color of thermoplastic resin applied to various thermoplastic resins is poor and appearance defect is caused due to generation of gas during processing.

Particularly, in the case of the maleimide-based copolymer, there are three types of copolymerization, which are emulsion polymerization, suspension polymerization and solution polymerization.

First, in the case of the emulsion polymerization process, when the content of maleimide is high, since the softening point is high in the recovery process of the polymer product after the completion of polymerization, recovery from the emulsion system is impossible, , The impact strength is lowered due to the influence of the residual emulsifier, the discoloration of the hue of the natural color is severe during molding, and a further coagulation facility is required.

Second, in the case of suspension polymerization, maleimide and unsaturated vinyl monomers are likely to form alternating copolymers with each other. Therefore, if a copolymer having a high maleimide content is to be obtained, heterogeneous copolymers having different compositions are likely to be formed In addition, it has the disadvantage of requiring a filtering facility.

Third, in the case of solution polymerization, it is necessary to remove the solvent used in the polymerization and to extract the additional polymer product from the solution system using the solvent / non-solvent system. In addition, all of the above-mentioned polymerization processes (emulsion polymerization process, suspension polymerization process and solution polymerization process) can be applied only to a batch process, which is a polymerization process with low productivity.

 The solution-polymerized maleimide-aromatic vinyl monomer copolymer according to Japanese Patent No. JP 1982-98536 has a high heat resistance and a high melt viscosity to have a high processing temperature, poor natural color, poor coloring property, and an ABS (Acrylonitrile-Butadiene- : Hereinafter referred to as ABS resin) and an AS (acrylonitrile-styrene copolymer: hereinafter referred to as AS resin) resin is large, the kneading property is deteriorated. The solution-polymerized N-substituted maleimide-aromatic vinyl monomer copolymer according to Japanese Patent No. JP 1983-162616 requires a solvent recovery apparatus and a separate solvent tank, which are applied at the time of polymerization, and is not practical because of high production cost. In the case of the N-substituted maleimide-aromatic vinyl monomer copolymer solution-polymerized in accordance with Japanese Patent Application JP 2003-41080, the final polymerization product synthesized by solution polymerization is adopted to precipitate in methanol, and a large amount of methanol solvent It is inefficient in manufacturing cost. The α-alkylstyrene-N-substituted maleimide-unsaturated nitrile-aromatic vinyl monomer copolymer according to Japanese Patent Publication JP 1985-147414 adopts suspension polymerization, and thus heterogeneous copolymers having different compositions are easily formed, A filtration equipment is required and other large amount of additive such as a suspension agent remains in the polymer product, which has a disadvantageous effect on physical properties. The N-substituted maleimide-unsaturated nitrile-maleic anhydride copolymer according to Japanese Patent Registration Nos. JP 1987-280249 and JP 1990-189361 is a solution polymerized product and thus has a high production cost due to its low practicality and high melt viscosity, In particular, there is a problem that the blendability is lowered when blended with ABS.

The bulk polymerized alpha alkyl styrene-unsaturated nitrile copolymers according to U.S. Pat. Nos. 4874829 and 6593424 are good in processability, but they have α-alkyl styrene as a main component, and their heat resistance is significantly reduced. Solution-polymerized N-substituted maleimide-unsaturated nitrile-aromatic vinyl monomer copolymer according to US Patent No. US 5478903, US 5565537 and solution polymerized N-substituted maleimide-aromatic In the case of the vinyl monomer copolymer, a solution polymerization process is adopted, so that the production cost is considerably high, the heat resistance and the melt viscosity are too high and the processing temperature is also high, and the processability and the blendability due to the difference in melting point when blended with other thermoplastic resins There is a problem that the impact resistance is deteriorated due to deterioration.

Accordingly, the present inventors have found that a conventional maleimide-based copolymer has a high degree of heat resistance (high heat resistance) and a low melting point (high melting point) depending on the high maleimide content, There is a problem of low impact resistance due to degradation, high cost of production cost due to solution polymerization or suspension polymerization applied, and low heat resistance (low heat resistance), low processability, In order to simultaneously solve problems such as poor appearance quality of a molded product and poor color tone of natural color when blended with a resin, maleimide having excellent heat resistance and thermal stability in the PCT / KR2007 / 004392, And the heat-resistant effect and thermal stability of α-alkylstyrene, which is lower than that of maleimide but is excellent in impact resistance, are applied together. However, by using less expensive maleimide, (High productivity) and low-cost production (low price production) of polymerized products, and also to achieve a high melt viscosity and a low melt viscosity point due to the reduced maleimide content By supplementing the lack of heat resistance with an appropriate amount of alpha-alkylstyrene, unsaturated nitrile, which is a monomer having excellent chemical resistance and serves as a solvent for the solid type maleimide, is applied to make the polymerization system homogeneous, And the aromatic vinyl monomer having excellent processability and coloring property is applied to significantly decrease the melt viscosity of the polymerized product and to maximize the kneading property with other (other) thermoplastic resin. In the polymerization process, By developing and applying the adhered continuous bulk polymerization process, it is possible to finally achieve excellent thermal stability and heat resistance at a high temperature The melt viscosity is remarkably low. Thus, the thermoplastic resin is excellent in not only the processability but also the productivity, processability and moldability of the thermoplastic resin when blended with other (other) thermoplastic resin, ) And high-efficiency (three-component) copolymers, and a manufacturing process thereof.

However, there has been a demand in the market for improved heat resistance while maintaining the improved productivity, processability and moldability of the conventional three-dimensional block copolymers.

A problem to be solved by the present invention is to provide a continuous melt-polymerization method of a low-melt viscosity maleimide-? Alkylstyrene-based heat resistant tri (co) copolymer excellent in thermal stability, heat resistance, processability and kneadability at high temperature In the continuous bulk process, a new bulk polymerization process capable of further improving the heat resistance of the final product is provided.

Another object to be solved by the present invention is to provide a continuous block of a low melting point viscosity maleimide-alpha alkyl styrene heat resistant tri (co) copolymer excellent in thermal stability, heat resistance, processability and kneading property at high temperature And to provide a novel three-dimensional block copolymer which is further improved in heat resistance of a final product in a polymerization process (Continuous Bulk Process).

In the present invention, it has been found that by reducing the content of oligomers contained in the maleimide-α alkylstyrene-unsaturated nitrile ternary copolymer, improvement in heat resistance can be achieved while maintaining productivity, processability and moldability, It has been surprisingly discovered that the content of the oligomer can be reduced by simply preventing the contact between the unsaturated nitrile monomer and the maleimide monomer, leading to the present invention.

Accordingly, in order to solve the above problems, the present invention provides a process for producing a terpolymer of N-substituted maleimide monomer, an alkylstyrene monomer, and an unsaturated nitrile monomer, A mixture of the substituted maleimide monomer and the unsaturated nitrile monomer is prepared, separated from the? Alkylstyrene monomer, and introduced into the polymerization tank. Although it is not theoretically limited, it is possible to inhibit the generation of polymerization inhibiting components by the contact of the N-substituted maleimide and the? Alkylstyrene monomer before the polymerization, and to suppress the oligomer generation of the final product.

In the present invention, the term " oligomer " means not only dimers and trimers of monomers, but also low molecular weight polymers having a molecular weight of 1000 or less.

In the present invention, the mixture of the N-substituted maleimide monomer and the unsaturated nitrile monomer is obtained by dissolving the N-substituted maleimide monomer in the solid state at room temperature in the unsaturated nitrile monomer, separating the monomer from the alpha alkylstyrene monomer in a solution state, .

In the practice of the present invention, the maleimide-? Alkylstyrene-based copolymer is obtained by continuously separating a mixture of an N-substituted maleimide monomer and an unsaturated nitrile monomer from an? Alkylstyrene monomer and polymerizing the monomer mixture into a polymerization vessel containing at least one stirring tank reactor Inputting; Continuously polymerizing the monomer mixture charged into the polymerization vessel; And transferring the polymer and unreacted monomer mixture to a devolatilizer and separating them.

In the present invention, the N-substituted maleimide monomer is at least one selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-cyclohexyl maleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, Hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-benzylmaleimide and a small amount copolymerizable therewith Of monomers.

In the present invention, the? -Alkylstyrene monomer is a monomer containing? -Methylstyrene,? -Ethylstyrene, methyl? -Methylstyrene and a small amount of a monomer copolymerizable therewith.

In the present invention, examples of the unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, and? Chloroacrylonitrile.

In the present invention, at least one stirring tank reactor may be continuously connected to the polymerization tank in which the introduced monomers are polymerized. The mixture of the polymer discharged from each of the stirring tank reactors and the unreacted monomer is introduced into the next stirred tank reactor to further increase the conversion rate, or is introduced into the devolatilizer to separate unreacted monomers.

In one embodiment of the present invention, the mixture of the polymer and the monomer formed through the first stirring tank reactor is transferred through the lower portion of the first stirring tank reactor, is introduced into the upper portion of the second stirring tank reactor, 2 stirred tank reactor and then introduced into the upper portion of the third stirred tank reactor, and the same process is carried out to reach the fifth stirred tank reactor.

Further, in a preferred embodiment of the present invention, each of the stirring tank reactors may be further connected to an additive or a monomer input line in order to control the viscosity or the composition of the final product.

The mixture of polymer and monomer through each stirred tank reactor is transferred to the next stirred tank reactor or transferred directly to the devolatilizer in each of the stirred tank reactors to separate unreacted monomer and polymer.

The recovered unreacted monomer mixtures are fed back to the upper portion of the first stirred tank reactor via a condenser. The molten polymer passed through a devolatilizer is passed through an extruder equipped with a vacuum device, Maleimide monomers, alpha-alkylstyrene monomers, unsaturated nitrile monomers, and the like.

In the present invention, the polymerization baths can be operated under pressure or under reduced pressure, and the temperature of the inner polymer and monomer mixture in each polymerization bath during the polymerization is maintained at 60-180 Lt; 0 > C.

In the present invention, the devolatilizer may be installed to separate the unreacted monomer from the polymer generated by the reaction, and the devolatilizer may include one or more devolatilizers. In the practice of the present invention, the devolatilizer may be composed of two or more devolatilizers, and each devolatilizer may be connected to the following devolatilizer or extruder. For example, after the transferred polymer and monomer mixture is passed through the first devolatilizer and then transferred to the second devolatilizer or directly to the extruder or the molten polymer passed through the second devolatilizer, 3 to the third devolatilizer or directly to the extruder. The devolatilizer attached at the end can be connected directly to the extruder. In the practice of the present invention, the devolatilizer may be operated under reduced pressure for easy separation of the unreacted monomer, and preferably the internal pressure is operated in the range of 0 to -760 mmHg.

In the present invention, the unreacted monomer mixture recovered from the devolatilizer is condensed again in its original form as it passes through a condenser, and is analyzed by a component analyzer, preferably a GC (Gas Chromatography, CP-3800 / VARIAN) And its content is reanalyzed and put into the upper part of the polymerization tank No. 1, and this series of processes is continuously repeated until the production is completed.

In the present invention, the final polymerization conversion ratio of the polymer and the monomer mixture transferred to the devolatilizer, preferably the first devolatilizer, can be maintained in the range of 20 to 80 wt%. At this time, if the final polymerization conversion rate is 20 wt% or less, the melt viscosity of the polymer and monomer mixture is too low to be transferred through the polymer pump. Even if the final polymerization conversion rate is 80 wt% or more, the melt viscosity becomes rather high, It becomes difficult.

In the present invention, the extruder is equipped with a vacuum device which maintains a vacuum state in the range of 0 to -760 mmHg so as to additionally remove unreacted monomers, and the cylinder temperature is set to 100 to 350 ° C.

In the present invention, the terpolymer produced through the bulk polymerization comprises 5 to 60% by weight of N-substituted maleimide, 10 to 70% by weight of? -Alkylstyrene monomer and 5 to 50% by weight of unsaturated nitrile monomer, Has an average molecular weight (Mw) of 7 to 200,000 and a glass transition temperature of 130 to 200 占 폚 and has a low melt viscosity.

In the present invention, the monomer mixture may optionally further comprise an organic solvent at 20 wt.% Or less and contain 0 to 5000 ppm of an initiator. In the practice of the present invention, the solvent may be a single organic solvent having a boiling point of 60 to 200 ° C or a mixture thereof, and the initiator may be azobisisobutyronitrile, benzoyl peroxide, t-butyl peroxy- -Ethyl-hexanoate, cumylperoxide, t-butylperoxide, 1,1-di (t-butylperoxy) cyclohexane, or mixtures thereof.

According to the present invention, a copolymer having improved heat resistance can be produced in the production of a three-dimensional bulk copolymer having the same composition. The method for producing a block copolymer according to the present invention can reduce the content of oligomers due to side reactions, thereby improving the heat resistance and solving the problem caused by gas generation in post-processing such as injection molding.

1 is a process diagram of a polymerization process according to an embodiment of the present invention.
2 is a flow chart of a polymerization process according to a comparative example of the present invention.
FIG. 3 is a graph showing the measurement of oligomers according to Examples and Comparative Examples according to the present invention.

The present invention will be described in more detail by way of the following examples. The following examples illustrate the invention in detail, but are for the purpose of illustrating the invention and are in no way to be construed as limiting thereof.

Example

Examples 1 to 4

First, as shown in Fig. 1, N-phenylmaleimide (1) and acrylonitrile (2), which are main raw materials, were added to the first preparation (5) at room temperature and dissolved by stirring at the ratios described in Table 1 . When the dissolution is completed, the temperature of the polymerization bath is raised to an appropriate temperature while gradually introducing the monomer mixture of Preparation 1 (5) and? -Methylstyrene (3) through the separate charging line in the ratio shown in Table 1 . In this process, the solvent and the initiator were gradually added to the stirred tank reactor 11 from the upper part in the amounts shown in Table 1. During the polymerization, N, N-phenylmaleimide and acrylonitrile solutions were prepared in the same manner as in the preparation of the above-mentioned first, second, third, fourth and fifth preparations (not shown) Respectively.

When the conversion rates in the five stirred tank reactors (11), (12), (13), (14) and (15) connected in series reached the conversion ratios shown in Table 1, the polymer and monomer mixture Was transferred to the first devolatilizer (31) through a polymer pump. During the transfer, the temperature was increased to the operating temperature of the first devolatilizer 31 while passing through the first heat exchanger (21). The first devolatilizer 31 was operated at 350 ° C. under a vacuum of 350 torr to recover unreacted monomers. After raising the temperature to the operating temperature of the second devolatilizer (32) through the second devolatilizer (22) after passing through the first devolatilizer (31), a second devolatilization The remaining unreacted monomer was recovered via the device 32.

Such a series of continuous processes is continuously repeated until production is completed. The unreacted remaining monomers are volatilized and recovered through the condenser 51 in the process of passing through the first and second devolatilizers, The ratio was calculated and then introduced into the polymerization tank from the top of the polymerization tank. This series of devolatilization continuous processes is continuously repeated until the production of the polymer product is completed.

The molten polymer having almost no unreacted residual monomer remaining after passing through both of the first and second devolatilizing apparatuses 31 and 32 has an extruder 41 equipped with a vacuum device having a cylinder temperature set at 180 to 260 ° C, , And finally a maleimide-? Alkylstyrene-based heat resistant three-terminal copolymer in the form of a pellet was prepared. The composition of the thus prepared terpolymer in the polymer was determined by EA (Elementary analysis, Vario EL / ELEMENTAR), ¹ H / ¹³ C NMR (Nuclear Magnetic Resonance, 400 MHz / VARIAN) and Fourier Transform Infrared Spectroscopy , FTS-60A / VIO-RAD). The molecular weight was determined as the relative value of a standard PS (Standard Polystyrene) sample through GPC (Gel Permeation Chromatography, Shimadzu VP) using THF (tetrahydrofuran) as an eluate The glass transition temperature was analyzed by DSC (Differential Scanning Calorimetry, Diamond / Perkin-Elmer). Unreacted residual monomer was analyzed by GC (Gas Chromatography, CP-3800 / VARIAN) The stability was measured using a TGA (Thermogravimetric analysis, Pyris 6 / Perkin-Elmer) at a temperature corresponding to 1 wt% reduction in the initial weight, and the results are shown in Table 1 and Table 2.

Comparative Examples 1 to 4

As shown in Fig. 2, this comparative example is a method in which N-phenyl maleimide (1), acrylonitrile (2) and alpha methyl styrene (3), which are main raw materials, And the mixture was stirred at the ratio shown in Table 1 and dissolved. When the dissolution is completed, the temperature of the polymerization bath is gradually raised to an appropriate temperature while gradually supplied from the top of the polymerization bath. In this process, the solvent and the initiator were slowly added from the upper part of the polymerization vessel in the amounts shown in Table 1. In the second, third, fourth and fifth preparations (not shown) during the polymerization, the mixed monomers are prepared in the same manner as mentioned above, and then, when the raw materials of the first preparation are exhausted, Respectively.

When the conversion rates in the five stirred tank reactors (11), (12), (13), (14) and (15) connected in series reached the conversion ratios shown in Table 1, the polymer and monomer mixture Was transferred to the first devolatilizer (31) through a polymer pump. During the transfer, the temperature was increased to the operating temperature of the first devolatilizer 31 while passing through the first heat exchanger (21). The first devolatilizer 31 was operated at 350 ° C. under a vacuum of 350 torr to recover unreacted monomers. After the temperature of the second devolatilizer (32) is raised to the operating temperature through the first devolatilizer (31) and then through the second heat exchanger (22), the second devolatilizer And the remaining unreacted monomer was recovered through the separator 32.

Such a series of continuous processes is continuously repeated until production is completed. The unreacted remaining monomers are volatilized and recovered through the condenser 51 in the process of passing through the first and second devolatilizers, The ratio was calculated and then introduced into the polymerization tank from the top of the polymerization tank. This series of devolatilization continuous processes is continuously repeated until the production of the polymer product is completed.

The molten polymer having almost no unreacted residual monomer remaining after passing through both of the first and second devolatilizing apparatuses 31 and 32 has an extruder 41 equipped with a vacuum device having a cylinder temperature set at 180 to 260 ° C, , And finally a maleimide-? Alkylstyrene-based heat resistant three-terminal copolymer in the form of a pellet was prepared. The composition of the thus prepared terpolymer in the polymer was determined by EA (Elementary analysis, Vario EL / ELEMENTAR), ¹ H / ¹³ C NMR (Nuclear Magnetic Resonance, 400 MHz / VARIAN) and Fourier Transform Infrared Spectroscopy , FTS-60A / VIO-RAD). The molecular weight was determined as the relative value of a standard PS (Standard Polystyrene) sample through GPC (Gel Permeation Chromatography, Shimadzu VP) using THF (tetrahydrofuran) as an eluate The glass transition temperature was analyzed by DSC (Differential Scanning Calorimetry, Diamond / Perkin-Elmer). Unreacted residual monomer was analyzed by GC (Gas Chromatography, CP-3800 / VARIAN) The stability was measured using a TGA (Thermogravimetric analysis, Pyris 6 / Perkin-Elmer) at a temperature corresponding to 1 wt% reduction in the initial weight, and the results are shown in Table 1 and Table 2.

[Table 1]

In Table 1 above, Tol. Refers to Toluene, and a) refers to 1,1-Di (t-butylperoxy) cyclohexane.

[Table 2]

&Quot; One Peak " means that the kneading property with other resins is excellent. As described above, the oligomer content and the unreacted residual amount due to the side reaction of the polymer were decreased by 10-20% or more per a unit, and the glass transition temperature was increased by 5-10 ° C.

Claims (9)

A method for producing a maleimide-? -Alkylstyrene-based block copolymer by continuously introducing a mixture of an N-substituted maleimide monomer,? -Alkylstyrene, and an unsaturated nitrile monomer into a polymerization vessel in which one or more polymerization baths are connected in series,
The N-substituted maleimide monomer forms a mixture dissolved in the unsaturated nitrile monomer, separates it from the? -Alkylstyrene monomer and puts it into the first polymerization vessel,
Wherein the unreacted N-substituted maleimide monomer, the unsaturated nitrile monomer, and the? -Alkylstyrene are recovered and re-introduced into the first polymerization reactor. delete delete The process of claim 1, wherein the N-substituted maleimide monomer is selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- But are not limited to, butyl maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-cyclohexylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, 1 in the group consisting of maleimide, N-lauryl maleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N- Or two or more of them are selected. The process for producing a block copolymer according to claim 1, wherein the? -Alkylstyrene monomer is selected from the group consisting of? -Methylstyrene,? -Ethylstyrene and methyl? -Methylstyrene. The positive photosensitive composition according to claim 1, wherein the unsaturated nitrile monomer is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile, and? -Chloroacrylonitrile Mass - copolymer manufacturing process. The mass-copolymerization process according to claim 1, wherein the unreacted monomer mixture recovered from the devolatilizer is introduced into a raw material feed line via a condenser, and the polymer is produced through an extruder equipped with a vacuum device. The process for producing a block copolymer according to claim 1, wherein the monomer mixture further comprises 20 parts by weight or less of an organic solvent based on 100 parts by weight of the mixture, and 0 to 5000 ppm of an initiator. 9. The method according to claim 8, wherein the solvent is a single organic solvent having a boiling point of 60 to 200 DEG C or a mixture thereof, and the initiator is azobisisobutyronitrile, benzoyl peroxide, t-butyl peroxy- Ethyl-hexanoate, cumyl peroxide, t-butyl peroxide, 1,1-di (t-butylperoxy) cyclohexane or mixtures thereof.

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