KR20150088199A - Method for producing polymer composition, polymer composition thereby and formed article thereof - Google Patents

Abstract

The present invention provides a polymer composition comprising a methacryl resin having a side chain including a cycloaliphatic hydrocarbon group and/or an aromatic hydrocarbon group and a molded article prepared therefrom, wherein the polymer composition has low coloring property and excellent transparency. Accordingly, the present invention relates to a method for preparing a polymer composition comprising a methacryl resin having a side chain including a cycloaliphatic hydrocarbon group and/or an aromatic hydrocarbon group, which comprises the steps of: successively feeding a source material including a source monomer and a polymerization initiator into one or more reactor to perform a successive polymerization; and successively withdrawing the polymer composition from the reactor, wherein the source monomer comprises; (a) 50-95 wt% of methyl methacrylate, (b) 5-50 wt% of (meth)acrylate including a cycloaliphatic hydrocarbon group and/or an aromatic hydrocarbon group; and (c) 0-20 wt% of a monomer which can be co-polymerized with the monomer (a) and/or the monomer (b), with respect to 100 wt% of the source monomer.

Description

FIELD OF THE INVENTION The present invention relates to a method for producing a polymer composition,

The present invention relates to a method for producing a polymer composition comprising a methacrylic resin having a side chain containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, as well as a polymer composition and a molded article thereof.

For example, a methacrylic resin having a side chain containing an alicyclic hydrocarbon group such as a cyclohexyl group or an aromatic hydrocarbon group such as a phenyl group may be used as a thermoplastic resin having a main polymer chain containing an aromatic ring, It has excellent compatibility with polycarbonate resin. Thus, these resins can be mixed to provide a clear polymer blend (or a polymer composition that can be referred to as a polymer blend or polymer alloy) (see, for example, Patent Documents 1 and 2 below). Such a polymer blend is characterized by its polycarbonate resin properties such as transparency, excellent weatherability (particularly excellent resistance to ultraviolet light) and two properties due to methacrylic resin, such as enhanced surface hardness, and excellent heat resistance, and It has mechanical properties such as impact resistance. Accordingly, the application thereof is expected in various fields, particularly in the optical field.

Patent Document 1: JP S63-90551 A Patent Document 2: JP S64-1749 A

Patent Literatures 1 and 2 disclose a method of producing a transparent polymer composition by suspension polymerization which has a side chain containing an alicyclic hydrocarbon group such as a cyclohexyl group and is capable of mixing with an aromatic polycarbonate resin and then discharging the mixture to produce a transparent polymer mixture A methacrylic resin is produced.

However, the methacrylic resins obtained according to the procedures disclosed in Patent Documents 1 and 2 are contaminated with some impurities such as unreacted starting monomers, oligomers obtained and stabilizers for suspension polymerization during suspension polymerization. The methacrylic resin tends to be deteriorated in its transparency or hue. Such drawbacks can degrade the transparency of the resultant polymer composition. Therefore, the optical characteristics of the methacrylic resin prepared in the suspension polymerization are insufficient, and further improvement is required.

Accordingly, it is an object of the present invention to provide polymeric compositions having low colorability and good transparency as well as molded articles thereof, including methacrylic resins having side chains containing alicyclic hydrocarbon groups and / or aromatic hydrocarbon groups .

The present invention provides those described in the following items [1] to [14], but the present invention is not limited to those described below.

[One]

A process for producing a polymer composition comprising a methacrylic resin having side chains containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group,

 A raw material containing a raw material monomer and a polymerization initiator is continuously supplied to at least one reactor and continuous polymerization is carried out in the reactor to obtain a polymer comprising a methacrylic resin having a side chain containing an alicyclic hydrocarbon group and / A continuous polymerization step of producing a composition and continuously withdrawing the polymer composition from the reactor,

Here, the raw material monomers are used in an amount of 100% by weight based on the total weight of the raw material monomers,

(a) from 50 to 95% by weight of methyl methacrylate,

(b) 5 to 50% by weight of a (meth) acrylate represented by the formula (I)

(Wherein,

R ¹ represents a hydrogen atom or a methyl group,

R ² represents an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, an alkyl group substituted with a phenyl group, a phenyl group, a phenyl group substituted with an alkyl group, an alkyl group substituted with a naphthyl group, a naphthyl group, , Dicyclopentanyl group or dicyclopentenyl group), and

(c) 0 to 20% by weight of a monomer copolymerizable with methyl methacrylate and / or (meth) acrylate represented by the formula (I) (hereinafter may be referred to as "copolymerizable monomer"),

≪ / RTI >

[2]

The method according to item [1], wherein the continuous polymerization is continuous bulk polymerization.

[3]

In the item [1] or [2], the polymer composition continuously taken out from the reactor is continuously fed to a devolatilizing extruder, at least a part of the volatile component is removed from the polymer composition in a devolatilizing extruder, Further comprising a devolatilization step of continuously extruding the resulting polymer composition after removing at least a portion of the polymer composition.

[4]

The method according to item [3], wherein the mixing temperature in the devolatilization extruder is in the range of 180 to 320 ° C and the shear rate in the devolatilization extruder is in the range of 10 to 500 sec ^-1 .

[5]

The method according to item [3], further comprising a separation-recovery step of separating and recovering the (meth) acrylate represented by the formula (I) from the volatile component removed in the devolatilizing extruder.

[6]

The method according to item [3], further comprising a step of supplying a thermoplastic resin having a main polymer chain containing an aromatic ring to the polymer composition before extruding the polymer composition from a devolatilizing extruder.

[7]

The method according to any one of items [1] to [6], wherein the polymer composition comprises a thermoplastic resin in addition to the methacrylic resin.

[8]

The method according to item [6] or [7], wherein the polymer composition contains the thermoplastic resin in a weight ratio of 5 to 90% by weight based on 100% by weight of the total weight of the methacrylic resin and the thermoplastic resin.

[9]

The method according to any one of items [6] to [8], wherein the thermoplastic resin is at least one selected from the group consisting of an aromatic polycarbonate and a polyethylene terephthalate.

[10]

The methacrylic resin according to any one of items [1] to [9], wherein the methacrylic resin is at least one selected from the group consisting of methyl methacrylate, (meth) acrylate represented by the formula (I) (Meth) acrylate and 0 to 20% by weight, based on 100% by weight, of polymerized units, respectively, of 50 to 95% by weight of methyl methacrylate, 5 to 50% ≪ / RTI > of a copolymerizable monomer.

[11]

The method according to any one of items [1] to [10], wherein the (meth) acrylate represented by the formula (I) is selected from the group consisting of cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, Wherein the at least one monomer is at least one selected from the group consisting of methacrylate, methacrylate, naphthyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, and dicyclopentenyl methacrylate.

[12]

The method according to any one of items [1] to [11], wherein the copolymerizable monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate and butyl acrylate.

[13]

A polymer composition obtainable / obtainable by a method according to any one of items [1] to [12].

[14]

A molded article obtainable / obtainable by molding a polymer composition according to item [13].

The present invention can provide a molded article thereof as well as a polymer composition having excellent optical properties such as low coloring property and excellent transparency, including a methacrylic resin having a side chain containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group.

Figure 1 is a schematic illustration illustrating an apparatus for continuous polymerization, which is used in a preferred embodiment of the present invention.

The present invention relates to a process for preparing a polymer composition comprising a methacrylic resin having side chains containing alicyclic hydrocarbon groups and / or aromatic hydrocarbon groups.

The present invention relates to a process for the production of a methacrylic resin having a side chain containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group by continuously feeding raw materials containing raw material monomers and a polymerization initiator into one or more reactors, And a continuous polymerisation step of continuously withdrawing the polymer composition from the reactor. ≪ Desc / Clms Page number 3 >

According to the present invention, a methacrylic resin having a side chain containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group in the continuous polymerization step can be produced. Thereby, during the polymerization, the amount of contamination by contaminating impurities (for example, unreacted raw monomer (s), oligomer (s), etc.) (or residual amounts thereof) can be significantly reduced. Thus, opacification of polymer compositions comprising methacrylic resins and methacrylic resins as well as coloration and discoloration can be significantly inhibited.

Thus, in the present invention, such a continuous polymerization step for producing a methacrylic resin having a side chain containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group is advantageous in that a polymer composition having excellent optical properties such as low coloring property and excellent transparency And a shaped article thereof.

Here, the polymer composition as described above, which has excellent optical properties such as low coloring property and excellent transparency, and molded articles thereof, can be used in a continuous polymerization step for the production of a methacrylic resin having side chains containing alicyclic hydrocarbon groups and / or aromatic hydrocarbon groups Quot; is not limited by the above-described theory.

Here, the polymer composition obtained by the production method according to the present invention and molded articles thereof have extremely low coloring property. This means that the yellow index (YI) as an index indicating the degree of coloring is small. More specifically, the value of YI measured according to JIS K 7105 is defined to be 1.1 or less.

The polymer compositions according to the invention and their molded articles have very good transparency. This means that its visually observed appearance is colorless and transparent. More specifically, it is defined that the total light transmittance (Tt) measured according to JIS K 7361-1 is 90% or more and YI is 1.1 or less.

Raw monomer

The raw material monomers used in the present invention may be composed of a methacrylic resin having a side chain containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group. The raw monomer includes at least the following:

(a) methyl methacrylate (hereinafter may be abbreviated as "monomer (a)"), and

(meth) acrylate (hereinafter abbreviated as "monomer (b)") or (meth) acrylate having an alicyclic hydrocarbon group or aromatic hydrocarbon group represented by the formula (I) Quot; acrylate ", or simply "(meth) acrylate").

Further, the starting monomer may be used as any monomer (c) or a monomer copolymerizable with the above-mentioned methyl methacrylate and / or the (meth) acrylate represented by the above-mentioned formula (I) Quot; or "copolymerizable monomer ", or simply" monomer ").

These monomers (a), (b) and (c) are described in more detail below.

The monomer (a)

The monomer (a) is commercially available methyl methacrylate. As the monomer (a), a commercially available product may be used as such, or methyl methacrylate which has been previously synthesized according to a conventionally known procedure may be used.

The amount of the monomer (a) to be used is not particularly limited. For example, the amount is generally in the range of 50 to 95% by weight, preferably in the range of 60 to 90% by weight, based on the total weight of the raw monomers (as 100% by weight). When the content of the monomer (a) is too small, the optical properties of the resultant methacrylic resin are lowered. When the content of the monomer (a) is too large, when the polymer composition contains other thermoplastic resin, transparency of the obtained polymer composition is lowered.

The monomer (b)

The monomer (b) is a (meth) acrylate having at least one alicyclic hydrocarbon group or at least one aromatic hydrocarbon group represented by the following formula (I)

In the formula (I), R ¹ represents a hydrogen atom or a methyl group, preferably a methyl group.

In the formula (I), R ² represents an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, an alkyl group substituted with a phenyl group, a phenyl group, , "Naphthyl group", "naphthyl group substituted with an alkyl group", "dicyclopentanyl group" or "dicyclopentenyl group".

Therefore, according to the present invention, the (meth) acrylate of the formula (I) may be produced by continuously polymerizing an alicyclic hydrocarbon group such as a cycloalkyl group, a dicyclopentanyl group and a dicyclopentenyl group and / or an aromatic hydrocarbon group such as a phenyl group and a naphthyl group May be used as a raw material monomer for introduction into the side chain of the methacrylic resin synthesized by the above step. When the methacrylic resin contains such alicyclic hydrocarbon groups and / or aromatic hydrocarbon groups, compatibility with other thermoplastic resin (s) can be increased due to their hydrophobicity or lipophilicity, if present. Thus, transparent polymer compositions containing such other thermoplastic resin (s) can be obtained. The properties such as heat resistance and low-hygroscopicity of the obtained methacrylic resin are improved due to alicyclic hydrocarbon groups and / or aromatic hydrocarbon groups.

The "alkyl group" of the "alkyl group substituted with a cycloalkyl group" represented by R ² is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, , tert-butyl group and the like. The "cycloalkyl group" as the substituent is preferably a cycloalkyl group having 5 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclododecyl group. The number of the "cycloalkyl group" as the substituent and the moiety substituted on the alkyl group are not particularly limited. For example, the "alkyl group substituted with a cycloalkyl group" represented by R ² includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, (S) having 5 to 12 carbon atoms in place of at least one hydrogen atom (H) in the alkyl group.

The "cycloalkyl group" represented by R ² is preferably a cycloalkyl group having 5 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclododecyl group. Optionally, the cycloalkyl group may be substituted with any substituent such as a hydroxyl group, an amino group, a sulfone group and the like.

The "cycloalkyl group" of the "cycloalkyl group substituted with an alkyl group" represented by R ² is preferably a cycloalkyl group having 5 to 12 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, . The "alkyl group" as the substituent is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, The number of the "alkyl group" as the substituent and the substitution moiety on the cycloalkyl group are not particularly limited. For example, the "cycloalkyl group substituted with an alkyl group" represented by R ² includes a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group and the like, each of which may have at least one (S) having 1 to 4 carbon atoms in place of the hydrogen atom (H).

The "alkyl group" of the "alkyl group substituted with a phenyl group" represented by R ² is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, n-propyl group, isopropyl group, butyl group and the like. The number of the "phenyl group" as the substituent and the substitution moiety on the alkyl group are not particularly limited. For example, the "alkyl group substituted with a phenyl group" represented by R ² includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert- (S) in place of at least one hydrogen atom (H) in the alkyl group, and includes, for example, a benzyl group and a phenethyl group.

The "phenyl group" represented by R ² is not particularly limited. Optionally, the phenyl group may be substituted with any substituent such as a hydroxyl group, an amino group, a sulfone group and the like.

The "alkyl group" as the substituent on the phenyl group of the "phenyl group substituted with an alkyl group" represented by R ² is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, n-propyl group, isopropyl group, Isobutyl group, tert-butyl group and the like. The number of the "alkyl group" as the substituent and the substitution moiety on the phenyl group are not particularly limited. For example, the "alkyl group-substituted phenyl group" represented by R ² includes o-tolyl group, m-tolyl group, p-tolyl group and the like.

The "alkyl group" of the "alkyl group substituted with a naphthyl group" represented by R ² is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, , tert-butyl group and the like. The number of the "naphthyl group" as the substituent and the substitution moiety on the alkyl group are not particularly limited. For example, the "alkyl group substituted with a naphthyl group" represented by R ² includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, (S) in place of at least one hydrogen atom (H) in the alkyl group, and examples thereof include a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group and a 2-naphthylethyl group.

The "naphthyl group" represented by R ² is not particularly limited. Optionally, the naphthyl group may be substituted with a substituent such as a hydroxyl group, an amino group, a sulfone group or the like.

The "alkyl group" as the substituent on the naphthyl group of the "naphthyl group substituted with an alkyl group" represented by R ² is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, Isobutyl group, tert-butyl group and the like. The number of the "alkyl group" as the substituent and the substitution moiety on the naphthyl group are not particularly limited. For example, the "naphthyl group substituted with an alkyl group" represented by R ² includes a methylnaphthyl group, an ethylnaphthyl group, and the like.

Optionally, represented by "dicyclopentanyl group" and R ² being represented by R ² "dicyclo pentenyl group" may be substituted with a substituent such as each represents an alkyl group, a hydroxyl group, an amino group, a sulfone group. The alkyl group as a substituent is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group or tert-

In the present invention, as long as R ² can provide an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group to the obtained methacrylic resin, R ² is not limited to those described above.

R ² is preferably a cycloalkyl group (preferably a cyclohexyl group), a phenyl group, a naphthyl group, a dicyclopentanyl group and a dicyclopentenyl group, more preferably a cyclohexyl group and a phenyl group.

According to the present invention, the (meth) acrylate of the formula (I) is preferably a cyclohexyl acrylate (wherein R ¹ is a hydrogen atom and R ² is a cyclohexyl group), cyclohexyl methacrylate (Wherein R ¹ = a methyl group and R ² = a cyclohexyl group), phenyl acrylate (wherein R ¹ is a hydrogen atom and R ² is a phenyl group), phenyl methacrylate (wherein R ¹ is a methyl group and, R ² = phenyl group Im), naphthyl of acrylates (wherein, R ¹ = hydrogen, R ² = naphthyl group), a naphthyl, and methacrylate (in the formula, R ¹ = methyl, R ² = (Wherein R ¹ is a hydrogen atom and R ² is a dicyclopentanyl group), dicyclopentanyl methacrylate (wherein R ¹ is a methyl group and R ² is a dicyclopentanyl group), dicyclopentanyl acrylate A cyclopentanyl group), dicyclopentenyl acrylate (wherein R ¹ is a hydrogen atom, R ² is a dicyclopentenyl group), and dicyclopentene Carbonyl meter (in the formula, and R ¹ = methyl, R ² = dicyclopentenyl group) acrylate, more preferably cyclohexyl acrylate (wherein, R ¹ = hydrogen, R ² = cyclohexyl Im ), Cyclohexyl methacrylate (wherein R ¹ is a methyl group and R ² is a cyclohexyl group), phenyl acrylate (wherein R ¹ is a hydrogen atom and R ² is a phenyl group) and phenyl methacrylate (Wherein R ¹ is a methyl group and R ² is a phenyl group), still more preferably cyclohexyl methacrylate (wherein R ¹ is a methyl group and R ² is a cyclohexyl group) and phenyl methacrylate a (wherein, R ¹ = methyl group, R ² = phenyl group Im) rate.

For example, the amount of (meth) acrylate (or monomer (b)) of formula (I) used is generally in the range of 5 to 50% by weight, based on the total weight of the starting monomers Is in the range of 10 to 40% by weight. When the content of the monomer (b) is less than 5% by weight, when the polymer composition includes other thermoplastic resins described below such as a thermoplastic resin having a main polymer chain containing an aromatic ring, the content of the methacrylic resin and the thermoplastic resin The transparency of the obtained polymer composition may be lowered because compatibility may be deteriorated. On the other hand, in the case where the content of the monomer (b) is more than 50% by weight, the obtained polymer composition (b) can be obtained as in the case where the polymer composition includes other thermoplastic resins described below such as a thermoplastic resin having a main polymer chain containing an aromatic ring (In particular, resistance to ultraviolet rays) of the film can be lowered.

As the monomer (b), one (meth) acrylate of the formula (I) may be used alone, or two or more (meth) acrylates of the formula (I) may be used in any combination.

The monomer (c)

The monomer (c) is a monomer copolymerizable with the monomer (a) (i.e., methyl methacrylate) and / or the monomer (b) (i.e., the (meth) acrylate of the formula (I)). Monomer (c) may optionally be added to the raw material (s). The monomer (c) may be a polyfunctional monomer or a monofunctional monomer. The monomer (c) is preferably a monofunctional monomer from the viewpoint of controllability in continuous polymerization, molding processability, and the like.

For example, monofunctional monomers that can be used as monomer (c) include alkyl (meth) acrylates ( provided that monomer (a) (i.e., methyl methacrylate) and monomer (b) (Meth) acrylate)), alkenyl cyanide compounds (e.g., acrylonitrile, methacrylonitrile and the like), acrylic acid, methacrylic acid, maleic anhydride and the like. Of these, alkyl (meth) acrylates, i.e. alkyl methacrylates and alkyl acrylates, are preferred.

Examples of the alkyl methacrylate that can be used as the monomer (c) include, but are not limited to, those copolymerizable with the monomer (a) and / or the monomer (b), such as an alkyl moiety, Alkyl methacrylates including linear or branched or cyclic alkyl groups such as ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and the like. Of these, alkyl methacrylates in which the alkyl group has 2 to 4 carbon atoms are preferred.

The alkyl acrylates which can be used as the monomer (c) include, but are not limited to, those copolymerizable with the monomer (a) and / or the monomer (b), such as an alkyl moiety, Alkyl acrylates containing linear or branched or cyclic alkyl groups such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, butyl acrylate (e.g. n-butyl acrylate, Acrylate, sec-butyl acrylate, isobutyl acrylate), 2-ethylhexyl acrylate, and the like. Of these, alkyl acrylates having an alkyl group of 1 to 4 carbon atoms are preferable, and methyl acrylate, ethyl acrylate and butyl acrylate are more preferable.

Here, one monomer (c) may be used alone, or two or more monomers (c) may be used in any combination.

For example, the amount of the monomer (c) to be used is 0 to 20% by weight ( provided that the amount of the monomer (c) is 0% by weight based on 100% by weight of the total weight of the starting monomer) c) is not present), preferably in the range of 0.1 to 20 wt%, more preferably in the range of 0.1 to 10 wt%, still more preferably in the range of 0.2 to 5 wt%. The use of the monomer (c) as the raw material monomer is not limited to the obtained methacrylic resin having a side chain containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, as well as the thermal stability and fluidity of a polymer composition containing such a methacrylic resin Thereby improving the characteristics. On the other hand, when the content of the monomer (c) is more than 20% by weight, the transparency of the obtained methacrylic resin and the polymer composition comprising such a methacrylic resin may be lowered.

According to the present invention, in addition to the monomers (a), (b) and / or (c) described above, the starting material may optionally contain other monomer (s). It should be noted that the total% of the raw monomer is not more than 100% by weight.

Polymerization initiator

The polymerization initiator that can be used in the continuous polymerization according to the present invention can be appropriately selected depending on the kind of the methacrylic resin to be polymerized and the raw monomer used in the polymerization reaction. The polymerization initiator is not particularly limited. For example, the polymerization initiator includes a radical polymerization initiator and the like.

Examples of the radical polymerization initiators described above include azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, 1,1'-azobis (1-acetoxy-1-phenylethane) , Dimethyl 2,2'-azobisisobutylate and 4,4'-azobis-4-cyanovaleric acid; Organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, caprylyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, acetylcyclohexylsulfonyl peroxide, t- T-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxy-2-ethylhexanoate, 1,1-di (t-butylperoxy) Hexane, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, Propyl peroxydicarbonate, diisobutyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-n-butyl peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate , Bis (4-t-butylcyclohexyl) peroxydicarbonate, t-amylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-ethylhexa Trimethylpropyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropyl monocarbonate, t-amyl peroxyisopropyl monocarbonate, t-butyl peroxy- Butyl peroxy allyl carbonate, t-butyl peroxyisopropyl carbonate, 1,1,3,3-tetramethylbutylperoxyisopropyl monocarbonate, 1, 2-ethylhexyl carbonate, , 1,2-trimethylpropylperoxyisopropyl monocarbonate, 1,1,3,3-tetramethylbutylperoxyisononate, 1,1,2-trimethylpropylperoxy-isononate, and t- Butyl peroxybenzoate, and the like. Such radical polymerization initiators may be used alone or in any combination of two or more thereof.

The radical polymerization initiator includes, but is not particularly limited to, those described above, preferably those having a half life of not less than 0.1 second and not more than 60 seconds at the polymerization temperature. If the initiator has a half life of 60 seconds or less, the reaction rate can be increased, and in particular, the continuous polymerization reaction can proceed successfully. On the other hand, if the initiator has a half life of less than 0.1 second at the polymerization temperature, the polymerization may be carried out at the inlet front line of the reactor (e.g., the feed port 10a illustrated in Figure 1) , Thereby providing an obstacle to the piping.

The amount of the polymerization initiator to be added is not particularly limited. The amount is generally in the range of 0.001 to 1% by weight based on 100% by weight based on the total weight of the monomers contained in the raw material.

Continuous polymerization step

The production method according to the present invention is characterized in that a raw material containing raw material monomers and a polymerization initiator is continuously fed to one or more reactors and continuous polymerization of the raw material monomers is carried out in the reactor to obtain an alicyclic hydrocarbon group containing an alicyclic hydrocarbon group and / And a continuous polymerization step of continuously producing a methacrylic resin having side chains and continuously taking out the resulting polymer composition containing the methacrylic resin from the reactor.

As long as continuous polymerization for providing a methacrylic resin, preferably continuous bulk polymerization, can be carried out, the reactor which can be used in the present invention is not particularly limited.

More specifically, the reactor may be equipped with a feed port and an effluent port, and preferably a stirrer for agitating the jacket and its contents therein as a means for controlling the temperature of the outer surface of the reactor. The wastewater port can be mounted in position on the top of the reactor. On the other hand, the feed port can generally be located at a suitable location in the reactor lower part. The reactor may further be equipped with a temperature sensor as temperature detecting means for detecting the temperature in the reactor.

The stirrer may be any suitable stirring blade (s), such as a MIG impeller, a MAXBLEND impeller (trade name of Sumitomo Heavy Industries, Ltd.), a paddle impeller, a double spiral ribbon impeller, a FULLZONE impeller (Kobelco Eco-Solutions Co.). Ltd., trade name). To increase the effectiveness of any stirring in the reactor, a reactor equipped with baffle (s) (baffle (s)) is preferred. The reactor may have any other suitable configuration in place of the stirrer.

The continuous polymerization step described above is used in the present invention in which raw materials are continuously supplied and polymerized in the reactor. Therefore, any substance which can become an impurity such as a stabilizer for suspension polymerization is not used. Thus, coloring of the obtained polymer composition due to such impurities can be prevented. Here, according to the present invention, the reaction in the reactor may be a complete mixing type. Therefore, the coloring of the polymer composition can be further prevented.

According to the invention, for example, the temperature in the reactor is in the range of about 100 ° C to 200 ° C in the continuous polymerization stage. The time during which the raw material is applied to the continuous polymerization stage is understood as the average residence time in the reactor. The average residence time can be suitably determined according to the productivity of the polymer for the polymer fraction and the like. For example, the average residence time is within the range of 15 minutes to 6 hours, but is not particularly limited thereto.

In the continuous polymerization step, the continuous polymerization can be carried out under the conditions that the reactor is filled with the reaction mixture (hereinafter referred to as a full-charge condition) without substantially the presence of the gaseous phase. The full-charge condition can prevent the occurrence of any problems such as gel adhesion and growth on the inside surface of the reactor in advance, such that the gel is mixed into the reaction mixture to degrade the quality of the finally obtained polymer composition I will. Furthermore, since full-charge conditions make it possible to use all of the internal volume of the reactor as a reaction space, higher productivity can be achieved.

Since the wastewater port of the reactor can be located at the top of the reactor, full-charge conditions can be simply realized by continuously carrying out withdrawing from the reactor.

In the continuous polymerization step, the continuous polymerization is preferably carried out under conditions which are substantially free from heat transfer from outside the reactor (hereinafter referred to as adiabatic conditions). This adiabatic condition can prevent the occurrence of any problems such as gel adhesion to the inner surface of the reactor and growth thereon, which gel is mixed into the reaction mixture to degrade the quality of the finally obtained polymer composition I will. Furthermore, adiabatic conditions can stabilize the polymerization reaction and can cause self-regulating characteristics for suppression of uncontrolled reactions.

The adiabatic condition can be realized by making the temperature inside the reactor and the temperature of the outer surface thereof generally equal to each other. More specifically, it uses a control device (not shown) to detect the temperature of the outer surface of the reactor set by the jacket (or temperature control means) and the temperature of the reactor Can be realized by adjusting the supply amount of the starting monomer and the polymerization initiator into the reactor by using a pump so that the temperatures are equal to each other. Since extra heat is added into the reactor, it is not desirable to set the temperature of the reactor outer surface much higher than the temperature in the reactor. The smaller the difference between the temperature in the reactor and the temperature of the outer surface of the reactor, the more preferable. More specifically, it is preferable to adjust the temperature difference to within about +/- 5 DEG C range.

Here, any chain transfer agent may optionally be used in the continuous polymerization according to the present invention in order to control the molecular weight of the obtained methacrylic resin. As a chain transfer agent, a monofunctional or multifunctional chain transfer agent may be used. More specifically, examples thereof include alkyl mercaptans such as propyl mercaptan (e.g., n-propyl mercaptan and isopropyl mercaptan), butyl mercaptan (e.g., n-butyl mercaptan and t-butyl mercaptan) (E.g. n-hexyl mercaptan), octyl mercaptan (e.g., n-octyl mercaptan), 2-ethylhexyl mercaptan, dodecyl mercaptan (e.g., n-dodecyl mercaptan and t- Mercaptans); Aromatic mercaptans such as phenyl mercaptan and thiocresol; Mercaptans having 18 or less carbon atoms such as ethylene thioglycol; Polyalcohols such as ethylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol and sorbitol; 1,4-dihydronaphthalene, 1,4,5,8-tetrahydronaphthalene,? -Terpinene, terpinolene, 1,4-cyclohexadiene, hydrogen sulfide and the like. These may be used alone or in combination of two or more thereof.

The amount of the chain transfer agent to be added is not particularly limited, because the amount may vary depending on the kind of the chain transfer agent to be used. The amount is preferably in the range of 0.01 to 5 parts by weight based on 100 parts by weight based on the total weight of the monomers contained in the raw material. For example, when a mercaptan-based chain transfer agent is used, the amount thereof is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight, based on the total weight of the monomers contained in the raw material Sub-range.

In the continuous polymerization according to the present invention, a release agent, an ultraviolet absorber and / or an antioxidant may be further added as a raw material.

Release agent

Examples of the release agent that can be used in the present invention include, but are not limited to, esters of higher fatty acids, higher fatty alcohols, higher fatty acids, higher fatty acid amides, and metal salts of higher fatty acids. As release agents, they can be used alone or in combination of two or more kinds thereof. The release agent may be used and added thereto in an amount within a range of preferably 0.01 to 1.0 part by weight, more preferably 0.01 to 0.50 part by weight based on 100 parts by weight of the methacrylic resin contained in the obtained polymer composition.

Ultraviolet absorber

Examples of ultraviolet absorbers that can be used in the present invention include, but are not limited to, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, cyanoacrylate- do.

Triazine-based ultraviolet absorber

Examples of triazine based ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4- Hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy- 4-diphenyl- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4- , 3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4- -Hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy- Azine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine and the like.

Benzophenone-based ultraviolet absorber

Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy- Hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydro 4,4'-dimethoxy-benzophenone, 2,2 ', 4,4'-tetrahydroxy-benzophenone, and the like.

Benzotriazole-based ultraviolet absorber

Examples of the benzotriazole ultraviolet absorber include 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'- Benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'- Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 3 '- (3 ", 4", 5 ", 6" - (2'- Methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol- Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'- Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'- -Hydroxy-3 ', 5'-di-tert-butylphe Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlorobenzotriazole and the like.

Benzoate-based ultraviolet absorber

Examples of the benzoate-based ultraviolet absorber include 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, 2,6- 3 ', 5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-t- Di-t-butyl-4-hydroxybenzoate, and the like.

Cyanoacrylate ultraviolet absorber

Examples of the cyanoacrylate ultraviolet absorber include 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3- (3 ', 4'-methylenedioxyphenyl ) -Acrylate and the like.

The ultraviolet absorber may be commercially available. For example, triazine-based ultraviolet absorbers include "Kemisorb 102" by CHEMIPRO KASEI KAISHA, LTD and "Adekastab LAF 70" by ADEKA CORPORATION. The benzotriazole ultraviolet absorber includes "Adekastab LA 31" by ADEKA CORPORATION.

The ultraviolet absorber preferably has a weight average molecular weight within the range of from 500 to less than 1000, more preferably from 550 to 700. When the weight average molecular weight is too small, the smoke can be easily released during molding of the obtained composition. If the weight average molecular weight is too large, compatibility with the thermoplastic resin (if present) may be easily deteriorated.

The ultraviolet absorber has a molar absorption coefficient at a wavelength at its maximum absorption value, preferably at least 10 L / mol-cm, more preferably at least 15 L / mol-cm. When the molar absorption coefficient of the ultraviolet absorber is within the above-defined range, the ultraviolet absorptive capacity of the ultraviolet absorber becomes better, so that the content of the ultraviolet absorber can be reduced.

Antioxidant

The antioxidant that can be used in the present invention is not particularly limited, but includes sterically hindered phenol antioxidants, phosphorus antioxidants, and sulfur antioxidants.

The sterically hindered phenolic antioxidant is not particularly limited and may be commercially available. Commercially available sterically hindered phenolic antioxidants include the trade names Irganox 1010, 1035, 1076 and 1222 (each manufactured by Chiba-Geigy K.K.); Antigene P, 3C, FR, Sumilizer S and Sumilizer GA 80 (each manufactured by Sumitomo Chemical Co., Ltd.); Adekastab AO 70, AO 80 and AO 503 (each manufactured by ADEKA CORPORATION), and the like. Each of which may be used alone or in any combination thereof.

Examples of phosphorus antioxidants include tris (2,4-di-t-butylphenyl) phosphite, 2- [[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, ] [1,3,2] dioxaphospepin-6-yl] oxy] -N, N-bis [2- [[2,4,8,10-tetrakis (1,1- dimethylethyl) (d, f] [1,3,2] dioxaphospepin-6-yl] oxy] -ethyl] ethanamine, diphenyltridecylphosphite, triphenylphosphite, 2,2- Butylphenyl) octyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and the like. Among these, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite is preferable.

Examples of sulphate antioxidants include dimethyl disulfide, diethyl disulfide, di-n-propyl disulfide, di-n-butyl disulfide, di-sec-butyl disulfide, di- -Methyldisulfide, dicyclohexyl disulfide, di-tert-octyl disulfide, di-n-dodecyl disulfide, di-tert-dodecyl disulfide and the like. Of these, di-tert-alkyl disulfides are preferable, and di-tert-dodecyl disulfide is more preferable.

Devolatilization extrusion step

The obtained polymer composition containing the methacrylic resin taken out of the reactor may contain, in addition to the resulting methacrylic resin, other components such as unreacted starting monomer and polymerization initiator. Optionally, such a polymer composition is further applied to the devolatilization extrusion step. In this devolatilizing step, it is preferable to apply the raw material monomer to the devolatilization and then to the separation-recovery in the separation-recovery step described below.

Specifically, the polymer composition is optionally delivered to the preheater through a wastewater line. The amount of heat required for the devolatilization of the volatile components containing primarily unreacted starting monomer (s) can be applied, in part or in whole, to the polymer composition in the preheater. The polymer composition can then be delivered to a devolatilizing extruder through a pressure regulating valve (not shown). The volatile components are at least partially removed in the devolatilizing extruder. The residual extrudate may be shaped, for example, in the form of pellets. The pellets can be discharged from the discharge line. Thus, a polymer composition from which at least some of the volatile components have been removed can be prepared.

Separation-recovery step

Volatile components removed from the devolatilization extruder include unreacted raw monomer (s). Thus, such unreacted starting monomer (s) can be separated and recovered from the polymer composition. The obtained volatile component may be stored in a recovery tank (for example, the recovery tank 15 for the raw monomer (s) illustrated in Fig. 1). Optionally, the volatile component is transferred to the tank for the raw monomer (s) and then recycled as the raw monomer (s).

The volatile component may contain, in addition to unreacted starting monomer (s), a polymerization initiator and the like. Thus, the polymerization inhibitor is present in the recovery tank and in the tank for the raw monomer (s), for example, in the range of 2 to 8 ppm, so that the polymerization reaction does not occur in the tank for the recovery tank and the raw monomer (s) desirable. When the unreacted raw monomer (s) are stored for a long time in the recovery tank, the unreacted raw monomer (s) is preferably stored at a low temperature, for example, at a temperature within the range of 0 to 5 占 폚.

Methacrylic resin

According to the present invention, a methacrylic resin can be produced by a continuous polymerization step from at least the above-described starting monomer (a) and (b), and optional monomer (c). In particular, the methacrylic resin is characterized by containing an alicyclic hydrocarbon group derived from the monomer (b) and / or a side chain containing an aromatic hydrocarbon group. Since the methacrylic resin as described above has a side chain containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, the methacrylic resin is a thermoplastic resin, especially a thermoplastic resin having a main polymer chain containing an aromatic ring, such as an aromatic polycarbon Nate, polyethylene terephthalate, and the like. Thus, the methacrylic resin can successfully provide a mixture or composition (or polymer blend or polymer alloy) with such a thermoplastic resin. According to the present invention, due to such excellent compatibility between the methacrylic resin and the thermoplastic resin, not only the polymer composition containing such a resin but also molded articles thereof (each having excellent transparency) can be provided.

With respect to the methacrylic resin, each weight percentage of the polymerized units derived from the starting monomer is described herein (as 100% by weight) based on the total amount of the polymerized units derived from the starting monomer in the present invention. Preferably, the amount of the monomer (a) (that is, the amount of the monomer (a)) as the polymerized unit is 100% by weight based on the total weight of the monomers (a), (b) Methyl methacrylate) is in the range of 50 to 95% by weight, preferably in the range of 60 to 90% by weight; The percentage of monomer (b) (i.e. (meth) acrylate of formula (I) as polymerized units) is in the range of 5 to 50% by weight, preferably in the range of 10 to 40% by weight; The percentage of the monomer (c) (that is, the monomer copolymerizable with the monomer (a) and / or the monomer (b)) as the polymerized unit is in the range of 0 to 20% by weight, preferably in the range of 0.1 to 20% , More preferably in the range of 0.1 to 10 wt%, still more preferably in the range of 0.2 to 5 wt%.

When the percentage of each raw monomer is within the defined range, the resultant polymer composition has low colorability and good transparency. Further, even if the polymer composition further comprises other thermoplastic resins such as a thermoplastic resin having a main polymer chain containing an aromatic ring described below, the resulting polymer composition has excellent transparency. This is because the methacrylic resin contained in the polymer composition produced by the present invention has a side chain containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, and the alicyclic hydrocarbon group and / or the aromatic hydrocarbon group may be substituted with other thermoplastic Because it has excellent compatibility with the resin (s).

The methacrylic resin produced by the present invention generally has a molecular weight within the range of 70000 to 300000, preferably within the range of 70000 to 250000, and more preferably within the range of 70000 to 200000. The molecular weight of the methacrylic resin is described as weight-average molecular weight. The weight-average molecular weight can be determined using high performance gel permeation chromatography (GPC), such as HLC-8120 GPC manufactured by TOSOH CORPORATION, and PMMA as a standard.

Polymer composition

The polymer composition according to the present invention is a resin composition containing the methacrylic resin (s) produced by the continuous polymerization described above. The polymer composition may be substantially composed of the methacrylic resin described above. However, the presence of any reaction by-product (s) such as raw monomer (s) and other raw material (s) and / or oligomer (s) is not ruled out.

The polymer composition according to the present invention may contain conventional additives (s), such as a compatibilizer, a colorant, a foaming agent, a lubricant, an antistatic agent, a flame retardant, a flame retardant, a dye, Pigments, polymerization inhibitors, reinforcing agents, and the like.

Further, in the polymer composition according to the present invention as described above, alicyclic hydrocarbon groups and / or aromatic hydrocarbon groups in the methacrylic resin may have excellent compatibility with other thermoplastic resins (if present). Thus, in addition to the methacrylic resin, the polymer composition may contain other thermoplastic resin (s). By adding other thermoplastic resin (s) to the polymer composition according to the invention in addition to the methacrylic resin, it is possible to add any additional function (s) to the polymer composition, if desired, such as impact resistance, thermal stability, low hygroscopicity, And the like can be provided.

When the methacrylic resin does not contain any alicyclic hydrocarbon group and / or aromatic hydrocarbon group, compatibility between the methacrylic resin and the other thermoplastic resin deteriorates, so that the resulting mixture of the methacrylic resin and the thermoplastic resin And the transparency thereof is considered to be significantly lowered.

In the methacrylic resin contained in the polymer composition produced by the present invention, the alicyclic hydrocarbon group is, for example, 5-20 carbon atoms, preferably 5-16 carbon atoms, and the aromatic hydrocarbon group is, for example, Preferably 6 to 14 carbon atoms.

Here, as defined above, "thermoplastic resin (s)" may be added to the polymer composition prepared by the method according to the present invention.

The "thermoplastic resin " which can be added to the polymer composition according to the present invention includes, but is not limited to, for example," a thermoplastic resin having a main polymer chain containing an aromatic ring "

In the present invention, the "thermoplastic resin having a main polymer chain containing an aromatic ring" is not particularly limited, but those having a main polymer chain (that is, a polymer main chain) containing at least one aromatic ring, Borate, polyethylene terephthalate, and the like.

The "aromatic polycarbonate" which can be used in the present invention includes conventionally known aromatic polycarbonates, especially conventionally known aromatic polycarbonates prepared using bisphenol A or derivatives thereof as raw materials do. Such aromatic polycarbonates may be used without any particular limitation. The aromatic polycarbonate is commercially available or may be used after it has been synthesized in advance.

According to the present invention, the addition of the aromatic polycarbonate can provide the obtained polymer composition with excellent mechanical properties such as excellent heat resistance, impact resistance, and the like without lowering the transparency of the methacrylic resin.

The aromatic polycarbonate preferably has a viscosity-average molecular weight within the range of 5000 to 100000, more preferably within the range of 5000 to 50,000. Aromatic polycarbonate viscosity-average molecular weight (Mv) is methylene chloride solution using a [h] the intrinsic viscosity at 20 ℃ from, Schnell equation: can be calculated according to ^{[η] = 1.23x10 -4 Mv 0.83} .

As the "polyethylene terephthalate" which can be used in the present invention, conventionally known polyethylene terephthalate, specifically known polyethylene terephthalate prepared by using terephthalic acid or its derivative as a raw material, and the like are included. Such polyethylene terephthalate may be used without any particular limitation. The polyethylene terephthalate is commercially available or can be used after it has been synthesized in advance.

According to the present invention, the addition of polyethylene terephthalate can provide excellent properties such as tensile elongation and workability to the resulting polymer composition without deteriorating the transparency of the methacrylic resin.

The polyethylene terephthalate has a molecular weight, preferably a weight-average molecular weight (Mw) in the range of 5,000 to 30,000, more preferably 8,000 to 26,000, still more preferably 12,000 to 24,000, from the viewpoint of heat resistance or viscosity thereof. Respectively. As the weight-average molecular weight of the polyethylene terephthalate, for example, these values were measured using HLC-8120 GPC manufactured by TOSOH CORPORATION using hexafluoroisopropanol as a solvent, and by using the polymethyl methacrylate (PMMA) Value can be measured by the same calculation.

Here, the thermoplastic resin which can be used in any combination with the methacrylic resin is not particularly limited to the "thermoplastic resin having the main polymer chain containing an aromatic ring" described above. Depending on the desired application of the polymer composition, other thermoplastic resin (s), if desired, such as other methacrylic resins other than the methacrylic resins described above, other polycarbonate resins which are not aromatic polycarbonates described above, Such as linear or branched polycarbonate resins, etc., can be appropriately selected and added to the composition.

When the polymer composition includes other thermoplastic resins, the percentage of the thermoplastic resin to be added is, as a total weight basis (as 100% by weight) of the methacrylic resin and the thermoplastic resin, from the viewpoint of low colorability and excellent transparency of the obtained polymer composition, , Preferably in the range of 5 to 90 wt%, more preferably in the range of 10 to 90 wt%, still more preferably in the range of 10 to 80 wt%. If the percentage of the thermoplastic resin is less than 5% by weight, the mechanical properties of the polymer composition may be insufficient. On the other hand, when the percentage of the thermoplastic resin is more than 90% by weight, the transparency of the polymer composition may be insufficient.

Here, the thermoplastic resin may be added after the continuous polymerization to produce the methacrylic resin. Thus, the resulting polymer composition has a thermal hysteresis less than that obtained by mixing the polymer composition extruded from the devolatilization extruder with other thermoplastic resin (s). Thus, the resulting polymer composition has low colorability and good transparency.

In a preferred embodiment of the present invention

Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the continuous polymerization apparatus illustrated in FIG. In the continuous polymerization apparatus illustrated in FIG. 1, the reactor 6 is not particularly limited, but a reactor in which continuous polymerization for methacrylic resin, preferably continuous bulk polymerization can be carried out, more preferably, And complete mixing type reactors which can be made into complete mixing conditions. Hereinafter, a case in which a fully mixed type reactor is used, in which continuous bulk polymerization is carried out will be described in detail.

More specifically, the reactor 6 is equipped with at least a supply port 10a and a waste water port 10b, and preferably a jacket 7 and a stirrer 8 for stirring the contents therein are added as temperature control means for controlling the temperature of the outer surface of the reactor Respectively. The wastewater port 10b may be mounted to be positioned at the top of the reactor. On the other hand, the supply port 10a may generally be mounted at a suitable location in the lower portion of the reactor. The above arrangement is not limited to this embodiment. The reactor 6 may be equipped with a temperature sensor T as temperature detecting means for detecting the temperature in the reactor. Here, two or more reactors may be mounted. The two or more reactors may be arranged back and forth or in parallel.

Stirrer 8 is mounted to make the reactor interior substantially complete mixing conditions. The agitator 8 may be equipped with any suitable agitating blade (s).

Generally, in the case of having a higher stirring efficiency, the reactor 6 is preferable. However, from the viewpoint of avoiding an unnecessary amount of heat being added to the reactor by the stirring operation, it is preferable that the agitating force is not more than necessary. The agitating force is not particularly limited, but is preferably in the range of 0.5 to 30 kW / m ³ , and more preferably in the range of 1 to 15 kW / m ³ . As the viscosity of the reaction system increases (or as the content ratio of the polymer in the reaction system gradually increases), it is desirable to set the agitation force to a higher level.

As shown in the figure, the supply port 10a of the reactor 6 is connected to the monomer feed tank 1 (or the source of the raw monomer (s)) and the polymerization initiator feed tank 2 Or, if desired, a source of polymerization initiator that may contain the raw monomer (s). In this embodiment, the source of the raw monomer and the polymerization initiator are the monomer feed tank 1 and the polymerization initiator feed tank 2, respectively. However, the number of raw materials of the starting monomer and the polymerization initiator, the form of the starting monomer and the polymerization initiator (in the case of a mixture, for example, a composition thereof) and the like are not limited as long as the starting monomer and the polymerization initiator can be appropriately supplied to the reactor 6 , And is not particularly limited.

It is preferable that the member and the means described above are appropriately connected to a control device (not shown in the figure), respectively, with reference to Fig. 1, and that the control device is completely configured to control its operation. Thus, with respect to the reactor 6, to make the temperature of the reactor outer surface, which is set by the jacket (or temperature control means) 7, coincide with the temperature in the reactor detected by the temperature sensor T And the temperature of the outer surface of the reactor set by the jacket 7 can be adjusted by adjusting the supply amount of the raw material monomer and the polymerization initiator of the reactor 3 by the operation of the pumps 3 and 4, respectively.

In this embodiment, the preheater 11 and the devolatilization extruder 12 can be mounted downstream of the wastewater line 9 connected to the wastewater port 10b. A pressure regulating valve (not shown) may be mounted between the preheater 11 and the devolatilizer extruder 12.

At devolatilizer extruder 12, at least a portion of the volatile components in the polymer composition may be removed. Thus, in this embodiment, this is accomplished by continuously feeding the continuously drawn polymer composition from the reactor to a devolatilizing extruder, removing at least a portion of the volatile component from the polymer composition in a devolatilizing extruder, removing at least a portion of the volatile component , And a step of "devolatilization extrusion" in which the obtained polymer composition is continuously extruded from a devolatilizing extruder. In the present invention, the above-described devolatilization extrusion step is not particularly limited as described below.

The extrudate of the obtained polymer composition can be discharged from the discharge line 13. The shear rate in this devolatilization step is preferably in the range of 10 to 500 sec < ^-1 > in view of the low colorability and excellent transparency of the obtained polymer composition. If the shear rate is less than 10 sec ^-1 , the residence time becomes longer and the composition can easily be colored. If the shear rate is more than 500 sec ^-1 , the composition can easily be colored due to heat by shearing.

During this period, the mixing temperature in the devolatilization extruder is preferably in the range of 180 to 320 ° C. During the above period, the degree of the vacuum of the front ventilation hole is, for example, in the range of 400 to 1200 Torr, and the vacuum degree of the rear ventilation hole is preferably in the range of 10 Torr to 100 Torr, for example.

In accordance with the present invention, in the devolatilization extrusion step, there is no further particular limitation on other conditions when at least some of the volatile components contained in the polymer composition can be removed. It is preferred that the weight percentage of volatile components can be less than 1% by weight of the composition.

Here, the preheater 11 includes any suitable heater as long as the heater can heat any viscous fluid. The devolatilizer extruder 12 includes a uniaxial or multiaxial devolatilization extruder.

Further, in accordance with the present invention, one or more distillation columns, such as the distillation columns 14 and 20 illustrated in FIG. 1, can be separated from the volatilization component (s) in the devolatilizer extruder 12, (A), (b) and / or (c)) described above (i.e., the monomers (a), (b) and / Or copolymers, each of which may have two or more polymerized units, each of which may contain a low molecular weight volatile component).

In this embodiment, it is referred to as the " separation-recovery step "for separating and recovering the raw monomer (s) and / or the oligomer (s) from the volatile components removed in the devolatilizing extruder. In the present invention, the separation-recovery step is not particularly limited to those described below.

In the separation-recovery step, the conditions can be suitably determined according to the boiling point or weight% of each of the raw monomers. For example, two distillation columns may be used. Initially, from the oligomer (s) obtained by polymerization of monomer (b) and of at least one kind of two or more monomers as components having a higher boiling point in the first distillation column, monomers ( a) and monomer (c) can be separated. Subsequently, monomer (b) can be separated from the oligomer (s) in the second distillation column, respectively, for the component having a higher boiling point, obtained by the first distillation column. The recovered monomer (s) containing mainly monomer (b) as well as the recovered monomers mainly containing monomers (a) and (c) can be recovered independently. These monomers can be recycled.

Further, in the continuous polymerization apparatus which can be used in the present invention, not only the recovery tank 15 (for example, unreacted raw monomers (a) and (c) can be stored therein) for the raw monomer (s) (Here, for example, unreacted raw monomer (b) and oligomer (s) can be stored) for the oligomer (s) and oligomer (s)

Further, the distillation column 20, the recovery tank 21 for the raw monomer (s) (here, the monomer (b) can be stored), the recovery tank 22 (for the oligomer Can be mounted downstream of the recovery tank 16 for the raw material monomer (s) and oligomer (s). In devolatilizer extruder 12, distillation column 14 and distillation column 20, volatile components can be at least partially separated and recovered. Therefore, in the polymer composition obtained by being discharged from the discharge line 13, since the content of the volatile component is reduced, the purity of the methacrylic resin is increased, the coloring property is reduced, and the transparency is increased.

The degree of vacuum in the distillation column 14 or 20 is preferably measured within the range of 100 to 500 Torr. In order to separate the unreacted starting monomer (s) and oligomer (s), each having a higher boiling point than the monomers, the temperature in the distillation column is measured within the range of 100 to 200 ° C, more preferably within the range of 110 to 150 ° C .

In the present invention, among the unreacted starting monomers that can be separated and recovered from the polymer composition, the monomer as a component having a lower boiling point can be stored in the recovery tank 15 for the starting monomer (s). The monomer as a component having a higher boiling point can be stored in the recovery tank 21 for the raw monomer (s). If required, these raw material monomers can be appropriately supplied again to the monomer supply tank 1, respectively. These raw material monomers can be repeatedly applied to the polymerization reaction. Here, the recovered unreacted starting monomer (s) and oligomer (s) are not particularly limited to those described below. While the raw monomer (s) and oligomer (s) are stored in the recovery tanks 15 and 21 for raw material monomer (s), recovery tank 22 for oligomer (s), and monomer supply tank 1, polymerization inhibitors Topnol A "and the like) is added thereto in a proportion within the range of 2 to 8 ppm, and the oxygen concentration in the gas phase portion thereof is measured within 2 to 8% by volume, and the raw monomer (s) and oligomer Is preferably stored at a reduced temperature, for example, at a temperature in the range of about 0 to 5 DEG C, using cooling so as not to proceed the polymerization reaction. Thus, the storage of the unreacted monomer (s) and oligomer (s) can prevent them from participating in the polymerization reaction, and the raw monomer (s) and oligomer (s) can be stored therein for a long period of time.

Further, in the present invention, the above-described methacrylic resin-containing polymer composition can be taken out from the reactor and, if desired, before the polymer composition is extruded from the devolatilizer extruder 12, other thermoplastic resins other than the methacrylic resin described above (S) may be fed to the polymer composition at any location and time.

In the present invention, this is referred to as "thermoplastic resin feeding step" in which other thermoplastic resin is fed to the raw material (s) and / or polymer composition before the polymer composition containing the methacrylic resin described above is extruded from the devolatilizing extruder. In the present invention, the step of supplying the thermoplastic resin is not particularly limited to those disclosed in this embodiment.

The thermoplastic resin that can be supplied to the polymer composition is preferably a thermoplastic resin having a main polymer chain containing the aromatic ring described above, particularly preferably a thermoplastic resin such as aromatic polycarbonate and polyethylene terephthalate.

For example, in the method of supplying the thermoplastic resin, a solution containing a thermoplastic resin dissolved in a solvent (for example, ethyl acetate or the like) is supplied from the thermoplastic resin supply tank 17 through the thermoplastic resin supply line 18, And supplied to the devolatilizing extruder 12. Therefore, by supplying the thermoplastic resin to the devolatilizer 12 through the feed line 19, the thermoplastic resin and the methacrylic resin are mixed in a molten state to continuously produce a polymer composition containing both a methacrylic resin and a thermoplastic resin have.

Alternatively, as indicated by the dashed line in FIG. 1, the thermoplastic resin can be removed from the thermoplastic resin feed tank 17, if desired, by, for example, one or more piping or lines between the reactor 6 and the devolatilizer extruder 12 9, a line between the preheater 11 (if present) and the devolatilization extruder 12, etc.) through a pump similar to the thermoplastic resin feed pump 18.

Other methods may be used, including a method of separating the thermoplastic resin into a devolatilizer extruder by means of a screw and a further extruder attached to one vent of a cylinder of the devolatilization extruder, Transferring the resin to the injection block through a short pipe, and combining and mixing these resins.

Here, the solvent used to dissolve the thermoplastic resin (s) can be removed as volatile component (s) in devolatilizer extruder 12.

The polymer composition according to the present invention can be molded and processed into a desired shape to provide a molded article having low coloring property and excellent transparency (or optical property) and mechanical strength. Such molded articles may be used in various fields, particularly in the field of optics, for example, electro-optical materials (e.g., lenses, optical disk substrates, materials for light- guiding panels, etc.), coating materials , Resin grazing materials, and the like.

The polymer composition according to the invention can be molded, for example, by extruding the composition in a devolatilization extruder 12. The polymer composition discharged from the devolatilizing extruder 12 through the discharge line 13 (if present) can be independently molded into the desired dimensions and shape. Alternatively, the polymer composition may be applied to a desired size (e.g., a desired size) in an additionally mounted melt-kneading machine, where the polymer composition is melt-kneaded, connected to a devolatilizer extruder 12 or to an outlet line 13 And shape. Alternatively, the polymer composition extruded from the devolatilizer extruder 12 may be molded into a pellet-like shape, and then the pellets may be discharged from the discharge line 13 (if present), and then separately molded into an injection molding machine and a hydraulic press such as a press machine, where molten molding or compression molding of the pellets can be carried out.

Here, the shape and dimensions of the molded polymer composition are not particularly limited.

The forming temperature is generally in the range of about 150 to 350 占 폚, preferably in the range of about 180 to 320 占 폚, more preferably in the range of about 180 to 300 占 폚.

Here, by the continuous polymerization step described above according to the present invention, not only the polymer composition including a methacrylic resin having a side chain containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, but also molded articles thereof, The total light transmittance in the range of 90% or more, for example, in the range of 90 to 93%, preferably in the range of 90 to 92% when measured according to K 7361-1 and 1.1 or less, for example, (YI) showing a degree of coloration within a range of 0.1 to 1.0, preferably 0.1 to 1.0. When the total light transmittance is 90% or more and the yellowness index (YI) is 1.1 or less for the polymer composition and molded articles thereof, excellent visual characteristics are obtained because the visually observed appearance thereof is colorless and transparent.

Surprisingly, the polymer composition according to the present invention and molded articles thereof can be produced by mixing a methacrylic resin as described above, for example, a thermoplastic resin having a main polymer chain containing an aromatic ring, in particular an aromatic polycarbonate, polyethylene terephthalate, (S) is contained therein, it has excellent transparency. The reason for this is that the methacrylic resin itself, which has an alicyclic hydrocarbon group, or the polymer composition containing such a resin has inherently low coloring property and excellent transparency, and the alicyclic group contained in the methacrylic resin It is believed that this is because the hydrocarbon groups and / or aromatic hydrocarbon groups have excellent compatibility with methacrylic resins and other thermoplastic resin (s) (especially thermoplastic resins including aromatic rings).

Furthermore, according to the present invention, by performing continuous polymerization, in particular continuous polymerization (preferably continuous bulk polymerization) is carried out by using a reactor of a completely mixed type, as compared with the case of using ordinary suspension polymerization, And the possible contamination with impurities such as oligomer (s) is significantly reduced. Thus, low colorability and good transparency of the polymer composition and molded articles thereof can be achieved.

Here, as described above, after the continuous polymerization, the above-mentioned thermoplastic resin can be continuously supplied to the obtained composition and combined with the methacrylic resin therein. Therefore, compatibility with the methacrylic resin can be further improved, and a more transparent polymer composition and molded articles thereof can be obtained.

Hereinafter, the polymer composition according to the present invention and the method for producing the molded article thereof will be more specifically described with reference to the following examples.

Example

Example 1

In this embodiment, diagrammatically, continuous polymerization is carried out according to the preferred embodiment described above with reference to Fig. 1 to obtain a polymer composition comprising a methacrylic resin having side chains containing alicyclic hydrocarbon groups in the form of pellets . The details are described in more detail below.

73.75 parts by weight of methyl methacrylate, 20.0 parts by weight of cyclohexyl methacrylate and 1.00 parts by weight of methyl acrylate were mixed to obtain a mixture, 0.15 part by weight of n-octyl mercaptan as chain transfer agent and 0.10 part by weight of stearate as a release agent Aryl alcohol was added to the mixture to prepare a raw material monomer-mixed liquid.

Separately, 99.72 parts by weight of methyl methacrylate and 0.28 parts by weight of [1,1-di (t-butylperoxy) cyclohexane] as a polymerization initiator were mixed to prepare a polymerization initiator-mixed liquid.

A fully mixed reactor (volume: 13 L) was used as reactor 6. The raw monomer-mixed liquid and the polymerization initiator-mixed liquid thus prepared were poured into the monomer feed tank 1 and the polymerization initiator feed tank 2, respectively.

The raw monomer-mixed liquid and the polymerization initiator-mixed liquid are supplied continuously from the monomer feed tank 1 and the polymerization initiator feed tank 2 via the feed port 10a located at the lower portion of the reactor 6 to the reactor 6 through the feed line 5 Respectively.

The feed of the raw monomer-mixed liquid and the polymerization initiator-mixed liquid to the reactor 6 was performed such that the flow rates of these liquids were 17: 1 and the average residence time in the reactor 6 was 33 minutes. The temperature in the reactor 6 was set at 175 ° C and the temperature of the jacket 7 surrounding the outer surface of the reactor 6 was set at 175 ° C. Continuous polymerization was carried out under adiabatic conditions in which no heat was substantially introduced or discharged. This continuous polymerization was carried out under conditions filled with the reaction mixture (or mixed liquid) in reactor 6 without substantially any gas (as a full charge condition).

The reaction mixture in reactor 6 was continuously withdrawn from waste water port 10b located at the top of reactor 6. The resulting polymer composition was passed through a wastewater line 9 and then heated in a preheater 11 to 200 DEG C and volatile components such as unreacted raw monomer (s) were removed at 230 DEG C in a devolatilizer 12 equipped with a vent. The devolatilized polymer composition was extruded into a molten state, then cooled with water, then cut and discharged from the discharge line 13 to the pellet. Thus, a polymer composition comprising a methacrylic resin having side chains containing alicyclic hydrocarbon groups was prepared in the form of pellets.

Comparative Example 1

78.6% by weight of methyl methacrylate, 20.0% by weight of cyclohexyl methacrylate and 1.0% by weight of methyl acrylate were mixed to prepare a monomer composition. To the monomer composition, 0.2% by weight of lauryl peroxide was added as a polymerization initiator. Additionally, 0.2 wt% n-octyl mercaptan as a chain transfer agent was added to the monomer composition and dissolved therein to prepare a monomer mixture.

The reactor was charged with 100 parts by weight of the monomer mixture, 285 parts by weight of ion-exchanged water, and 0.18 parts by weight of sodium polyacrylate aqueous solution (at a concentration of 1.2% by weight) as a stabilizer for suspension polymerization. Suspension polymerization was carried out at 80 캜 for 3 hours. The reaction solution obtained as a slurry was dehydrated in a dehydrator, washed, and then dried to prepare a polymer in bead form.

The resultant bead polymer was filtered, washed with water, dried at 85 DEG C for 8 hours, then applied to an extruder, and extruded at its cylinder temperature of 230 DEG C to form pellets. A methacrylic resin in the form of pellets was obtained.

The total weight percent of residual methyl methacrylate and cyclohexyl methacrylate in each of the pellets prepared in Example 1 and Comparative Example 1 was measured as follows. The results are shown in Table 1 below. The smaller the value, the more the resin composition having a higher purity is obtained.

Determination of the amount of residual methyl methacrylate and cyclohexyl methacrylate

Each of the pellets of Example 1 and Comparative Example 1 was added to dichloromethane to prepare a dichloromethane solution containing pellets at a concentration of 0.05 wt%. The amounts of residual methyl methacrylate and cyclohexyl methacrylate contained in the respective pellets of Example 1 and Comparative Example 1 were measured using a gas chromatograph (Type GC-5A, manufactured by Shimadzu Corporation) As a total weight% by comparing the peak area of a standard solution containing methyl methacrylate and cyclohexyl methacrylate with its peak area in a given amount. As a standard sample of methyl methacrylate, methyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd.) was used. As a standard sample of cyclohexyl methacrylate, Light ester CH (manufactured by KYOEISHA CHEMICAL Co., LTD.) Was used.

Manufacture of molded articles

Each of the pellets prepared in Example 1 and Comparative Example 1 was injection-molded at 250 DEG C using an injection molding machine IS-130 (manufactured by TOSHIBA CORPORATION) to obtain a molded article (or a molded article having a panel shape of 5.0 mm x 5.0 mm x 3.4 mm).

Total light transmittance

The total light transmittance (Tt (%)) was measured using HR-100 (manufactured by MURAKAMI COLOR RESEARCH LABORATORY CO., Ltd.) according to JIS K 7361-1 for light passing through a molded article Respectively. The larger the value of the total light transmittance, the better the transparency is secured. The results are shown in Table 1 below.

YI value

Using a spectrophotometer (Hitachi Spectrophotometer U-4000, Hitachi High-Tech Fielding Corporation), the yellowness index (YI) indicating the coloration of the molded article was measured according to JIS K 7105. The lower the yellowness value, the less yellowing the article means, and the lower the coloring property is. The results are shown in Table 1 below.

Transparency

If the article has a colorless and transparent appearance visually observed and has a total light transmittance (Tt) of 90% or more and a yellowness index (YI) of 1.1 or less with respect to the transparency of the molded article, Quot; in "). If the item fails to meet the definition of success described above, it is evaluated as "failed" (see "None" in Table 1). The results are shown in the table below.

With respect to Comparative Example 1 described above, a methacrylic resin containing a cyclohexyl group as an alicyclic hydrocarbon group was synthesized by a conventional batch-type suspension polymerization. Therefore, there is a tendency to remain in the methacrylic resin obtained and the polymer composition containing it, as well as raw monomer such as methyl methacrylate and cyclohexyl methacrylate as well as suspension polymerization stabilizers such as sodium polyacrylate used during suspension polymerization . By this, it is considered that transparency is lowered because the molded article obtained has an increased YI value.

On the other hand, the methacrylic resin of Example 1 according to the present invention was synthesized by continuous polymerization. Thus, the raw monomers can be continuously supplied and polymerized with each other. Here, if present, unreacted starting monomer (s) can be separated and recovered and then recycled. Thus, the amount of impurities can be significantly reduced (to half or less). Here, in comparison with the suspension polymerization described above, the use of any stabilizing agent for suspension polymerization is not required. As a result, a polymer composition having low coloring property and excellent transparency and a molded article therefrom could be produced.

Further, as shown in Table 1, according to Example 1 of the present invention, the value of Tt increased and the value of YI decreased. Therefore, excellent transparency can be secured.

The polymer composition obtained by the production process according to the present invention and the molded article therefrom have excellent color characteristics and excellent transparency, so that they have colorless and transparent excellent optical properties.

Therefore, the polymer composition according to the present invention and the molded article therefrom can be used as materials for transparent films, sheets and the like in various fields where the above-mentioned optical characteristics are required. Particularly, the present invention can be preferably used as an electro-optical part such as a lens, an optical disk substrate and a light guide plate, or a material therefor in an optical field in which excellent transparency is required.

This application claims priority and benefit to Japanese Patent Application No. 2014-10549, filed on January 23, 2014, the entire contents of which are incorporated herein by reference.

1: monomer supply tank
2: Polymerization initiator supply tank
3: monomer feed pump
4: Polymerization initiator feed pump
5: raw material supply line
6: Reactor (or fully mixed reactor)
7: Reactor jacket
8: Stirrer
9: Wastewater line
10a: supply port
10b: waste water port
11: Preheater
12: devolatilization extruder
13: discharge line
14: distillation column
15: Recovery tank for raw material monomer (s)
16: Recovery tank for raw material monomer (s) and oligomer (s)
17: thermoplastic resin supply tank
18: Thermoplastic resin feed pump
19: Thermoplastic resin supply line
20: distillation column
21: Recovery tank for raw material monomer (s)
22: Recovery tank for oligomer (s)
T: temperature sensor (or temperature detecting means)

Claims (14)

A process for producing a polymer composition comprising a methacrylic resin having side chains containing an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group,
A raw material containing a raw material monomer and a polymerization initiator is continuously supplied to at least one reactor and continuous polymerization is carried out in the reactor to obtain a polymer comprising a methacrylic resin having a side chain containing an alicyclic hydrocarbon group and / A continuous polymerization step of producing a composition and continuously withdrawing the polymer composition from the reactor,
Here, the raw material monomers are used in an amount of 100% by weight based on the total weight of the raw material monomers,
(a) from 50 to 95% by weight of methyl methacrylate,
(b) 5 to 50% by weight of a (meth) acrylate represented by the formula (I)

(Wherein,
R ¹ represents a hydrogen atom or a methyl group,
R ² represents an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, an alkyl group substituted with a phenyl group, a phenyl group, a phenyl group substituted with an alkyl group, an alkyl group substituted with a naphthyl group, a naphthyl group, , Dicyclopentanyl group or dicyclopentenyl group), and
(c) 0 to 20% by weight of a monomer copolymerizable with methyl methacrylate and / or (meth) acrylate represented by the formula (I)
≪ / RTI > The process according to claim 1, wherein the continuous polymerization is continuous bulk polymerization. 3. A process according to claim 1 or 2, wherein the polymer composition continuously withdrawn from the reactor is continuously fed to a devolatilizing extruder, at least a portion of the volatile component is removed from the polymer composition in a devolatilizer extruder, Further comprising a devolatilization extrusion step of continuously extruding the resulting polymer composition after removing at least a portion thereof. 4. The process according to claim 3, wherein the mixing temperature in the devolatilization extruder is in the range of 180 to 320 DEG C and the shear rate in the devolatilization extruder is in the range of 10 to 500 sec < ^{-1 &} gt ;. The process according to claim 3, further comprising a separation-recovery step of separating and recovering the (meth) acrylate represented by the formula (I) from the volatile component removed in the devolatilizing extruder. 4. The method of claim 3, further comprising supplying a thermoplastic resin to the polymer composition having a main polymer chain containing aromatic rings before extruding the polymer composition from a devolatilizing extruder. 7. The method according to any one of claims 1 to 6, wherein the polymer composition comprises a thermoplastic resin in addition to the methacrylic resin. The method according to claim 6 or 7, wherein the polymer composition contains the thermoplastic resin in a weight ratio of 5 to 90 wt% based on 100 wt% based on the total weight of the methacrylic resin and the thermoplastic resin. 9. The method according to any one of claims 6 to 8, wherein the thermoplastic resin is at least one selected from the group consisting of an aromatic polycarbonate and a polyethylene terephthalate. The thermosetting resin composition according to any one of claims 1 to 9, wherein the methacrylic resin is at least one selected from the group consisting of methyl methacrylate, the (meth) acrylate represented by the formula (I) (Meth) acrylate and 0 to 20% by weight, based on 100% by weight, of polymerized units, respectively, of 50 to 95% by weight of methyl methacrylate, 5 to 50% ≪ / RTI > of a copolymerizable monomer. 11. The composition according to any one of claims 1 to 10, wherein the (meth) acrylate represented by the formula (I) is at least one selected from the group consisting of cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, naphthyl acrylate Wherein the at least one monomer is at least one selected from the group consisting of methacrylate, methacrylate, naphthyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, and dicyclopentenyl methacrylate. 12. The method according to any one of claims 1 to 11, wherein the copolymerizable monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate and butyl acrylate. A polymer composition obtainable / obtainable by a process according to any one of claims 1 to 12. A molded article obtainable / obtainable by molding the polymer composition according to claim 13.

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