KR101870452B1 - Apparatus and process for producing polymer - Google Patents

Abstract

The present invention provides a polymer production apparatus which can be operated stably and continuously for a long period of time.
In a polymer production apparatus comprising a reactor, a pressure-regulating valve and a devolatilizing extruder so that the polymer composition obtained from the reactor is fed to the devolatilizing extruder through a pressure-regulating valve, the pressure- regulating valve 20 is connected to the valve element 1, A stem 5 for supporting and controlling the valve element 1; a guide 13 for slidably guiding the stem 9; The fluid containing the polymerization inhibitor is transferred to the gap 11 between the surface of the stem 9 and the inner surface of the guide 13 through the fluid transfer port. The gap 11 communicates with the space 3 in the body 5 and the fluid transferred from the fluid transfer port 17 flows into the space 3.

Description

[0001] APPARATUS AND PROCESS FOR PRODUCING POLYMER [0002]

The present invention relates to an apparatus and a method for producing a polymer.

A process for producing a polymer such as a (meth) acrylic polymer, in which a solution polymerization or a bulk polymerization is carried out in order to provide a polymer composition comprising a polymer and an unreacted monomer in a reactor, It is known that volatile components containing unreacted monomers are removed from the polymer composition using a devolatilizing extruder (see, for example, Patent Documents 1 to 4).

JP-A-50-40688 JP-A-2003-96105 JP-A-2000-211010 JP-A-2005-112870

In this process for producing polymers, the pressure-regulating valve is used to adjust the pressure in the reactor, and the polymer composition obtained by passing through a pressure-regulating valve is fed to a devolatilizing extruder (see Patent Document 4).

However, the conventional apparatus for producing a polymer using a normal pressure-regulating valve has a problem that, if the apparatus is continuously operated for a long period of time, the movement of the pressure-regulating valve becomes difficult, and continuous operation for a long period of time is impossible.

It is an object of the present invention to provide a polymer production apparatus which can be operated stably and continuously for a long period of time, and a method for producing a polymer which is carried out using the apparatus.

In a normal pressure-regulating valve, the stem for supporting and controlling the valve element is inserted into the guide to guide the stem through the guide. The polymer composition is introduced into the gap between the surface of the stem and the inner surface of the guide, where unreacted monomers in the polymer composition are polymerized (e.g., by heat) and the resulting polymer is attached to the stem and / . Thereafter, when the device for continuously producing the polymer is operated for a long period of time, the adhered polymer inhibits the sliding of the stem, thereby making it difficult to exercise the pressure-regulating valve (i.e., smoothly controlling the valve element as intended It becomes impossible to do so. The present inventors have seriously contemplated a polymer manufacturing apparatus capable of preventing the adhesion of the polymer to the stem and / or guide of the pressure-regulating valve, and finally completed the present invention.

The present invention provides the following [1] to [6].

[1] A polymer producing apparatus comprising a reactor, a pressure-regulating valve and a devolatilizing extruder so that a polymer composition obtained from a reactor is fed to a devolatilizing extruder through a pressure-regulating valve,

The pressure-regulating valve includes a valve element, a body having a space for receiving the valve element, a stem for supporting and controlling the valve element, a guide for slidably guiding the stem, and a fluid feed port, The fluid containing the polymerization inhibitor is transferred through the fluid transfer port to the gap between the surface of the stem and the inner surface of the guide, and the gap communicates with the space in the body, so that the fluid transferred from the fluid transfer port flows into the space.

[2] In the polymer manufacturing apparatus according to the above-mentioned [1], the pressure-regulating valve further includes a lantern ring at a sealing portion between the stem and the guide, and the fluid transfer port is located adjacent to the lantern ring .

[3] A method for producing a polymer using the polymer production apparatus according to the above-mentioned [1] or [2]

Polymerizing a raw material containing a monomer and a polymerization initiator in a reactor while adjusting a pressure of the reactor by a pressure-adjusting valve, and then withdrawing a polymer composition containing a polymer and an unreacted monomer from the reactor;

Passing a fluid containing polymerization inhibitor from a fluid delivery port in a pressure-regulating valve and passing the polymer composition drawn from the reactor through a space in the body of the pressure-regulating valve to obtain a polymer composition mixed with the fluid, And

After feeding the polymer composition mixed with the fluid obtained through the pressure-regulating valve to the devolatilizing extruder, the volatile components including the unreacted monomers are withdrawn from the devolatilizing extruder at least partially removed from the polymer composition, And obtaining a polymer as a material.

[4] In the method for producing a polymer according to the above [3], a fluid containing a polymerization inhibitor is formed by dissolving a polymerization inhibitor in a monomer.

[5] In the method for producing a polymer according to the above-mentioned [3] or [4], the content of the polymerization inhibitor in the fluid containing the polymerization inhibitor is 5 to 2,000 ppm by weight based on the total weight of the fluid.

[6] The method for producing a polymer according to any one of [3] to [5], wherein the ratio of the supply flow rate of the polymer composition to the pressure-regulating valve to the supply flow rate of the fluid including the polymerization inhibitor to the pressure- Is from 80:20 to 99.9: 0.1.

According to the present invention, it is possible to prevent the adhesion of the polymer to the stem and / or the guide of the pressure-regulating valve, thereby providing a polymer manufacturing apparatus which can be operated stably and continuously for a long period of time. In addition, there is provided a method of making a polymer that is carried out using an apparatus.

1 shows a schematic cross-sectional view of a pressure-regulating valve used in a polymer production apparatus in an embodiment of the present invention. Fig. 1 (a) shows a pressure-regulating valve in an open state, and Fig. 1 (b) shows a pressure-regulating valve in a closed state.
Fig. 2 (a) shows a schematic partial enlarged view of the pressure-regulating valve shown in Fig. Fig. 2 (b) shows a schematic partial enlarged view of a modification of the pressure-regulating valve of Fig. 2 (a).
3 shows a schematic view of a polymer preparation apparatus in an embodiment of the present invention.

The polymer preparation apparatus of the present invention has at least a reactor, a pressure-regulating valve and a devolatilizing extruder. Hereinafter, first, after the pressure-regulating valve is described, an apparatus for producing a polymer of the present invention using a pressure-regulating valve and a method for producing the polymer of the present invention performed using the apparatus are described.

The pressure-regulating valve 20 used in the polymer production apparatus of the present invention is a valve having a valve element 1, a body 3 having a space 3 for accommodating the valve element 1, A stem 9 for supporting and controlling the valve element 1 and a guide 13 for slidably guiding the stem 9 inside the valve element 1 (in other words, for guiding the slidable stem 9) A fluid containing a polymerization inhibitor (hereinafter also referred to as a polymerization inhibitor-containing fluid) is supplied through the fluid transfer port to the surface of the stem 9 and a guide 13 (Not shown). The gap 11 is communicated with the space 3 in the body 5 so that the polymerization inhibitor-containing fluid transferred from the fluid transfer port 17 flows into the space 3 in the body 5.

The pressure-regulating valve 20 is used to adjust the pressure in the reactor described below. The polymer composition obtained from the reactor is fed from the inlet port 7a of the body (or valve box) 5, through the space 3 in the body 5 and out through the outlet port 7b , The direction of flow of the polymer composition is indicated by a hollow arrow). The rate of outflow of the polymer composition from the outlet port 7b in the pressure-regulating valve 20 is regulated by the valve element 1, consequently the pressure in the reactor is regulated.

The valve element (or disc) 1 is slidable in the axial direction of the stem 9 (in the embodiment shown in FIG. 1) by sliding the stem 9 along the inner surface of the guide 13 by the drive 19 By moving the stem 9 up and down). While the stem 9 is slidingly operated, the valve element 1 is held in a state of being supported by the stem 9.

Figure 1 shows a so-called globe valve type pressure-regulating valve 20. The stem 9 is moved upward and downward within the guide 13 by the driving part 19 so that the valve element 1 supported at the tip of the stem 9 is also simultaneously moved up and down. When the valve element 1 is located on the floor (see Fig. 1 (b)), the valve element 1 is engaged (or pressed) with the seat portion (or valve seat) 5a in the body 5 , The flow of the polymer composition through the space 3 is stopped (closed state). When the valve element 1 is located at the uppermost position (see Fig. 1 (a)), the polymer composition is passed through the flow space 3 (open state) between the valve element 1 and the seat portion 5a. The rate of outflow of the polymer composition from the pressure-regulating valve 20 and hence the pressure in the reactor can then be adjusted by adjusting the position (opening) of the valve element 1 in the longitudinal (up and down) direction by the stem 9 . The seat portion 5a may be integrated with the body 5 or may be a portion separated from the body.

However, the pressure-regulating valve which can be used in the present invention is not limited to this, and the valve element 1 supported by the stem 9 can be operated by sliding the stem 9 in the guide 13, As a result, any suitable configuration can be applied so long as the rate of outflow of the polymer composition from the pressure-regulating valve 20 and thus the pressure in the reactor can be adjusted. For example, in the pressure-regulating valve 20 shown in FIG. 1, the inlet port and the outlet port may be reversed (i.e., the inlet port 7a and the outlet port 7b may be reversed ), The polymer composition may flow in a direction opposite to the direction indicated by hollow hollow arrows in Fig. In addition, other configurations, such as so-called gate valves, needle valves (in these configurations, the stem supporting the valve element can be moved up and down in the axial direction) can be used and the shape of the valve element 1 and the shape of the body 5 ) Can be suitably selected according to the configuration.

With respect to the stem 9 and the guide 13, a gap 11 exists between the stem and the guide so that the stem 9 can slide along the inner surface of the guide 13. [ The gap 11 also functions as a flow passage for the polymerization inhibitor-containing fluid which is conveyed from the fluid conveyance port 17. The value of the size of the gap 11 (representative value obtained by subtracting the outer diameter of the stem 9 from the inner diameter of the guide 13 and divided by 2) is, for example, 0.01 to 15 mm, preferably 0.1 to 10 mm, It does not. When the gap size is less than the above-mentioned upper limit value, the stem 9 can slide properly in the guide 13. The polymerization inhibitor-containing fluid transferred from the fluid transfer port 17 to the gap 11 easily flows into the space 3 and is prevented from flowing into the gap 11 when the gap size is not less than the lower limit described above Can be guaranteed.

The gap 11 between the stem 9 and the guide 13 is generally sealed to the sealing portion 15 at the opposite end to the valve element 1. By providing the sealing portion 15, the pressure can be maintained in the space 3 of the body 5, and impurities can be prevented from being contained in the polymer composition from the outside. A known shaft seal may be applied to the sealing portion 15. In this embodiment, although gland packing is used for the sealing portion 15, as shown in Figs. 1 and 2 (a), the sealing portion 15 is not limited to the gland packing O-ring seals, bellows seals, and the like.

One or more fluid delivery ports 17 may be provided at any suitable location so long as the polymerization inhibitor containing fluid can be transferred to the gap 11 between the surface of the stem 9 and the inner surface of the guide 13. [ have. For example, as shown in Figs. 1 and 2 (a), the fluid transfer port 17 may be located between the sealing portion 15 and the space 3. In addition, for example, as shown in Fig. 2 (b), a sealing portion 15 is provided between the packing 15a and the lantern ring 15b (the lantern ring 15b, as shown in the figure, The fluid transfer port 17 may be located adjacent to the lantern ring 15b when the fluid transfer port 17 includes, but is not limited to,

By using this pressure-regulating valve 20 to adjust the pressure in the reactor, the polymerization inhibitor-containing fluid transferred from the fluid transfer port 17 flows into the space 3 in the body 5 through the gap 11 The flow of the polymerization inhibitor-containing fluid effectively prevents the introduction of the polymer composition into the clearance 11. Further, the polymerization inhibitor in the polymerization inhibitor-containing fluid prevents further polymerization of the unreacted monomers contained in the polymer composition. As a result, the adhesion of the polymer to the stem 9 and / or the guide 13 can be effectively prevented, so that even when the pressure-regulating valve is continuously operated for a long time, the pressure-regulating valve 20 is preferably operated without repair Lt; / RTI >

Next, an apparatus for producing a polymer of the present invention using such a pressure-regulating valve 20 will be described.

The polymer preparation apparatus 100 of the present invention has at least a reactor 40, a pressure-regulating valve 20 and a devolatilizing extruder 60 as shown in Fig. 3, and the polymer composition obtained from the reactor 40 Is supplied to the devolatilizing extruder (60) through the pressure-regulating valve (20).

In this embodiment, the polymer manufacturing apparatus 100 may further include a raw material monomer tank 31 and a polymerization initiator fluid tank 33. These tanks 31 and 33 are connected to the supply port 41a of the reactor 40 and the raw material supply line 39 via the pumps 35 and 37, respectively.

Preferably, the reactor 40 is a fully mixed reactor. Specifically, the reactor 40 has a supply port 41a and an outlet port 41b, and is preferably provided with a jacket 43 as a temperature regulating means for regulating the temperature of the outer surface of the reactor, And further includes an agitator 45. The outlet port 41b is preferably located at the top of the reactor, but this embodiment is not limited thereto. On the other hand, the supply port 41a is generally disposed at a suitable position in the lower portion of the reactor, but this embodiment is not limited thereto. The reactor 40 may also have a temperature sensor T for detecting the temperature of the reactor and a pressure sensor P for detecting the pressure inside the reactor. The detection unit of the pressure sensor P does not necessarily have to be located inside the reactor as long as it can detect the pressure in the reactor. The detection portion of the pressure sensor P is connected to the outside of the reactor 40, for example, a connecting line connecting the outlet port 41b to downstream devices (indicated by the symbol P surrounded by a dotted line in Fig. 3) Lt; RTI ID = 0.0 > 41b. ≪ / RTI >

Additionally, in this embodiment, the polymer manufacturing apparatus 100 may further include a preheater 50 between the reactor 40 and the pressure-regulating valve 20. [ The outlet port 41b of the reactor 40 is connected to the inlet port of the preheater 50 and the outlet port of the preheater 50 is connected to the inlet port 7a of the pressure- As long as the viscous fluid can be heated, as the preheater 50, any suitable heater can be used. When the polymer manufacturing apparatus 100 includes the preheater 50, the pressure sensor P is connected to the outlet port 41b of the preheater 50 (indicated by the symbol P surrounded by a dotted line in Fig. 3) May be located adjacent to the outflow port 41b on the line.

The pressure-regulating valve 20 is as described above. The discharge port 7b of the pressure-regulating valve 20 is connected to the supply port 61 of the devolatilizing extruder 60. [ Additionally, in this embodiment, the polymer manufacturing apparatus 100 may further include a fluid tank 51 containing a polymerization inhibitor. The tank 51 is connected to the fluid delivery port 17 of the pressure-regulating valve 20 through a pump 53. [

As the devolatilizing extruder 60, a single or multiple screw devolatilizing extruder may be used. The extruded material obtained after devolatilization is withdrawn from the discharge line (65). Further, in this embodiment, the polymer manufacturing apparatus 100 may have a recovery tank 67 for storing monomers separately recovered from volatile components (mainly containing unreacted monomers) separated in the devolatilizing extruder 60 have.

Next, a method of producing a polymer performed using such an apparatus will be described.

The method for producing a polymer of the present invention uses the above-described polymer manufacturing apparatus 100,

After controlling the pressure of the reactor by the pressure-regulating valve 20, the raw material containing the monomer and the polymerization initiator is polymerized in the reactor 40, and then the polymer composition containing the polymer and the unreacted monomer is fed from the reactor 40 Withdrawing step (polymerization step);

The polymerization inhibitor-containing fluid is transferred from the fluid delivery port 17 in the pressure-regulating valve 20 and the polymer composition withdrawn from the reactor 40 is introduced into the space 5 in the body 5 of the pressure- 3) to obtain a polymer composition mixed with the polymerization inhibitor containing fluid (pressure-regulating valve passing step), and

After feeding the polymer composition mixed with the polymerization inhibitor-containing fluid obtained through the pressure-regulating valve 20 to the devolatilizing extruder, the extruded material, in which the volatile components including unreacted monomers are at least partially removed from the polymer composition, (Devolatilizing and extruding step) of obtaining a polymer as an extruded material by drawing it out of the extruder 60.

Hereinafter, the production of the raw material and the fluid containing the polymerization inhibitor and each step will be described in detail. In this embodiment, the case where the continuous polymerization of the methacrylic ester monomer is carried out, that is, the case where the methacrylic ester polymer is produced as a polymer is described as an example, but the present invention is not limited thereto. Additionally, in this embodiment, the polymerization step may use bulk polymerization or solution polymerization, but the case of using bulk polymerization without solvent will be described.

ㆍ Preparation of raw materials

Initially, a monomer, a polymerization initiator and the like are prepared as raw materials.

As raw material monomers, a methacrylic ester monomer is used in this embodiment.

Examples of methacrylic ester monomers include,

- single alkyl methacrylates in which the alkyl group has 1 to 4 carbons, or

- a mixture of at least 80% by weight alkyl methacrylate (the alkyl group of which has from 1 to 4 carbons) and up to 20% by weight of other vinyl monomers copolymerizable therewith.

Examples of the alkyl methacrylate (whose alkyl group has 1 to 4 carbons) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, and the like. Among them, methyl methacrylate is preferable. The above-mentioned examples of the alkyl methacrylate may be used alone or at least two of the examples may be used in combination.

Examples of copolymerizable vinyl monomers include methacrylic monomers such as benzyl methacrylate and 2-ethylhexyl methacrylate (except for the alkyl methacrylates described above (whose alkyl groups have 1 to 4 carbons) Esters; Acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic acid anhydride or acid anhydrides thereof; Hydroxy groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and monoglycerol methacrylate - containing monomers; Nitrogen-containing monomers such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, diacetone acrylamide, and dimethylaminoethyl methacrylate; Epoxy group-containing monomers such as allyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate; And styrene-based monomers such as styrene and? -Methylstyrene. The above-mentioned examples of the copolymerizable vinyl monomers may be used alone or at least two of them may be used in combination.

As the polymerization initiator, for example, a radical initiator is used in this embodiment.

Examples of the radical initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, 1,1'-azobis (1-acetoxy-1-phenylethane), dimethyl 2,2'- Azobisisobutylate, and azo compounds such as 4,4'-azobis-4-cyanovaleric acid; Benzoyl peroxide, lauroyl peroxide, acetyl peroxide, caprylyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, acetyl cyclohexylsulfonyl peroxide, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxy-2-ethylhexanoate, 1,1-di (t-butylperoxy) cyclohexane, Di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, diisopropylperoxydicarbonate Di-n-butyl peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisobutyl peroxydicarbonate, di- , t-amylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-ethylhexanoate, 1 Butyl peroxyisopropyl monocarbonate, t-amyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyisopropyl monocarbonate, t- -Butylperoxyallylcarbonate, t-butylperoxyisopropylcarbonate, 1,1,3,3-tetramethylbutylperoxyisopropylmonocarbonate, 1,1,2-trimethylpropylperoxyisopropylmonocarbonate, 1 , 1,3,3-tetramethylbutylperoxyisononate, 1,1,2-trimethylpropylperoxy-isononate, and t-butylperoxybenzoate. These polymerization initiators may be used alone or in combination of at least two of them.

The polymerization initiator is selected depending on the kind of the polymer to be produced and the raw monomers used. For example, although the present invention is not particularly limited, radical polymerization initiators having a half-life of 1 minute or less at the polymerization temperature are preferable. When the half life at the polymerization temperature is 1 minute or less, the reaction rate is not too slow, so the initiator is suitable for the polymerization reaction in the continuous polymerization apparatus.

The amount of the polymerization initiator (radical initiator) to be fed is generally 0.001 to 1 part by weight based on 100 parts by weight of the raw material monomer (the raw material monomer fed to the reactor 40), but is not particularly limited. When two or more polymerization initiators are used in combination, the total weight should be within the above-mentioned range.

In addition to the above-described starting monomer and polymerization initiator, any suitable other component (s) may also be used, such as, for example, rubber polymers such as chain transfer agents, release agents, butadiene and styrene-butadiene rubber (SBR). The chain transfer agent is used to control the molecular weight of the polymer to be produced. The release agent is used to improve the moldability (or processability) of the obtained polymer.

As the chain transfer agent, either monofunctional or multifunctional chain transfer agent may be used. Specifically, these examples include n-propylmercaptan, isopropylmercaptan, n-butylmercaptan, t-butylmercaptan, n-hexylmercaptan, n-octylmercaptan, 2-ethylhexylmercaptan, n- Alkyl mercaptans such as dodecyl mercaptan, and t-dodecyl mercaptan; Aromatic mercaptans such as phenyl mercaptan and thiocresol; Mercaptans having up to 18 carbons such as ethylene thioglycol; Polyhydric alcohols such as ethylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol; Dihydronaphthalene, 1,4,5,8-tetrahydronaphthalene,? -Terpinene, terpinorene, 1,4-dihydronaphthalene, 1,4-dihydronaphthalene, 1,4-cyclohexanedicarboxylic acid, - cyclohexadiene, hydrogen sulfide, and the like. This may be used alone or in combination of two or more thereof.

The supply amount of the chain transfer agent is not particularly limited as it varies depending on the kind of the chain transfer agent used and the like. For example, when mercaptans are used, it is preferably used in an amount of 0.01 to 3 parts by weight, and more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the starting monomer (the starting monomer fed to the reactor 40) to be. The amount used within this range is preferable because it maintains the thermal stability without deteriorating the physical properties of the polymer. When two chain transfer agents are used in combination, the total weight should be within the aforementioned range.

Although the mold release agent is not particularly limited, examples thereof include esters of higher fatty acids, higher fatty alcohols, higher fatty acids, higher fatty acid amides, and metal salts of higher fatty acids. The release agent may be used alone or in combination of two or more thereof.

Examples of esters of higher fatty acids include, for example, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, octyl laurate, methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate, But are not limited to, octyl palmitate, methyl stearate, ethyl stearate, propyl stearate, butyl stearate, octyl stearate, stearyl stearate, myristyl myristate, methyl behenate, ethyl behenate, And saturated fatty acid alkyl esters such as octyl behenate; Unsaturated fatty acid alkyl esters such as methyl oleate, ethyl oleate, propyl oleate, butyl oleate, octyl oleate, methyl linoleate, ethyl linoleate, propyl linolate, butyl linoleate, and octyl linolate; There may be mentioned stearic acid esters such as lauric monoglyceride, lauric monoglyceride, lauric diglyceride, lauric triglyceride, palmitic monoglyceride, palmitic diglyceride, palmitic triglyceride, stearic monoglyceride, stearic diglyceride, stearic triglyceride, behenic monoglyceride, Saturated fatty acid glycerides such as glyceride, and behenic triglyceride; And unsaturated fatty acid glycerides such as oleic monoglyceride, oleic diglyceride, oleic triglyceride, linolenic monoglyceride, linolenic diglyceride and linolenic triglyceride. Of these, methyl stearate, ethyl stearate, butyl stearate, octyl stearate, stearic monoglyceride, stearic diglyceride, and stearic triglyceride are preferred.

Specific examples of the higher fatty alcohols include saturated fatty (or aliphatic) alcohols such as lauryl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, myristyl alcohol and cetyl alcohol ; And unsaturated fatty (or aliphatic) alcohols such as oleyl alcohol and linolyl alcohol. Of these, stearyl alcohol is preferred.

More specifically, examples of the higher fatty acids include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, And saturated fatty acids such as 12-hydroxyoctadecanoic acid; And unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, cetoleic acid, erucic acid, and ricinoleic acid.

Specific examples of the higher fatty acid amides include saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide; Unsaturated fatty acid amides such as oleic acid amide, linoleic acid amide, and erucic acid amide; And amides such as ethylene-bis-lauric acid amide, ethylene-bis-palmitic acid amide, ethylene-bis-stearic acid amide, and N-oleyl stearamide. Among them, stearic acid amide and ethylene-bis-stearic acid amide are preferable.

As the metal salts of higher fatty acids, examples thereof include sodium salts, potassium salts, calcium salts and barium salts of the above-mentioned higher fatty acids.

The amount of the releasing agent used is preferably controlled in the range of 0.01 to 1.0 part by weight, more preferably in the range of 0.01 to 0.50 part by weight, based on 100 parts by weight of the polymer contained in the obtained polymer composition.

Referring to FIG. 3, a raw monomer fluid containing at least a monomer is prepared by appropriately mixing the above-mentioned monomer and other components such as a chain transfer agent (mixture of one or more) if necessary. This is charged to the raw monomeric fluid tank 31. On the other hand, the polymerization initiator fluid containing at least the polymerization initiator is prepared by appropriately mixing the above-mentioned polymerization initiator and the monomer selectively and with other components such as a chain transfer agent, if necessary. This is filled into the polymerization initiator fluid tank 33. The polymerization initiator fluid may be a homopolymerization initiator or a mixture of a monomer and a polymerization initiator (which may further include other component (s) such as a chain transfer agent, if necessary). In the latter case, the polymerization initiator fluid is preferably a polymerization initiator solution formed by completely dissolving the polymerization initiator in the monomer.

ㆍ Preparation of Fluid Containing Polymerization Inhibitor

On the other hand, a polymerization inhibitor-containing fluid is produced.

The fluid containing the polymerization inhibitor is preferably a fluid formed by dissolving the polymerization inhibitor in a solvent which does not promote the polymerization reaction of the unreacted monomer although any fluid can be used as long as it contains the polymerization inhibitor.

Examples of solvents include organic solvents such as, for example, toluene, xylene, ethylbenzene, methylisobutylketone, methyl alcohol, ethyl alcohol, octane, decane, cyclohexane, decalin, butyl acetate, and pentyl acetate; And a monomer used as a raw material of the polymer to be produced, and in particular, a monomer used as a raw material of the polymer to be produced is preferably used. The monomers used as raw materials for the polymer to be produced are usually liquid. When the above-mentioned monomer is used as a solvent, impurities can be prevented from being included in the produced polymer. Additionally, the polymerization inhibitor-containing fluid comprises a polymerization inhibitor, and polymerization of the monomer as a solvent in this fluid is also inhibited.

Examples of the polymerization inhibitor include, for example, hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, 4-methoxy-1-naphthol, 1,4-naphthoquinone, 2,4- tert-butylphenol, phenothiazine, benzophenothiazine, dinitrobenzene, p-phenyldiamine, dimethyldithiocarbamic acid salt and the like. Of these, 2,4-dimethyl-6-tert-butylphenol is preferable in that it can be less adversely affected, such as coloration, even if it is kept in a polymer state. The polymerization inhibitor to be used is appropriately selected depending on the polymer to be produced and the monomer to be used as the raw material.

The content of the polymerization inhibitor in the polymerization inhibitor-containing fluid is preferably 5 to 2,000 ppm by weight, more preferably 10 to 500 ppm by weight, based on the total weight of the fluid. When the content is less than the above-mentioned upper limit value, the proportion of the polymerization inhibitor contained in the polymer is not too high, and the coloration of the finally obtained polymer (extruded material) can be effectively prevented. Additionally, when the content is above the lower limit described above, the polymerization of the unreacted monomer in the gap 11 of the pressure-regulating valve 20 can be effectively suppressed, and when the monomer is used as a solvent, Can be effectively suppressed.

Referring to FIG. 3, a polymerization inhibitor is added to the above-mentioned solvent to prepare a polymerization inhibitor-containing fluid. This is filled with the polymerization inhibitor-containing fluid tank 51.

ㆍ Polymerization step

The monomer and the polymerization initiator are continuously supplied from the raw material monomer tank 31 and the polymerization initiator fluid tank 33 to the reactor 40 through the supply port 41a. Specifically, the raw material monomer fluid containing the monomer is supplied from the raw material monomer fluid tank 31 by the pump 35, and the polymerization initiator fluid containing the polymerization initiator is supplied to the polymerization initiator fluid tank 33 by the pump 37, So that the fluids pass through the raw material supply line 39 together and are continuously supplied to the reactor 40 through the supply port 41a.

When the mixture of the monomer and the polymerization initiator is supplied as the polymerization initiator fluid from the polymerization initiator fluid tank 33 for the supply of the polymerization initiator to the reactor 40, the ratio A: B is in the range of 80:20 to 98: 2 Where A represents the supply flow rate (kg / h) of the raw material monomer fluid from the raw monomer fluid tank 31 and B represents the polymerization initiator fluid from the polymerization initiator fluid tank 33 , And the content of the polymerization initiator in the mixture is 0.002 to 10% by weight).

The monomers and the polymerization initiator supplied to the reactor 40 as described above are subjected to a polymerization reaction in the reactor 40 so that at least a part of the monomers are polymerized to provide a polymer. In this embodiment, the polymerization step is carried out by bulk polymerization, but the present invention is not limited thereto. In the reactor 40, the contents are stirred by a stirrer 45, preferably in a completely mixed state.

In the 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. When the outlet port 41b of the reactor 40 is located at the top of the reactor, the full charge condition is simply achieved by continuously feeding the reactor 40 and withdrawing it from the reactor 40.

Further, in the polymerization step, continuous polymerization is carried out under adiabatic conditions. The adiabatic condition can be achieved by making the inner temperature of the reactor 40 and the temperature of its outer surface approximately equal to each other. Specifically, the pumps 35 and 37 are operated so that the temperature of the outer surface of the reactor 40 set for the jacket 43 coincides with the temperature inside the reactor 40 detected by the temperature sensor T, The adiabatic condition can be realized by controlling the supply amount of the raw material containing the monomer and the polymerization initiator into the reaction vessel 40.

The continuous polymerization temperature in the polymerization step is understood as the temperature in the reactor 40 (detected by the temperature sensor T). The polymerization step is carried out at a temperature of, for example, 120 to 180 ° C, more preferably 130 to 180 ° C, although this is determined by the type of polymerization initiator used. When this temperature is too high, the syndiotacticity of the prepared polymer is reduced, the generation of oligomers is increased, and the thermal resistance of the finally obtained polymer (extruded material) tends to decrease. However, it should be noted that the temperature in the reactor may vary depending on various conditions until it reaches a static state.

The pressure of the continuous polymerization in the polymerization step is understood as the pressure (detected by the pressure sensor P) in the reactor 40. This pressure is controlled by the pressure-regulating valve 20 so as to prevent the evaporation of the raw monomers in the reactor and is the pressure above the vapor pressure of the raw monomer at the temperature in the reactor. The pressure is generally about 1.0 to 2.0 MPaG, preferably 1.2 to 3.5 MPaG (G: gauge pressure).

The continuous polymerization period in the polymerization step is understood as the average residence time in the reactor (40). The average residence time in the reactor 40 may be set according to the productivity of the polymer in the polymer composition and the like, for example, but not limited to, 15 minutes to 6 hours, preferably 20 minutes to 2 hours. When the period is exceeded, the generation of oligomers such as dimers and trimers increases and the thermal resistance of the finally obtained polymer (extruded material) tends to decrease. The average residence time in the reactor 40 can be adjusted by changing the supply amount (supply flow rate) of the monomers or the like to the reactor 40 using the pumps 35 and 37.

As described above, the polymer composition is continuously withdrawn at the outlet port 41b of the reactor 40. [ The obtained polymer composition includes the polymer produced and unreacted monomers, and may further contain an unreacted polymerization initiator, a decomposition material of the polymerization initiator, and the like. The major volatile component in the polymer composition is unreacted monomers.

The polymerization rate in the polymer composition is, for example, 40 to 70% by weight, but the present embodiment is not limited thereto. The degree of polymerization in the polymer composition suitably corresponds to the content of the polymer in the polymer composition. When the content of the polymer is too high, the mixing and heat transfer efficiency tends to decrease and the stability tends to decrease. When the content of the polymer is too low, the unreacted monomers tend to be difficult to separate the volatile components as the main components.

ㆍ Preheating stage

Referring to FIG. 3, the polymer composition withdrawn from the reactor 40 as described above is transferred to a preheater 50, if necessary, to be preheated, but this is not essential to the present invention.

The preheater 50 is used for the purpose of increasing the devolatilization efficiency in the devolatilizing extruder 60. The polymer composition obtains some or all of the heat required to volatilize the volatile components by preheating.

The preheating temperature in the preheater 50 is preferably 180 to 220 占 폚. When the preheating temperature is below the upper limit described above, evaporation of volatile components in the polymer composition can be prevented and the polymer composition can be delivered in a liquid state at a constant flow rate.

ㆍ Pressure - Adjustment valve passage phase (Outlet speed adjustment phase)

Next, referring to FIG. 3, the polymer composition obtained as described above (the polymer composition drawn from the reactor 40, preferably the polymer composition preheated in the preheater 50) is passed to the pressure-regulating valve 20.

The polymer composition obtained as described above is continuously supplied from the polymerization inhibitor-containing fluid tank 51 to the pressure-regulating valve 20 through the fluid transfer port 17 by the pump 53, Is continuously supplied to the space 3 in the body 5 of the pressure-regulating valve 20 through the opening 7a (see Figs. 1 (a) and 1 (b)).

The supply amount (feed rate) of the polymerization inhibitor-containing fluid to the pressure-regulating valve 20 is appropriately adjusted according to the size of the pressure-regulating valve 20, the flow rate of the polymer composition, It is preferable to adjust the ratio X: Y to 80:20 to 99.9: 0.1 where X represents the supply flow rate (kg / h) of the polymer composition to the pressure-regulating valve 20, Y represents the supply Flow rate (kg / h). The supply flow rate X of the polymer composition (kg / h) is obtained from the supply flow rate A (kg / h) of the raw monomer fluid from the raw material monomer tank 31 and the flow rate of the polymerization initiator fluid (A + B) of the supply flow rate (B) (kg / h) of the polymerization initiator (the content of the polymerization initiator is 0.002 to 10% by weight). When the supply amount of the polymerization inhibitor-containing fluid is within the above-mentioned range, the proportion of the polymerization inhibitor contained in the polymer does not become too high so that the coloring of the finally obtained polymer (extruded material) can be effectively prevented, And / or the effect of suppressing the adhesion of the polymer to the guide 13 can be ensured.

In the pressure-regulating valve 20, as the polymer composition passes through the space 3, the rate of outflow of the polymer composition is adjusted by the valve element 1 to adjust the pressure in the upstream reactor 40. More specifically, for example, the position (opening) of the valve element 1 in the longitudinal (up and down) direction is adjusted by the stem 9 to provide the desired pressure (upstream from the pressure-regulating valve).

On the upstream side of the pressure-regulating valve 20, the pressure of the polymer composition is, for example, 1.0 to 4.0 MPaG, preferably 1.2 to 3.5 MPaG (gauge pressure). The opening degree of the pressure-regulating valve 20 is adjusted so that the pressure in the reactor 40 detected by the pressure sensor P becomes a predetermined pressure. When the pressure of the polymer composition on the upstream side is within the aforementioned range, the pressure in the reactor 40 may be a pressure suitable for carrying out the polymerization step. In addition, the pressure downstream of the pressure-regulating valve 20 can be controlled by a pressure-regulating valve (not shown) located in the vent line (not shown) of the devolatilizing extruder 60, Is adjusted to -1.2 to 0.4 MPaG, preferably -0.09 to 0.35 MPaG (gauge pressure). When the pressure of the polymer composition on the downstream side is in the above range, devolatilization of the devolatilizing extruder 60 can be effectively performed.

In addition, in the pressure-regulating valve 20, the polymerization inhibitor-containing fluid transferred from the fluid transfer port 17 flows into the space 3 through the gap 11 and is mixed with the polymer composition in the space 3 do. The fluid containing the polymerization inhibitor is delivered from the fluid delivery port 17, so that the inside of the gap 11 is pressed. The pressure in the gap 11 is higher than in the space 3 of the body 5 so that the inflow of the polymer composition (for example, unreacted monomer and polymer) from the space 3 to the gap 11 can be sufficiently suppressed. For a suitable range of pressure in the gap 11, the size of the pressure-regulating valve 20, the flow rate of the polymer composition and the desired pressure. It is preferable to provide a safety device such as a relief valve to the body of the transfer pump for the fluid tank containing the polymerization inhibitor in order to prevent the pressure from becoming too high.

Thus, the polymer composition mixed with the polymerization inhibitor containing fluid is supplied from the space 3 of the pressure-regulating valve 20 through the discharge port 7b.

ㆍ Evaporation extrusion step

Next, referring to FIG. 3, the polymer composition obtained as described above (the polymer composition mixed with the polymerization inhibitor-containing fluid obtained by passing through the pressure-regulating valve 20) is fed through the feed port 61 to the devolatilizing extruder 60, And is subjected to a devolatilization process.

In the devolatilizing extruder 60, the volatile components containing unreacted monomers are at least partially removed from the polymer composition and discharged as a gaseous substance through a vent line (not shown in the figure), and the remaining extruded material is cut (Not shown in the drawing) and discharged from the discharge line 65. [

As a method of using a devolatilizing extruder, any suitable methods, for example, JP-A-3-49925, JP-B-51-29914, JP-B-52-17555, JP- -A-62-89710 and the like can be suitably used.

Generally, the devolatilization process is continuously carried out with a screw under heating to, for example, 200 to 290 DEG C so as to successively separate and remove at least a part, preferably the majority, more preferably substantially all, of the volatile components contained in the polymer composition ≪ / RTI > The pressure of the devolatilization process is, for example, about -1.2 to 0.4 MPaG (gauge pressure) as the aeration pressure.

Thus, the polymer can be obtained as extruded material after deviating extrusion. The extruded material consists essentially of a polymer and possibly other components, for example residues of polymerization inhibitors.

In addition, lubricating oils such as higher alcohols and higher fatty acid esters, ultraviolet absorbers, heat stabilizers, colorants, antistatic agents and the like can be added to the polymer before, during or after the devolatilization of the polymer composition in the devolatilizing extruder have.

On the other hand, the volatile components removed in the devolatilizing extruder 60 can be recycled as raw monomers for polymerization. The volatile components comprise unreacted starting monomers as the main component and may contain other volatile components such as, for example, impurities originally contained in the starting monomers, additives used if necessary, volatile byproducts (s) generated in the polymerization process, dimers Oligomers such as trimers, degradation products of polymerization initiators, etc., as well as polymerization inhibitors and impurities such as solvents (especially monomers) contained in the polymerization inhibitor-containing fluid. Generally, this is not preferable because a large amount of impurities causes the obtained resin composition to be colored. In that case, the volatile components (including the unreacted starting monomer as the main component and the impurity as described above) removed from the devolatilizing extruder 60 are removed from the monomer recovery tower (not shown) to remove impurities from the above- Not shown in the drawing), and may be treated by distillation, adsorption, or the like in the monomer recovery tower. Thus, unreacted starting monomers can be recovered at high purity, which can be suitably reused as starting monomers for polymerization. For example, continuous distillation is carried out in the monomer recovery tower to recover unreacted raw monomers as a distillate from the uppermost portion of the monomer recovery column, which is stored in the recovery tank 67 and then transferred to the raw monomer- Or it may be transferred to the raw material monomer fluid tank 31 and recycled without being stored in the recovery tank 67. On the other hand, the impurities removed from the monomer recovery column may be discarded as waste.

In order to prevent the recovered raw monomers from causing a polymerization reaction in the recovery tank 67 or the raw material monomer fluid tank 31, the polymerization inhibitor may be used in these tanks, for example, in a proportion of 2 to 8 ppm by weight relative to the starting monomers And more preferably, in addition, the oxygen concentration of the gaseous phase in these tanks is set to 2 to 8% by volume. If it is desired to store the recovered raw material monomer in the recovery tank 67 for a long period of time, it is preferable to store it at a low temperature of, for example, 0 to 5 占 폚.

Thus, as can be seen from the above description, according to the polymer preparation apparatus of the present invention and the polymer preparation method carried out using the apparatus, the stem 9 of the pressure-regulating valve 20 and / or the guide 13 The adhesion of the polymer can be effectively prevented, so that the operation can be stably continued for a long period of time.

In this embodiment, a case of performing bulk polymerization in the polymerization step is explained. However, the present invention is not limited thereto, and solution polymerization may be carried out in the polymerization step. In this embodiment, the solvent is used for solution polymerization, so that the polymer production apparatus can be used in combination with a solvent tank, a supply line, and a solvent tank for supplying a solvent to the reactor 40, in addition to a configuration similar to the apparatus described above with reference to FIG. And has an associated pump. The solvent may be supplied to the reactor (40) after being mixed with the raw material monomer and / or the polymerization initiator, or directly to the reactor (40). The polymerization step is carried out analogously to the polymerization step described above except that the solvent is used in the polymerization reaction. The solvent may be appropriately selected depending on the raw material monomers of the solution polymerization reaction and the like, and examples thereof include toluene, xylene, ethylbenzene, methylisobutylketone, methyl alcohol, ethyl alcohol, octane, decane, cyclohexane, decalin, Pentyl acetate, and the like. In this case, the ratio C: D is, for example, from 70:30 to 95: 5, preferably from 80:20 to 90:10, but not limited thereto, and C is the ratio of the raw monomer fluid Represents the supply flow rate (kg / h), and D represents the supply flow rate (kg / h) of the solvent to the reactor 40.

Example

Hereinafter, embodiments of the method for producing a polymer of the present invention are shown below, but the present invention is not limited to these embodiments.

(Example 1)

In this example, in general, the polymer preparation process as described above was carried out to prepare the polymer in the form of pellets. More specifically, this has been described below.

A raw monomer liquid having the following composition was prepared.

- methyl methacrylate 98.718 wt%

- methyl acrylate 0.908 wt%

- chain transfer agent (n-octylmercaptan) 0.261 wt%

- 0.113 wt% of a release agent (stearyl alcohol)

On the other hand, a polymerization initiator fluid having the following composition was prepared.

- methyl methacrylate 99.520 wt%

- Polymerization initiator [1,1-di (t-butylperoxy) cyclohexane] 0.480 wt%

Further, 2,4-dimethyl-6-tert-butylphenol as a polymerization inhibitor was dissolved in methyl methacrylate at 50 ppm by weight to prepare a polymerization inhibitor-containing fluid.

To prepare the polymer in this example, the polymer preparation apparatus shown in Fig. 3 was used. A fully mixed reactor having a capacity of 13 liters was used as the reactor 40. The monomer raw fluid and the polymerization initiator fluid prepared above were respectively charged into the raw material monomer tank 31 and the polymerization initiator fluid tank 33. Further, the polymerization inhibitor-containing fluid prepared above was filled into the fluid tank 51 containing the polymerization inhibitor.

The raw monomer fluid and the polymerization initiator fluid were respectively supplied from the raw material monomer tank 31 and the polymerization initiator fluid tank 33 to the reactor 40 through the supply port 41a.

The supply of the monomer feed fluid and the polymerization initiator fluid to the reactor 40 was performed such that the ratio of the monomer feed fluid and the polymerization initiator fluid was 17.6: 1 (by weight), and the average residence time in the reactor 40 was 26 minutes. The temperature in the reactor 40 and the temperature of the jacket 43 were 175 ° C.

The pressure of the reaction system was automatically controlled by using the pressure-regulating valve 20 shown in Fig. 1 such that the pressure in the reactor 40 was 1.60 MPaG (gauge pressure). The polymerization inhibitor-containing fluid was continuously transferred from the polymerization inhibitor-containing fluid tank 51 to the pressure-regulating valve 20 through the fluid transfer port 17. The pressure-regulating valve 20 was conveyed so that the ratio of the flow rate of the polymerization inhibitor-containing fluid to the total flow rate of the raw monomer fluid and the polymerization initiator fluid to the reactor 40 was 1: 79 (by weight).

The reaction mixture in the reactor 40 was continuously withdrawn as a polymer composition through the outlet port 41b. The polymer composition thus obtained was preheated by passing through a preheater 50 set at 200 占 폚. After passing the polymer composition through the pressure-regulating valve 20, volatile components such as unreacted feed monomers were removed in a devolatilizer 60 set at 240 캜 and the residue was extruded into a molten state, cooled with water, , The pellets were discharged from the discharge line 65. Thus, the polymer was prepared in the form of pellets.

The polymerization rate (% by weight) was determined by the feed weight per hour of the raw monomeric fluid and the polymerization initiator fluid and the production (discharge) weight of the pellets per hour. The polymerization rate was 56% by weight.

The polymer preparation operation described above lasted for 10 days. During this operation, the pressure in the reactor 40 can be adjusted to a range of 1.60 +/- 0.01 MPaG (gauge pressure).

(Comparative Example 1)

The polymer was prepared similarly to Example 1, except that methyl methacrylate was used instead of the polymerization inhibitor-containing fluid.

The above polymer preparation was carried out continuously. As a result, on the third day after starting operation, the movement of the pressure-regulating valve 20 became difficult and the operation was stopped after the pressure in the reactor 40 was increased to 1.65 MPaG (gauge pressure).

The present invention can be used to prepare polymers such as (meth) acrylic polymers.

Priority is claimed on Japanese Patent Application No. 2011-173503, filed on August 9, 2011, entitled " Polymer Manufacturing Apparatus and Method ". The entire contents of which are incorporated herein by reference.

1 valve element
3 spaces
5 Body
5a seat portion
7a inlet port
7b outlet port
9 Stem
11 Clearance
13 Guide
15 sealing parts
15a Packing
15b Lantern Ring
17 Fluid feed port
19 drive unit
20 Pressure-regulating valve
31 Raw material monomer fluid tank
33 Polymerization initiator Fluid tank
35, 37 pump
39 raw material supply line
40 reactor
41a supply port
41b outlet port
43 jackets
45 Stirrer
50 preheater
51 Fluid tank containing polymerization inhibitor
53 Pump
60 demolding extruder
61 Supply port
65 discharge line
67 Recovery tank
100 polymer manufacturing apparatus

Claims (6)

A (meth) acrylic polymer producing apparatus comprising a reactor, a pressure-regulating valve and a devolatilizing extruder so that the polymer composition obtained from the reactor is fed to the devolatilizing extruder through a pressure-regulating valve,
The pressure-regulating valve includes a valve element, a body having a space for receiving the valve element, a stem for supporting and controlling the valve element, a guide for slidably guiding the stem, and a fluid- Wherein a fluid containing a polymerization inhibitor is delivered through the fluid transfer port to a gap between a surface of the stem and an inner surface of the guide, the gap communicating with the space in the body, And the transferred fluid flows into the space. The method according to claim 1,
Wherein the pressure-regulating valve further comprises a lantern ring at a sealing portion between the stem and the guide, the fluid transfer port being located adjacent to the lantern ring. A process for producing a (meth) acrylic polymer using the (meth) acrylic polymer producing apparatus according to claim 1 or 2,
(Meth) acrylic monomer and an unreacted (meth) acrylic monomer from the reactor after the reactor containing the (meth) acrylic monomer and the polymerization initiator is polymerized in the reactor while the pressure of the reactor is adjusted by the pressure- Withdrawing the contained polymer composition;
The polymeric composition withdrawn from the reactor is passed through a space in the body of the pressure-regulating valve to transfer fluid containing the polymerization inhibitor from the fluid delivery port of the pressure-regulating valve, ; And
After feeding the polymer composition mixed with the fluid obtained through the pressure-regulating valve to the devolatilizing extruder, the extruded material in which the volatile components including the unreacted (meth) acrylic monomer are at least partially removed from the polymer composition, To obtain a (meth) acrylic polymer as an extruded material. The method of claim 3,
Wherein the fluid containing the polymerization inhibitor is a fluid formed by dissolving a polymerization inhibitor in a (meth) acrylic monomer. The method of claim 3,
Wherein the content of the polymerization inhibitor in the fluid containing the polymerization inhibitor is 5 to 2,000 ppm by weight based on the total weight of the fluid. The method of claim 3,
Wherein the ratio of the feed rate of the polymer composition to the pressure-regulating valve to the feed rate of the fluid comprising the polymerization inhibitor to the pressure-regulating valve is 80:20 to 99.9: 0.1.

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