WO2014088082A1 - メタクリル系重合体組成物の製造方法および成形体 - Google Patents
メタクリル系重合体組成物の製造方法および成形体 Download PDFInfo
- Publication number
- WO2014088082A1 WO2014088082A1 PCT/JP2013/082750 JP2013082750W WO2014088082A1 WO 2014088082 A1 WO2014088082 A1 WO 2014088082A1 JP 2013082750 W JP2013082750 W JP 2013082750W WO 2014088082 A1 WO2014088082 A1 WO 2014088082A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction tank
- polymerization
- raw material
- polymerization initiator
- composition
- Prior art date
Links
- YCSOOPXVDJVYIH-UHFFFAOYSA-N C(C1)C1C1C=CC=C1 Chemical compound C(C1)C1C1C=CC=C1 YCSOOPXVDJVYIH-UHFFFAOYSA-N 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N CC1CCCC1 Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a method for producing a methacrylic polymer composition and a molded product obtained from the methacrylic polymer composition obtained by the method.
- the methacrylic resin composition is excellent in transparency and weather resistance.
- a methacrylic resin composition is used as a molding material for light guide plates used for backlight unit members of various liquid crystal displays, and for vehicle members such as tail lamp covers, head lamp covers, and meter panels (Patent Documents). 1 and 2).
- a methacrylic resin composition a composition containing a high molecular weight polymer and a low molecular weight polymer is known (see Patent Documents 3 to 7).
- a methacrylic polymer composition containing both a high molecular weight polymer and a low molecular weight polymer has the advantages of having a broad molecular weight distribution and excellent solvent resistance and molding fluidity.
- methyl methacrylate and methyl acrylate were added in the presence of the methacrylic resin obtained by suspension polymerization, followed by suspension polymerization.
- the conventional method for producing a methacrylic resin composition having a wide molecular weight distribution has problems in controlling transparency, productivity, and molecular weight distribution.
- the method of individually preparing methacrylic resins having different average molecular weights and blending the individually prepared resins when the individually adjusted resin is taken out in the form of a pellet or powder, an extrusion process or a dehydration / drying process Etc., and an extrusion process is required during blending.
- multi-stage polymerization is efficient because the desired product can be obtained in a single extrusion process.
- Examples of methods for achieving multistage polymerization include suspension polymerization, solution polymerization, and bulk polymerization.
- a methacrylic polymer composition is produced by a multistage polymerization method of suspension polymerization, transparency is impaired because a dispersion stabilizer or an emulsifier is used (Patent Document 7).
- solution polymerization in general, there arises a problem that the heat decomposability of the polymer is lowered by the solvent, and the solvent and monomer recovery method becomes complicated.
- reaction control is difficult because the viscosity of the reaction mixture increases.
- Patent Document 4 As a method that enables reaction control in the two-stage polymerization in bulk polymerization that does not include a solvent, a method of polymerizing to a polymerization rate of 1 to 50% and then adding a chain transfer agent to polymerize to a polymerization rate of 60% or more Is known (Patent Document 4).
- the first stage polymerization condition is 130 ° C. for 2 hours
- the second stage polymerization condition is 60 ° C. for 10 hours.
- repolymerization is performed in the second stage under polymerization conditions milder than in the first stage. Therefore, this method requires a long time and productivity is not sufficient.
- an object of the present invention is to provide an efficient method for producing a methacrylic polymer composition having a wide molecular weight distribution by controlling the ratio of a low molecular weight polymer and a high molecular weight polymer.
- Another object of the present invention is to provide a molded product obtained from the methacrylic polymer composition obtained by the above-described method.
- a raw material composition A containing a raw material monomer A containing 50% by weight or more of methyl methacrylate, a polymerization initiator A and a chain transfer agent A is supplied from the supply port of the first complete mixing type reaction tank, A first polymerization step in which the raw material composition A is subjected to continuous bulk polymerization in the fully mixed reaction tank, and the resulting intermediate composition is extracted from the outlet of the first fully mixed reaction tank; A raw material monomer B containing 50% by weight or more of methyl methacrylate, a raw material composition B containing a polymerization initiator B and a chain transfer agent B, and an intermediate composition extracted in the first polymerization step are used as a second complete mixing type.
- the raw material composition B and the intermediate composition are further subjected to continuous bulk polymerization in the second complete mixing type reaction tank, and the resulting methacrylic polymer composition is subjected to the second complete mixing.
- a second polymerization step withdrawn from the outlet of the mold reaction tank, and the following formulas (I), (II), (III), (IV) and (V) 120 ⁇ T1 ⁇ 160 (I) 140 ⁇ T2 ⁇ 180 (II) 20 ⁇ T2-T1 ⁇ 60 (III) 1.7 ⁇ [S2] / [S1] (IV) 1 ⁇ Q1 / Q2 ⁇ 50 (V)
- T1 is the temperature (° C.) in the first fully mixed reaction vessel in the first polymerization step
- T2 is the temperature (° C.) in the second complete mixing reaction vessel in the second polymerization step, [S1].
- a mixture of a low molecular weight polymer and a high molecular weight polymer can be prepared easily and continuously.
- a methacrylic polymer composition having a broad molecular weight distribution and a controlled proportion of low molecular weight polymer and high molecular weight polymer can be produced with high productivity.
- the methacrylic polymer composition obtained by the method of the present invention can be suitably used as a material for a molded body.
- FIG. 1 is a schematic view for explaining a method for producing a methacrylic polymer composition in one embodiment of the present invention.
- FIG. 2 is a molecular weight distribution curve of the methacrylic polymer compositions of Examples 1 to 3 and Comparative Examples 1 and 2.
- FIG. 3 is a molecular weight distribution curve of the methacrylic polymer compositions of Examples 4 and 5.
- FIG. 4 is a molecular weight distribution curve of the methacrylic polymer compositions of Examples 6 and 7.
- the method for producing a methacrylic polymer composition of the present invention (hereinafter also simply referred to as “polymer composition”) is carried out using at least two completely mixed reaction vessels, and continuous bulk polymerization is performed in each reaction vessel. To be implemented.
- the method for producing the polymer composition of the present embodiment is performed using at least the first reaction tank 10 and the second reaction tank 20. Both of these reaction tanks 10 and 20 are complete mixing type reaction tanks, and are used in this embodiment for carrying out continuous bulk polymerization as continuous polymerization in the first polymerization step and the second polymerization step.
- the first reaction tank 10 has a supply port 11a and an extraction port 11b, and preferably the outer wall surface of the reaction tank as a temperature adjusting means for adjusting the temperature of the outer wall surface of the reaction tank. And a stirrer 14 for stirring the contents.
- the second reaction vessel 20 has a supply port 21a and an extraction port 21b, and preferably a jacket surrounding the outer wall surface of the reaction vessel as a temperature adjusting means for adjusting the temperature of the outer wall surface of the reaction vessel. 23 and a stirrer 24 for stirring the contents.
- the extraction ports 11b and 21b are provided at the top of each reaction tank.
- supply port 11a and 21a do not limit this embodiment, generally it can be provided in the appropriate position under each reaction tank.
- Each of these reaction tanks 10 and 20 may be provided with a temperature sensor T as temperature detection means for detecting the temperature in the reaction tank.
- the volumes of the first reaction tank 10 and the second reaction tank 20 may be the same or different from each other. By making the volume of the first reaction tank 10 and the volume of the second reaction tank 20 different, the average residence time is effectively made different between the first reaction tank 10 and the second reaction tank 20. Can do.
- agitators 14 and 24 With the agitators 14 and 24, the inside of the reaction vessel can be brought into a substantially complete mixed state.
- These agitators may be equipped with any appropriate agitating blade, such as a MIG wing, a Max blend wing (registered trademark, manufactured by Sumitomo Heavy Industries, Ltd.), a paddle wing, a double helical ribbon wing, a full zone. Wings (registered trademark, manufactured by Shinko Environmental Solution Co., Ltd.) may be provided.
- a baffle in the reaction vessel In order to increase the stirring effect in the reaction vessel, it is desirable to attach a baffle in the reaction vessel.
- the present embodiment is not limited to this, and may have any appropriate configuration in place of the stirrers 14 and 24 as long as the inside of the reaction vessel can be substantially completely mixed.
- the stirring power should not be larger than necessary from the viewpoint of not adding an excessive amount of heat to the reaction tank by the stirring operation.
- the stirring power is not particularly limited, but is preferably 0.5 to 20 kW / m 3 , and more preferably 1 to 15 kW / m 3 .
- the stirring power is preferably set larger as the viscosity of the reaction system becomes higher (or as the content of the polymer in the reaction system becomes higher).
- the supply port 11a of the first reaction tank 10 includes a raw material monomer tank (a supply source of raw material monomer and optionally a chain transfer agent) 1 and a polymerization initiator tank (a polymerization initiator and optionally a raw material monomer and / or Alternatively, a chain transfer agent supply source 3 is connected through a raw material supply line 9 via pumps 5 and 7, respectively.
- the raw material monomer, the polymerization initiator, and the chain transfer agent are supplied from the raw material monomer tank 1 and the polymerization initiator tank 3 in the first reaction tank 10, but the raw material monomer, the polymerization initiator, and the chain transfer.
- the number of the agent supply sources and their modes are not particularly limited as long as the raw material monomer, the polymerization initiator, and the chain transfer agent can be appropriately supplied to the first reaction vessel 10.
- another supply port 11c is provided in the first reaction tank 10, and this supply port 11c is connected to the polymerization initiator tank 3 with a pump 7 as shown by a dotted line in FIG. It may be connected via.
- the extraction port 11 b of the first reaction tank 10 is connected to the supply port 21 a of the second reaction tank 20 through the connection line 15.
- the extraction port 21 b of the second reaction tank 20 is connected to the extraction line 25.
- the 1st reaction tank 10 and the 2nd reaction tank 20 are connected in series. It is preferable that no pump exists on the connection line 15 between the extraction port 11b of the first reaction tank 10 and the supply port 21a of the second reaction tank 20.
- the second reaction tank 20 is connected to a polymerization initiator tank (new supply source of raw material monomer, polymerization initiator and chain transfer agent) 17 via a pump 19.
- the new supply source of the raw material monomer, the polymerization initiator and the chain transfer agent is the polymerization initiator tank 17, but the number of the new supply sources of the raw material monomer, the polymerization initiator and the chain transfer agent and those
- the aspect of (for example, composition in the case of a mixture) and the like are not particularly limited as long as the raw material monomer, the polymerization initiator, and the chain transfer agent can be appropriately supplied to the second reaction vessel 20 newly. As shown in FIG.
- the supply port 21 a of the second reaction tank 20 may be connected to the polymerization initiator tank 17 through a connection line 15 via a pump 19, or alternatively, to the second reaction tank 20.
- Another supply port 21c is provided, and this supply port 21c may be connected to the polymerization initiator tank 17 via a pump 19, for example, as shown by a dotted line in FIG.
- the pumps 5, 7 and 19 are not particularly limited, but are preferably pumps capable of setting the flow rates from the raw material monomer tank 1, the polymerization initiator tank 3 and the polymerization initiator tank 17 to a constant amount.
- a multiple reciprocating pump is preferable, and a non-pulsating constant pump such as a double non-pulsating metering pump or a triple non-pulsating metering pump is more preferable.
- the additional supply of chain transfer agent can be controlled.
- connection line 15 that connects the extraction port 11b of the first reaction tank 10 to the supply port 21a of the second reaction tank 20 adjusts the temperature of the connection line 15. It is preferable to provide a jacket (not shown) or the like surrounding the outer wall surface of the connection line 15 as the temperature adjusting means that can be used. Thereby, the temperature of the connection line 15 (more specifically, the temperature of the outer wall surface of the connection line, and thus the temperature of the connection line) is set so that the temperature is substantially the same as the temperature in the first reaction vessel 10. Can be adjusted.
- the temperature control means of the connection line 15 is the connection line 15. Can be controlled to be substantially the same as the temperature in the first reaction vessel 10 detected by the temperature sensor T.
- the temperature of the outer wall surface of the reaction tank set for the jackets (temperature adjusting means) 13 and 23 and the temperature in the reaction tank detected by the temperature sensor (temperature detection means) T are the first Adjusting the operation of the pumps 5 and 7 to supply the raw material monomer, the polymerization initiator and the chain transfer agent to the first reaction tank 10 so as to match each of the reaction tank 10 and the second reaction tank 20 Or by adjusting the temperature of the outer wall of the reaction vessel set for the jackets 13 and 23, or by adding raw material monomers, polymerization initiator and chain transfer agent to the second reaction vessel 20
- the supply amount can be controlled by adjusting the operation of the pump 19.
- the polymerization reaction of the intermediate composition (described later) extracted from the extraction port 11b may be caused by factors such as consumption of the supplied polymerization initiator. 15 does not proceed, that is, the polymerization reaction heat may not be generated in the connection line 15.
- the temperature of the jacket covering the connection line 15 is set to substantially the same temperature as the temperature in the first reaction vessel 10, or the connection line 15 is covered with a heat insulating material instead of the jacket.
- the temperature in the connection line 15 can be made substantially the same as the temperature in the first reaction vessel 10. In this case, the temperature in the connection line 15 may be considered to be substantially the same as the temperature of the jacket covering the connection line 15.
- the jackets 13 and 23 cover substantially the entire reaction tanks 10 and 20, respectively, and react by introducing a heat medium such as steam, hot water, or an organic heat medium from a heat medium supply path (not shown).
- the tanks 10 and 20 are appropriately heated or kept warm.
- the temperatures of the jackets 13 and 23 can be appropriately adjusted depending on the temperature or pressure of the supplied heat medium.
- the heat medium introduced into the jackets 13 and 23 is removed from the heat medium discharge path (not shown).
- the temperature and pressure of the jackets 13 and 23 are detected by a sensor such as a temperature sensor (not shown) provided on the heat medium discharge path.
- the location of the sensor such as the temperature sensor is not particularly limited, and may be on the heat medium supply path or in the jackets 13 and 23, for example.
- the connection line 15 includes a jacket, the jacket of the connection line 15 may have the same configuration as the jackets 13 and 23.
- the polymerization reaction in the reaction vessels 10 and 20 is required to be performed in the reaction vessels 10 and 20 at a substantially constant polymerization temperature from the viewpoint of making the quality of the produced polymer constant. Therefore, the temperature adjusting means (jackets 13 and 23) is controlled to a preset constant temperature so that the internal temperatures of the reaction vessels 10 and 20 can be kept substantially constant.
- the set temperature of the temperature adjusting means (jackets 13 and 23) is transmitted to the supply flow rate control means described later, and the supply flow rate is controlled by the raw material monomer supply means (pump 5) and the polymerization initiator supply means (pumps 7 and 19). This is data for determining whether or not it is necessary.
- the set temperature of the temperature adjusting means (jackets 13 and 23) can be adjusted by controlling the temperature or pressure of the heating medium.
- a control unit including a CPU, a ROM, a RAM, and the like
- the ROM of the control unit is a device for storing a program for controlling the pumps 5, 7, 19 and the like
- the RAM of the control unit is a reaction vessel detected by the temperature sensor T in order to execute the program.
- This is a device for temporarily storing temperature data in 10 and 20, data on set temperatures of jackets 13 and 23, and data on set temperatures of jackets of connection lines 15 when present.
- the CPU of the control unit executes the program stored in the ROM based on the temperature data in the reaction vessels 10 and 20 and the set temperature data of the jackets 13 and 23 stored in the RAM, and performs a reaction.
- the supply flow rate of the raw material monomer, the polymerization initiator and / or the chain transfer agent into the tanks 10 and 20 is controlled by the raw material monomer supply means (pump 5) and / or the polymerization initiator supply means (pumps 7 and 19).
- the connection line 15 is provided with a jacket as a temperature adjusting means
- the CPU of the control unit can store the temperature data in the reaction vessels 10 and 20 stored in the RAM and the jacket of the connection line 15 (not shown).
- To execute the program stored in the ROM (which may be a part of the program or a program different from the program) based on the set temperature data in FIG. The set temperature can be adjusted.
- control by the supply flow rate control means is shown below.
- the CPU executes the program in the ROM, for example, into the reaction vessel 10.
- the pump 7 is controlled so as to reduce the supply flow rate of the polymerization initiator.
- the pump 19 is controlled so as to decrease the flow rate of the polymerization initiator supplied into the reaction vessel 20, for example.
- the supply flow rate of the polymerization initiator into the reaction vessel 10 is increased by executing the program in the ROM by the CPU.
- the pump 7 is controlled.
- the polymerization initiator is supplied to the reaction tank 20 by the pump 19 and the polymerization is being performed, when the temperature of the reaction tank 20 falls below the set temperature of the jacket 23, the CPU executes the program in the ROM, for example, The pump 19 is controlled so as to increase the supply flow rate of the polymerization initiator into the reaction vessel 20.
- the heat of polymerization generated in the reaction vessel 10 and / or 20 can be increased, and as a result, the temperature in the reaction vessel 10 and / or 20 can be increased.
- the pumps 7 and 19 are controlled.
- control examples include the following control. That is, when the temperature in the reaction vessel 10 detected by the temperature sensor T exceeds the set temperature of the jacket 13 that is a temperature adjusting means, the supply flow rate of the raw material monomer is increased by controlling the pump 5 to react. The relative supply flow rate of the polymerization initiator into the tank 10 is decreased. Also by such control, the temperature in the reaction vessel 10 can be lowered.
- the ratio between the supply flow rate of the raw material monomer and the supply flow rate of the polymerization initiator may be appropriately set according to the type of polymer to be produced, the type of polymerization initiator to be used, and the like. Further, the degree of increase or decrease in the supply flow rate of the raw material monomer and the supply flow rate of the polymerization initiator is appropriately set according to the type of polymer to be produced, the type of polymerization initiator to be used, and the like.
- the polymerization initiator is not supplied alone into the reaction vessel 10 by the polymerization initiator supply means, but when a mixture of the polymerization initiator and the raw material monomer and / or chain transfer agent is supplied, and the reaction In the mixture of the polymerization initiator, raw material monomer, and chain transfer agent supplied into the tank 20, the supply flow rate of the polymerization initiator needs to be controlled in consideration of the content ratio of the polymerization initiator in the mixture.
- connection line 15 when the connection line 15 is provided with a jacket as a temperature adjusting means, the following control is exemplified. That is, when the temperature in the reaction vessel 10 detected by the temperature sensor T is different from the temperature in the connection line 15 (for convenience, the set temperature of the jacket of the connection line 15), for example, exceeds the range of ⁇ 5 ° C. At different times, the set temperature of the jacket of the connection line 15 is such that the temperature in the connection line 15 (for convenience, the set temperature of the jacket of the connection line 15) is substantially the same as the temperature of the reaction vessel 10. Adjust.
- a preheater 31 and a devolatilizing extruder 33 can be arranged downstream of the extraction line 25 from the extraction port 21b of the second reaction tank 20.
- a pressure regulating valve (not shown) may be provided between the preheater 31 and the devolatilizing extruder 33. The extrudate after devolatilization is taken out from the take-out line 35.
- the devolatilizing extruder 33 may be a screw type single-screw or multi-screw devolatilizing extruder.
- a recovery tank 37 for storing raw material monomers separated and recovered from volatile components (mainly including unreacted raw material monomers) separated by the devolatilizing extruder 33.
- a monomer containing methyl methacrylate is used as the raw material monomer.
- the raw material monomer supplied to the first reaction tank 10 is also referred to as a raw material monomer A
- the raw material monomer newly supplied to the second reaction tank 20 is also referred to as a raw material monomer B.
- Raw material monomers A and B may have the same composition or different compositions.
- the raw material monomer of the present invention contains 50% by weight or more of methyl methacrylate. By containing 50% by weight or more of methyl methacrylate, it is possible to impart transparency, weather resistance, heat resistance and the like, which are characteristics of the methacrylic resin, in the obtained methacrylic resin composition.
- the content of methyl methacrylate in the raw material monomer is preferably 80% by weight or more, and more preferably 90% by weight or more.
- the raw material monomer may contain other monomers copolymerizable with methyl methacrylate in addition to methyl methacrylate. These other monomers may be used alone or in combination of two or more.
- the content of other copolymerizable monomers in the raw material monomer is 50% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less.
- Examples of other monomers copolymerizable with methyl methacrylate include, for example, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate, and methacrylic acid.
- Alkyl methacrylate such as isobutyl and 2-ethylhexyl methacrylate (alkyl methacrylate having an alkyl group having 2 to 8 carbon atoms); aryl methacrylate such as benzyl methacrylate; methyl acrylate, ethyl acrylate, n-acrylate Acrylic acid esters such as propyl, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate; acrylic acid, methacrylic acid, Unsaturated carboxylic acids such as maleic acid, itaconic acid, maleic anhydride, itaconic anhydride or their anhydrides; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate, 2-hydroxy methacrylate Hydroxyl group-
- the polymerization initiator supplied to the first reaction tank 10 is also referred to as a polymerization initiator A
- the polymerization initiator newly supplied to the second reaction tank 20 is also referred to as a polymerization initiator B.
- the polymerization initiators A and B may have the same composition or different compositions.
- a radical initiator is used as the polymerization initiator.
- the radical initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), dimethyl 2,2′-azo.
- Azo compounds such as bisisobutyrate and 4,4′-azobis-4-cyanovaleric acid; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, caprylyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide Oxide, acetylcyclohexylsulfonyl peroxide, t-butylperoxypivalate, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-butylperoxy-2-ethylhexanoate, 1 , 1-Di ( -Butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane ,
- the polymerization initiator is selected according to the type of polymer to be produced and the raw material monomer to be used.
- the present invention is not particularly limited, but the radical polymerization initiator is preferably an agent having a half-life of 1 minute or less at the polymerization temperature. If the half-life at the polymerization temperature is within 1 minute, the reaction rate does not become too slow and is suitable for the polymerization reaction in a continuous polymerization apparatus.
- the half-life at the polymerization temperature is preferably 0.1 seconds or longer. If the half-life is less than 0.1 seconds, a rapid polymerization occurs at the site of connection to the reaction vessel, which may cause problems such as blockage of piping.
- the supply amount of the polymerization initiator is not particularly limited, but usually, the total supply amount of the polymerization initiator supplied to the reaction vessel 10 and the reaction vessel 20 is finally supplied to the reaction vessel 10. What is necessary is just to make it 0.001 to 1 weight% with respect to the total amount of a raw material monomer and the raw material monomer newly supplied to the reaction tank 20.
- FIG. 1 The supply amount of the polymerization initiator (radical initiator) is not particularly limited, but usually, the total supply amount of the polymerization initiator supplied to the reaction vessel 10 and the reaction vessel 20 is finally supplied to the reaction vessel 10. What is necessary is just to make it 0.001 to 1 weight% with respect to the total amount of a raw material monomer and the raw material monomer newly supplied to the reaction tank 20.
- chain transfer agent supplied to the first reaction tank 10 is also referred to as a chain transfer agent A
- chain transfer agent newly supplied to the second reaction tank 20 is also referred to as a chain transfer agent B
- Chain transfer agents A and B may have the same composition or different compositions. Chain transfer agents are used to adjust the molecular weight of the polymer produced.
- the chain transfer agent may be a monofunctional or polyfunctional chain transfer agent.
- chain transfer agent examples include n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, t-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, 2-ethylhexyl mercaptan, and n-dodecyl mercaptan.
- Alkyl mercaptans such as t-dodecyl mercaptan; aromatic mercaptans such as phenyl mercaptan and thiocresol; mercaptans having 18 or less carbon atoms such as ethylenethioglycol; ethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipenta Polyhydric alcohols such as erythritol, tripentaerythritol, sorbitol; hydroxyl group esterified with thioglycolic acid or 3-mercaptopropionic acid which was 1,4-dihydronaphthalene, 1,4,5,8-tetrahydronaphthalene, beta-terpinene, terpinolene, 1,4-cyclohexadiene, and the like hydrogen sulfide.
- chain transfer agents may be used alone or in combination of two or more.
- any appropriate other components such as release agents, rubbery polymers such as butadiene and styrene butadiene rubber (SBR), heat stabilizers, UV absorption An agent may be used.
- a mold release agent is used in order to improve the moldability of the resin composition obtained from a polymer composition.
- a heat stabilizer is used in order to suppress thermal decomposition of the produced polymer.
- An ultraviolet absorber is used in order to suppress deterioration by the ultraviolet-ray of the polymer to produce
- the release agent is not particularly limited, and examples thereof include higher fatty acid esters, higher aliphatic alcohols, higher fatty acids, higher fatty acid amides, and higher fatty acid metal salts.
- a mold release agent may be used independently and may be used in combination of 2 or more type.
- higher fatty acid esters include, for example, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, octyl laurate, methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate, and palmitate.
- methyl stearate, ethyl stearate, butyl stearate, octyl stearate, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride and the like are preferable.
- the higher aliphatic alcohol include saturated aliphatic alcohols such as lauryl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, myristyl alcohol, cetyl alcohol; oleyl alcohol, linolyl alcohol, and the like.
- saturated aliphatic alcohols such as lauryl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, myristyl alcohol, cetyl alcohol; oleyl alcohol, linolyl alcohol, and the like.
- unsaturated fatty alcohols Of these, stearyl alcohol is preferred.
- higher fatty acids include, for example, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and 12-hydroxyoctadecanoic acid.
- Fatty acids unsaturated fatty acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, cetreic acid, erucic acid, ricinoleic acid and the like.
- the higher fatty acid amide 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.
- higher fatty acid metal salts include sodium salts, potassium salts, calcium salts and barium salts of the higher fatty acids described above.
- the amount of the release agent used is preferably adjusted to be 0.01 to 1.0 part by weight with respect to 100 parts by weight of the polymer contained in the obtained polymer composition. It is more preferable to adjust so that it may become 50 weight part.
- the heat stabilizer is not particularly limited, and examples thereof include phosphorus heat stabilizers and organic disulfide compounds. Of these, organic disulfide compounds are preferred. In addition, a heat stabilizer may be used individually or may be used in combination of 2 or more types.
- Examples of the phosphorus-based heat stabilizer include tris (2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d.
- organic disulfide compounds include dimethyl disulfide, diethyl disulfide, di-n-propyl disulfide, di-n-butyl disulfide, di-sec-butyl disulfide, di-tert-butyl disulfide, di-tert-amyl disulfide, dicyclohexyl.
- examples thereof include disulfide, di-tert-octyl disulfide, di-n-dodecyl disulfide, di-tert-dodecyl disulfide and the like.
- di-tert-alkyl disulfide is preferable, and di-tert-dodecyl disulfide is more preferable.
- the amount of the heat stabilizer used is preferably 1 to 2000 ppm by weight based on the polymer contained in the resulting polymer composition.
- the molding temperature is set high for the purpose of increasing molding efficiency. Sometimes. In such a case, it is more effective to add a heat stabilizer.
- UV absorbers examples include benzophenone UV absorbers, cyanoacrylate UV absorbers, benzotriazole UV absorbers, malonic ester UV absorbers, and oxalanilide UV absorbers.
- An ultraviolet absorber may be used independently and may be used in combination of 2 or more type. Among these, benzotriazole type ultraviolet absorbers, malonic acid ester type ultraviolet absorbers, and oxalanilide type ultraviolet absorbers are preferable.
- benzophenone-based UV absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-octyloxybenzophenone, Examples include 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone.
- cyanoacrylate ultraviolet absorber examples include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.
- benzotriazole ultraviolet absorber examples include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole and 5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl). ) -2H-benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-pentyl-2- Hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl- 6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzo Riazor, and the like.
- 2- (1-arylalkylidene) malonic acid esters are usually used, and examples thereof include 2- (paramethoxybenzylidene) malonic acid dimethyl.
- 2-alkoxy-2'-alkyloxalanilides are usually used, and examples thereof include 2-ethoxy-2'-ethyloxalanilide.
- the amount of the ultraviolet absorber used is preferably 5 to 1000 ppm by weight with respect to the polymer contained in the obtained polymer composition.
- the above raw material monomers (one type or a mixture of two or more types) are appropriately prepared together with a chain transfer agent (and optionally other components such as a release agent) as necessary.
- the polymerization initiator as described above is appropriately prepared together with the raw material monomer and / or the chain transfer agent (if necessary, with other components such as a release agent).
- the polymerization initiator tank 3 may store the polymerization initiator alone or in the form of a mixture of the raw material monomer and the polymerization initiator (which may further include other components such as a mold release agent in some cases).
- the chain transfer agent supplied to the first reaction tank 10 is at least one of a mixture containing the raw material monomer prepared in the raw material monomer tank 1 and a mixture containing the polymerization initiator prepared in the polymerization initiator tank 3. It may be included.
- the polymerization initiator as described above is appropriately prepared together with the raw material monomer and the chain transfer agent (in some cases, with other components).
- the polymerization initiator tank 17 stores a raw material monomer, a mixture containing a polymerization initiator and a chain transfer agent (which may further contain other components depending on the case).
- a chain transfer agent which may further contain other components depending on the case.
- the supply port 11 c is connected to the polymerization initiator tank 3 via the pump 7, or when the supply port 21 c is connected to the polymerization initiator tank 17 via the pump 19, the polymerization initiator tank 3 or 17 is connected to the polymerization initiator tank 3.
- the polymerization initiator is stored alone, the polymerization initiator is supplied alone to the reaction tank 10 or the reaction tank 20, so that the polymerization reaction may locally proceed in the reaction tank 10 or the reaction tank 20.
- it stores in the form of the mixture of a raw material monomer and a polymerization initiator since the polymerization initiator is previously mixed with a part of raw material monomer, this possibility may be eliminated.
- a raw material composition containing a raw material monomer, a polymerization initiator and a chain transfer agent is supplied to the first reaction vessel.
- the raw material composition supplied to the first reaction tank is also referred to as a raw material composition A.
- the raw material monomer, the polymerization initiator and the chain transfer agent are supplied to the first reaction tank 10 from the supply port 11a from the raw material monomer tank 1 and the polymerization initiator tank 3 which are the supply sources of the raw material monomer, the polymerization initiator and the chain transfer agent. To do.
- the raw material monomer tank 1 and the raw material monomer and optionally the chain transfer agent are pumped 5 and the polymerization initiator tank 3 is supplied with a polymerization initiator (preferably a mixture of the raw material monomer, the polymerization initiator and optionally the chain transfer agent. ) Are fed together through the raw material supply line 9 by the pump 7 to the first reaction tank 10 from the supply port 11a.
- the polymerization initiator may be supplied from the polymerization initiator tank 3 to the first reaction tank 10 from the supply port 11c by the pump 7 as shown by a dotted line in FIG.
- the temperature of the raw material composition supplied to the first reaction tank 10 is not particularly limited. However, since the heat balance in the reaction tank is broken to cause the polymerization temperature to fluctuate, a heating / cooling device is appropriately used. It is preferable to adjust the temperature before being supplied to the reaction vessel 10 (not shown).
- the raw material composition supplied to the first reaction tank 10 as described above is subjected to continuous bulk polymerization (in other words, polymerization without a solvent) in the first reaction tank 10.
- This first polymerization step may be a step for allowing the polymerization reaction to proceed halfway.
- the intermediate composition is extracted from the extraction port 11 b of the first reaction tank 10.
- the continuous bulk polymerization is preferably carried out in a state where the reaction vessel is filled with the reaction mixture and substantially no gas phase is present (hereinafter referred to as “full solution state”). Due to this full liquid state, there is a problem that the gel adheres to the inner wall surface of the reaction vessel and grows, and a problem that the quality of the resin composition finally obtained is deteriorated when this gel is mixed into the reaction mixture. Occurrence can be prevented in advance. Furthermore, this full liquid state can effectively utilize the entire volume of the reaction tank in the reaction space, and thus high production efficiency can be obtained.
- a full liquid state can be realized simply by continuously supplying and extracting the first reaction tank 10 by placing the extraction port 11b of the first reaction tank 10 at the top of the reaction tank.
- the continuous bulk polymerization is preferably carried out in an adiabatic state (substantially no heat enters and exits from the outside of the reaction vessel). Due to this heat insulation state, problems such as the gel adhering to the inner wall surface of the reaction vessel and growing, and the problem that the quality of the resin composition finally obtained when this gel is mixed into the reaction mixture occur. This can be prevented in advance. Furthermore, this adiabatic state can stabilize the polymerization reaction and can provide self-controllability for suppressing the runaway reaction.
- the heat insulation state can be realized by making the temperature inside the first reaction tank 10 and the temperature of the outer wall surface thereof substantially equal. Specifically, the temperature of the outer wall surface of the first reaction tank 10 set for the jacket (temperature adjusting means) 13 and the temperature sensor (temperature detecting means) using the above-described control device (not shown). ) Adjusting the operation of the pumps 5 and 7 to supply the raw material monomer and the polymerization initiator to the first reaction tank 10 so that the temperature in the first reaction tank 10 detected by T matches. Can be realized. In addition, when the temperature of the outer wall surface of the reaction tank is set too high compared to the temperature in the reaction tank, extra heat may be applied to the reaction tank.
- the temperature difference between the inside of the reaction tank and the outer wall surface of the reaction tank is as small as possible.
- the polymerization heat and heat of stirring generated in the first reaction tank 10 are usually carried away when the intermediate composition is extracted from the first reaction tank 10. The amount of heat that the intermediate composition takes away is determined by the flow rate of the intermediate composition, the specific heat, and the temperature of the polymerization reaction.
- the temperature of the continuous bulk polymerization in the first polymerization step is understood as the temperature in the first reaction tank 10 (detected by the temperature sensor T).
- the first polymerization step is performed at a temperature of 120 to 160 ° C, preferably at a temperature of 120 to 150 ° C.
- the temperature in the reaction vessel may vary depending on various conditions until a steady state is reached.
- the temperature in the first reaction tank 10 depends on the heat of polymerization. The higher the polymerization initiator concentration in the raw material composition supplied to the first reaction tank 10, the higher the polymerization rate. As a result, the temperature in the first reaction tank 10 can be increased.
- the pressure of continuous bulk polymerization in the first polymerization step is understood as the pressure in the first reaction vessel 10.
- This pressure is set to a pressure equal to or higher than the vapor pressure of the raw material monomer at the temperature in the reaction vessel so that no gas of the raw material monomer is generated in the reaction vessel, and usually at a gauge pressure of about 1.0 to 2.0 MPa. is there.
- the time subjected to continuous bulk polymerization in the first polymerization step is understood as the average residence time of the first reaction vessel 10.
- the average residence time in the first reaction vessel 10 can be set according to the production efficiency of the polymer in the intermediate composition. The shorter the average residence time until reaching the predetermined polymerization rate, the higher the production efficiency. Therefore, the average residence time is preferably short, but is preferably set between 15 minutes and 2 hours and 45 minutes.
- the average residence time in the first reaction tank 10 can be adjusted by changing the supply amount (supply flow rate) of the raw material monomer or the like to the first reaction tank 10 using the pumps 5 and 7.
- the intermediate composition is extracted from the extraction port 11b of the first reaction tank 10 as described above.
- the obtained intermediate composition contains the produced polymer and unreacted raw material monomer, and may further contain an unreacted polymerization initiator, a polymerization initiator decomposition product, and the like.
- the polymerization rate in the intermediate composition is preferably 30 to 50% by weight.
- the polymerization rate in the intermediate composition corresponds to the polymer content in the intermediate composition.
- the second polymerization step is performed in series after the first polymerization step.
- the intermediate composition obtained as described above is extracted from the extraction port 11 b of the first reaction tank 10 and then supplied from the supply port 21 a to the second reaction tank 20 through the connection line 15.
- the intermediate composition is further subjected to continuous bulk polymerization in the second reaction vessel 20.
- the polymerization reaction is advanced to a desired polymerization rate.
- the obtained polymer composition (or polymerization syrup) is continuously extracted from the extraction port 21 b of the second reaction tank 20.
- the second polymerization step will be described with a focus on differences from the first polymerization step, and the same description as the first polymerization step will be applied unless otherwise specified.
- a raw material composition containing a raw material monomer, a polymerization initiator, and a chain transfer agent is supplied to the second reaction vessel.
- the raw material composition supplied to the second reaction tank is also referred to as a raw material composition B.
- the raw material composition containing the raw material monomer, the polymerization initiator and the chain transfer agent is supplied from the polymerization initiator tank 17 to the second reaction tank 20 through the connection line 15 from the supply port 21a or separately.
- a new polymerization initiator is added to the intermediate composition.
- the raw material composition containing the raw material monomer and the polymerization initiator from the polymerization initiator tank 17 is transferred from the pump 19 to the connection line 15 and is separated from the polymerization initiator tank 17. It is also possible to adjust the flow rates of the two pumps to obtain a desired chain transfer agent concentration by merging with a liquid chain transfer agent stored in a tank and sent from a pump different from the pump 19. .
- the temperature of the raw material composition B supplied from the polymerization initiator tank 17 to the second reaction tank 20 is not particularly limited, but it causes the heat balance in the reaction tank to be lost and the polymerization temperature to fluctuate. It is preferable to adjust the temperature appropriately before being supplied to the reaction vessel 20 by a heating / cooling device (not shown).
- the proportion of the polymerization initiator contained in the raw material composition B is preferably 0.002 to 10% by weight.
- a polymer having a lower average molecular weight is produced in the second reaction tank 20 than the polymer obtained in the first reaction tank 10. be able to.
- a polymer having a lower average molecular weight can be produced as the concentration of the chain transfer agent is increased. Therefore, by increasing the supply amount of the chain transfer agent to the second reaction tank 20, the weight obtained in the first reaction tank 10 can be increased. The difference in average molecular weight from the coalescence becomes large, and the molecular weight distribution can be widened.
- [S1] is the concentration (% by weight) of the chain transfer agent in the raw material composition (including the raw material monomer, the polymerization initiator, the chain transfer agent and optionally other components) supplied to the first reaction vessel
- S2] is the concentration of the chain transfer agent relative to the total amount of the raw material composition (including the raw material monomer, the polymerization initiator, the chain transfer agent and optionally other components) supplied to the second reaction tank (wt%) )
- the following formula 1.7 ⁇ [S2] / [S1] The supply amount of the chain transfer agent is adjusted so as to satisfy, preferably the following formula 2.0 ⁇ [S2] / [S1]
- the supply amount of the chain transfer agent is adjusted so as to satisfy the above condition.
- the upper limit of [S2] / [S1] is not particularly limited, but is preferably 100 or less, more preferably 50 or less, further preferably 20 or less, particularly preferably 15 or less, and most preferably 10 or less.
- [S1] is preferably less than 0.2, and more preferably less than 0.14. When [S1] is 0.2 or more, when the strand extruded from the extruder is drawn into a pellet by a pelletizer, the mechanical strength of the strand may be lowered. Therefore, the strand may be cut or the fine powder may increase.
- the lower limit of [S1] is preferably 0.05.
- [S1] When [S1] is less than 0.05, the molecular weight of the polymer obtained in the first reaction tank increases, and the syrup viscosity in the first reaction tank may increase. As a result, in the first reaction tank, it may be difficult to stir uniformly or liquid feeding may be difficult. Moreover, since the syrup viscosity is high, a runaway reaction in the first reaction tank may occur. Moreover, since the average molecular weight of the obtained polymer is high, the load in an extruder may increase. Furthermore, [S2] is expressed by the following equation: 0 ⁇ [S2] ⁇ 1 It is preferable to satisfy. The upper limit of [S2] is preferably 1.
- [S2] exceeds 1, the viscosity of the polymer obtained in the second reaction vessel may be considerably low. As a result, when the strand extruded from the extruder is taken out by a pelletizer and formed into a pellet, the mechanical strength of the strand may be lowered. Therefore, the strand may be cut or the fine powder may increase. [S2] is preferably larger than 0, more preferably 0.2 or more.
- the temperature of the connection line 15 is substantially the same as the temperature in the first reaction vessel 10.
- the viscosity of the intermediate composition in the connection line 15 is prevented from increasing, and the intermediate composition Can be stably supplied to the second reaction vessel 20.
- the temperature in the second reaction vessel is prevented from rising and finally obtained. Quality such as thermal stability of the resin composition can be maintained.
- a jacket is provided as a temperature adjusting means in the connection line 15 and the set temperature of the jacket is adjusted. Can do.
- a temperature-retaining material is provided in place of the jacket to keep the connection line 15 warm so that the temperature of the connection line 15 is equal to the temperature in the first reaction vessel 10. The temperature can be substantially the same.
- the flow rate of the intermediate composition supplied to the second reaction tank 20 is Q1 (cm 3 / min), and the raw material composition (raw material monomer, polymerization initiator and chain transfer agent) supplied to the second reaction tank 20 Q1 and Q2 are expressed by the following formula 1 ⁇ Q1 / Q2 ⁇ 50, where Q2 (cm 3 / min) Adjust pumps 5, 7 and 19 to meet.
- the chain transfer agent is diluted by adjusting the flow rate of the intermediate composition and the raw material composition supplied to the second reaction tank 20, diluting the chain transfer agent and supplying it to the second reaction tank 20.
- [S2] can be stably controlled because the influence on the change of Q1 and / or Q2 is mitigated as compared with the direct supply.
- a methacrylic polymer composition having an intended molecular weight distribution can be stably obtained.
- Q1 / Q2 exceeds 50, in order to produce a low molecular weight polymer, the concentration of the chain transfer agent in the raw material composition supplied to the second reaction tank must be considerably increased. In this case, since a minute change in Q2 greatly affects the molecular weight of the low molecular weight polymer, it is not preferable.
- Q1 / Q2 is less than 1, the polymer produced in the first reaction tank is diluted with the raw material composition supplied to the second reaction tank. As a result, production efficiency decreases.
- the continuous bulk polymerization is preferably performed in a full liquid state. Due to this full liquid state, there is a problem that the gel adheres to the inner wall surface of the reaction vessel and grows, and a problem that the quality of the resin composition finally obtained is deteriorated when this gel is mixed into the reaction mixture. Occurrence can be prevented in advance. Furthermore, this full liquid state can effectively utilize the entire volume of the reaction tank in the reaction space, and thus high production efficiency can be obtained.
- the full liquid state can be realized simply by continuously supplying and extracting the second reaction tank 20 by placing the extraction port 21b of the second reaction tank 20 at the top of the reaction tank.
- the continuous bulk polymerization is preferably carried out in an adiabatic state. Due to this heat insulation state, problems such as the gel adhering to the inner wall surface of the reaction vessel and growing, and the problem that the quality of the resin composition finally obtained when this gel is mixed into the reaction mixture occur. This can be prevented in advance. Furthermore, this adiabatic state can stabilize the polymerization reaction and can provide self-controllability for suppressing the runaway reaction.
- the heat insulation state can be realized by making the temperature inside the second reaction tank 20 and the temperature of the outer wall surface substantially equal. Specifically, the temperature of the outer wall surface of the second reaction tank 20 set for the jacket (temperature adjusting means) 23 and the temperature sensor (temperature detecting means) using the above-described control device (not shown). ) The supply amounts of the intermediate composition and the raw material composition B to the second reaction tank 20 are adjusted so that the temperature in the second reaction tank 20 detected by T matches the operation of the pumps 5, 7 and 19. It can be realized by adjusting. In addition, when the temperature of the outer wall surface of the reaction tank is set too high compared to the temperature in the reaction tank, extra heat may be applied to the reaction tank. It is preferable that the temperature difference between the inside of the reaction tank and the outer wall surface of the reaction tank is as small as possible.
- the temperature of continuous bulk polymerization in the second polymerization step is understood as the temperature in the second reaction vessel 20.
- the second polymerization step is performed at a temperature of 140 to 180 ° C.
- the temperature in the second reaction vessel 20 depends on the polymerization heat. The higher the concentration of the polymerization initiator relative to the total amount of the intermediate composition and the raw material composition B supplied to the second reaction tank 20, the higher the polymerization rate. As a result, the temperature in the second reaction tank 20 is increased. can do.
- the time subjected to continuous bulk polymerization in the second polymerization step is understood as the average residence time of the second reaction vessel 20.
- the average residence time in the second reaction vessel 20 can be set according to the production efficiency of the polymer in the polymer composition. Since the production efficiency improves as the average residence time until the predetermined polymerization rate is reached, the average residence time is preferably shorter. However, if the average residence time is too short, a large amount of friction may occur in the communication pipe between the first reaction tank and the second reaction tank, which may make it difficult to feed the pump. Therefore, the average residence time is preferably set between 15 minutes and 2 hours and 45 minutes.
- the ratio of the average residence time in the second reaction tank 20 to the average residence time in the first reaction tank 10 is preferably 9/1 to 1/9, more preferably 8/2 to 2/8. .
- the average residence time in the second polymerization step may be equivalent to the average residence time in the first polymerization step, but is preferably different from that.
- the average residence time in the second reaction tank 20 is adjusted by changing the supply amount (supply flow rate) of the intermediate composition and the raw material composition B to the second reaction tank 20 using the pumps 5, 7 and 19. it can.
- the total ( ⁇ 1 + ⁇ 2) of the average residence time ⁇ 1 in the first reaction tank 10 and the average residence time ⁇ 2 in the second reaction tank 20 is preferably 180 minutes or less. A coalescence composition can be obtained with good productivity.
- the polymer composition is extracted from the extraction port 21 b of the second reaction tank 20.
- the obtained polymer composition contains the produced polymer, and may further contain unreacted raw material monomers, unreacted polymerization initiator, polymerization initiator decomposition product, and the like.
- the polymerization rate (x) in the methacrylic polymer composition is preferably 40 to 60% by weight.
- the polymerization rate in a polymer composition is equivalent to the polymer content rate in a polymer composition.
- the higher the polymerization rate the higher the productivity of the polymer, but the viscosities of the intermediate composition and the polymer composition increase, and a large stirring power is required.
- the polymerization rate is increased, the amount of heat generated by polymerization increases, and local or rapid cooling of the reaction system tends to occur during heat removal for keeping the temperature in the polymerization reaction of the reaction system constant.
- the adhesion and growth of the gel on the inner wall surface of the reaction tank become more remarkable, and problems such as gelled products being mixed as impurities in the resulting polymer composition may occur.
- the lower the polymerization rate the lower the polymer productivity and the greater the burden for recovering unreacted raw material monomers. Therefore, it is preferable to set an appropriate polymerization rate as a target or a guide.
- the difference between the temperature of the continuous bulk polymerization in the second polymerization step and the temperature of the continuous bulk polymerization in the first polymerization step is related to the polymerization rate in the second polymerization step.
- the greater the temperature difference the greater the amount of polymer obtained in the second polymerization step.
- the ratio of the polymer obtained in the first polymerization step and the polymer obtained in the second polymerization step can be controlled by the temperature in each polymerization step.
- the first polymerization step is performed at 120 to 160 ° C., preferably 120 to 150 ° C.
- the second polymerization step is performed at 140 to 180 ° C.
- the second polymerization step is performed.
- the polymer obtained in the second polymerization step By setting the difference (T2-T1) between the temperature T2 of continuous bulk polymerization in T and the temperature T1 of continuous bulk polymerization in the first polymerization step to 20 ° C. or more and 60 ° C. or less, the polymer obtained in the second polymerization step The average molecular weight is lower than the average molecular weight of the polymer obtained in the first polymerization step, and the polymer composition can be obtained with good productivity while controlling the proportion of the low molecular weight according to the temperature of each polymerization step.
- the temperature of the first reaction tank is lower than 120 ° C., the polymerization rate obtained in the first reaction tank becomes low, and as a result, productivity is impaired.
- the temperature of the first reaction tank is higher than 160 ° C.
- the ratio of the high molecular weight polymer increases, and thus the target ratio of the low molecular weight polymer cannot be obtained.
- the temperature of the second reaction tank is lower than 140 ° C.
- the polymerization rate obtained in the second reaction tank is lowered, and as a result, productivity is impaired.
- the temperature of the second reaction vessel is higher than 180 ° C., depolymerization occurs, so that the target low molecular weight polymer ratio and the target low molecular weight polymer molecular weight cannot be achieved.
- many dimers which are a by-product will be produced
- T2-T1 When T2-T1 is lower than 20 ° C., the ratio of the low molecular weight polymer is too low, and the average molecular weight of the resulting polymer is high. As a result, the load on the extruder increases. When T2-T1 is higher than 60 ° C., the proportion of the low molecular weight polymer increases. As a result, when the strand coming out of the extruder is taken up by a pelletizer and formed into a pellet, the strand has a low mechanical strength, so the strand breaks or the fine powder increases.
- How to set the polymerization reaction conditions in each of the first polymerization step and the second polymerization step depends on the polymer to be produced, the raw material monomers to be used, the polymerization initiator and the chain transfer agent, the desired molecular weight distribution, It may vary depending on the proportion of low molecular weight, heat resistance, thermal stability and production efficiency.
- the polymer composition (polymerization syrup) extracted from the extraction port 21b of the second reaction tank 20 may contain unreacted raw material monomers, a polymerization initiator, and the like in addition to the produced polymer.
- this polymer composition does not limit this embodiment, it is preferable to devolatilize etc. and to isolate
- the polymer composition is extracted and transferred to the preheater 31 through the extraction line 25.
- the polymer composition is given a part or all of the amount of heat necessary for volatilization of volatile components mainly composed of unreacted raw material monomers.
- the polymer composition is then transferred to a devolatilizing extruder 33 via a pressure regulating valve (not shown), where volatile components are at least partially removed in the devolatilizing extruder, and the remaining extrudate is It is taken out by a pelletizer, formed into a pellet, and taken out from the take-out line 35.
- the resin composition containing a methacrylic ester polymer is manufactured in the form of pellets.
- JP-B-4-48802 As the method for transferring the polymer composition, the method described in JP-B-4-48802 is suitable.
- methods using a devolatilizing extruder include, for example, JP-A-3-49925, JP-B-51-29914, JP-B-52-17555, JP-B-1-53682, JP-A-62.
- the method described in JP-A-89710 is suitable.
- releasing agents 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 composition or extrudate and included in the resin composition.
- Volatile components removed by the devolatilizing extruder 33 are mainly composed of unreacted raw material monomers, impurities originally contained in the raw material monomers, additives used as necessary, and volatile by-products generated in the polymerization process. Impurities such as products, oligomers such as dimers and trimers, polymerization initiator decomposition products, and the like are included. Generally, an increase in the amount of impurities is not preferable because the resulting resin composition is colored.
- the volatile components removed by the devolatilizing extruder 33 (mainly composed of unreacted raw material monomers and including impurities as described above) are passed through a monomer recovery tower (not shown), and the monomer recovery tower
- the unreacted raw material monomer can be recovered with high purity, and is suitable as a raw material monomer for polymerization.
- Can be reused for example, in the monomer recovery tower, unreacted raw material monomer is recovered with high purity as a distillate from the top of the monomer recovery tower by continuous distillation, stored in the recovery tank 37, and then transferred to the raw material monomer tank 1. May be recycled, or may be transferred to the raw material monomer tank 1 for recycling without being stored in the recovery tank 37.
- impurities removed in the monomer recovery tower can be discarded as waste.
- the recovered raw material monomer is added with a polymerization inhibitor in the recovery tank 37 or the raw material monomer tank 1, for example, 2 to It is preferably present at a rate of 8 ppm by weight, and more preferably, the oxygen concentration in the gas phase part of the recovery tank 37 and the raw material monomer tank 1 is set to 2 to 8% by volume. Further, when it is desired to store in the recovery tank 37 for a long period of time, it is desirable to store at a low temperature of, for example, 0 to 5 ° C.
- the method for producing the polymer composition of the present invention has been described in detail through the embodiment of the present invention.
- the polymerization reaction conditions in the first polymerization process and the second polymerization process Specifically, temperature, time (average residence time), amount of chain transfer agent (ratio of chain transfer agent to raw material composition), amount of polymerization initiator (ratio of polymerization initiator to raw material monomer), etc. individually Can be set.
- the first polymerization step is performed at 120 to 160 ° C. by adding a chain transfer agent
- the second polymerization step is performed at 140 to 180 ° C.
- the ratio of the low molecular weight polymer and the high molecular weight polymer contained in the finally obtained polymer composition can be controlled. Therefore, a polymer composition having a sufficiently wide molecular weight distribution can be produced more efficiently.
- the molecular weight distribution is controlled by the amount of the chain transfer agent supplied to the first and second reaction tanks, but also the polymerization temperature in the first and second reaction tanks is changed. The proportion of the molecular weight body can be changed, and the range in which the molecular weight distribution can be controlled can be widened.
- the present invention is not limited to the above-described embodiment, and various modifications are possible.
- the polymerization may be performed in three or more stages in series using three or more reaction vessels.
- the method for producing the polymer composition is continuously carried out, but may be carried out in a batch manner.
- the polymer composition obtained by the method of the present invention can be suitably used as a material for a molded body.
- a molded body produced using the polymer composition obtained by the method of the present invention has an advantage of having high solvent resistance and molding fluidity.
- the obtained molded body is preferably used as a vehicle member such as a tail lamp cover, a head lamp cover, a visor, and a meter panel.
- Example 1 In this example, generally, according to the embodiment described above with reference to FIG. 1, continuous polymerization was performed in two stages to produce a polymer composition in the form of pellets (resin composition). More details are as follows.
- a raw material monomer mixed solution 1 was prepared. 99.840 parts by mass of methyl methacrylate and 0.160 parts by mass of t-amylperoxy-2-ethylhexanoate as a polymerization initiator were mixed to prepare a polymerization initiator mixed solution 1.
- the apparatus shown in FIG. 1 was used.
- a fully mixed reaction tank with a capacity of 13 L was used as the first reaction tank 10
- a fully mixed reaction tank with a capacity of 6 L was used as the second reaction tank 20.
- the raw material monomer mixed liquid 1, the polymerization initiator mixed liquid 1 and the polymerization initiator mixed liquid 2 prepared above were placed in the raw material monomer tank 1, the polymerization initiator tank 3 and the polymerization initiator tank 17, respectively.
- the raw material monomer mixed solution 1 and the polymerization initiator mixed solution 1 are respectively supplied from the raw material monomer tank 1 and the polymerization initiator tank 3 to the first reaction tank 10 through the raw material supply line 9 and the supply port located therebelow. It supplied continuously from 11a.
- Supplying the raw material monomer mixture 1 and the polymerization initiator mixture 1 to the first reaction tank 10 has a flow rate ratio of 17.10: 1.00, and the average residence time ( ⁇ 1 in the first reaction tank 10). ) was 63.6 minutes.
- the temperature (T1) in the first reaction tank 10 is 120 ° C.
- the temperature of the jacket 13 surrounding the outer wall surface of the first reaction tank 10 is 120 ° C.
- Polymerization was performed. This continuous polymerization was carried out in a state where the first reaction vessel 10 was filled with the reaction mixture (mixed solution) and substantially no gas phase was present (full solution state).
- the reaction mixture in the first reaction tank 10 was continuously extracted as an intermediate composition from the extraction port 11 b located at the top of the first reaction tank 10.
- the extracted intermediate composition was continuously supplied to the second reaction tank 20 through the connection line 15 from the supply port 21a located therebelow.
- the connecting line 15 is provided with a jacket that surrounds the outer wall surface. Using this jacket, the intermediate composition passing through the inside of the connecting line 15 has a temperature equal to the temperature in the first reaction tank (120 in this embodiment). C.) was maintained.
- the polymerization initiator mixed liquid 2 was continuously supplied from the polymerization initiator tank 17 to the second reaction tank 20 through another supply port 21c.
- the supply of the intermediate composition and the polymerization initiator mixed liquid 2 to the second reaction tank 20 was performed such that the flow rate ratio thereof was 9.54: 1.00.
- the average residence time ( ⁇ 2) in the second reaction tank 20 was 26.0 minutes.
- the temperature (T2) in the second reaction tank 20 is 175 ° C.
- the temperature of the jacket 23 surrounding the outer wall surface of the second reaction tank 20 is set to 175 ° C., and is continuously in an adiabatic state without substantial heat entry and exit.
- Polymerization was performed. This continuous polymerization was performed in a state where the second reaction vessel 20 was filled with the reaction mixture (mixed solution) and substantially no gas phase was present (full solution state).
- the concentration (wt%) of the chain transfer agent in the total amount of the raw material monomer mixed solution 1 and the polymerization initiator mixed solution 1 supplied to the first reaction tank and [S2] are supplied to the second reaction tank.
- [S1] and [S2] are calculated from the flow rate ratio with the concentration (wt%) of the chain transfer agent newly supplied to the second reaction tank in the total amount of the polymerization initiator mixture 2 and the intermediate composition. And 0.131% by weight and 0.286% by weight, respectively.
- the reaction mixture in the second reaction tank 20 was continuously extracted as a polymer composition from an extraction port 21b located at the top of the second reaction tank 20.
- the polymer composition thus obtained is extracted through a drawing line 25, heated to 200 ° C. by a preheater 31, and volatile such as unreacted raw material monomers at 240 ° C. by a vented devolatilizing extruder 33.
- the components were removed, and the devolatilized resin composition was extruded in a molten state. After cooling with water, the resin composition was cut and taken out from the take-out line 35 as pellets. Thereby, the resin composition was manufactured in the form of pellets.
- the polymerization rate (x: wt%) is determined from the supply weight per unit time of the raw material monomer mixture 1, the polymerization initiator mixture 1 and the polymerization initiator mixture 2 and the production (removal) weight of the pellets per unit time. It was.
- the molecular weight distribution of the obtained resin composition was measured by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- To create a GPC calibration curve use a methacrylic resin manufactured by Showa Denko KK, which has a narrow molecular weight distribution and a known molecular weight, as a standard reagent, create a calibration curve from the elution time and molecular weight, and calculate the molecular weight of each resin composition. Distribution was measured. Specifically, 40 mg of the obtained pellet-shaped resin composition was dissolved in 20 ml of tetrahydrofuran (THF) solvent to prepare a measurement sample.
- THF tetrahydrofuran
- A, B, and C are constants
- x is a logarithm of molecular weight
- y is a value obtained by differentiating a concentration fraction by a logarithmic value of molecular weight.
- A, B, C, D, E, and F are constants
- x is a logarithm of molecular weight
- y is a value obtained by differentiating a concentration fraction with a logarithmic value of molecular weight.
- Example 2 the resin composition was produced in the form of pellets in the same manner as in Example 1 except for the following points.
- a raw material monomer mixed solution 1 was prepared with the same composition as in Example 1. 99.823 parts by mass of methyl methacrylate and 0.177 parts by mass of t-amylperoxy-2-ethylhexanoate as a polymerization initiator were mixed to prepare a polymerization initiator mixed solution 1.
- a polymerization initiator mixed solution 2 was prepared.
- the temperature (T1) in the first reaction tank 10 is 130 ° C.
- the temperature of the jacket 13 surrounding the outer wall surface of the first reaction tank 10 is 130 ° C.
- the intermediate composition passing through the connection line 15 is 130 ° C. The temperature was adjusted to be maintained.
- the polymerization rate (x: wt%) was determined in the same manner as in Example 1. Further, in the same manner as in Example 1, GPC was measured for the obtained resin composition, a molecular weight distribution curve was calculated, and fitting was performed using the sum of two normal distribution functions. The obtained molecular weight distribution curves are shown in FIGS. 2 (b) and (f). Moreover, the low molecular weight body area ratio and molecular weight distribution Mw / Mn were calculated
- Example 3 the resin composition was produced in the form of pellets in the same manner as in Example 1 except for the following points.
- a raw material monomer mixed solution 1 was prepared with the same composition as in Example 1.
- a polymerization initiator mixed solution 1 was prepared by mixing 99.838 parts by mass of methyl methacrylate and 0.162 parts by mass of t-amylperoxy-2-ethylhexanoate as a polymerization initiator.
- a polymerization initiator mixed solution 2 was prepared.
- the temperature (T1) in the first reaction tank 10 is 150 ° C.
- the temperature of the jacket 13 surrounding the outer wall surface of the first reaction tank 10 is 150 ° C.
- the intermediate composition passing through the connection line 15 is 150 ° C. The temperature was adjusted to be maintained.
- the polymerization rate (x: wt%) was determined in the same manner as in Example 1. Further, in the same manner as in Example 1, GPC was measured for the obtained resin composition, a molecular weight distribution curve was calculated, and fitting was performed using the sum of two normal distribution functions. The obtained molecular weight distribution curves are shown in FIGS. 2 (c) and (f). Moreover, the low molecular weight body area ratio and molecular weight distribution Mw / Mn were calculated
- Example 4 the resin composition was produced in the form of pellets in the same manner as in Example 1 except for the following points.
- a raw material monomer mixed solution 1 was prepared.
- 99.840 parts by mass of methyl methacrylate and 0.160 parts by mass of t-amylperoxy-2-ethylhexanoate as a polymerization initiator were mixed to prepare a polymerization initiator mixed solution 1.
- a polymerization initiator mixed solution 2 was prepared.
- Supplying the raw material monomer mixture 1 and the polymerization initiator mixture 1 to the first reaction tank 10 has a flow rate ratio of 17.10: 1.00, and the average residence time ( ⁇ 1 in the first reaction tank 10). ) was 63.6 minutes.
- the temperature (T1) in the first reaction tank 10 is 140 ° C.
- the temperature of the jacket 13 that surrounds the outer wall surface of the first reaction tank 10 is 140 ° C.
- it is continuously insulated in a heat-insulating state substantially free of heat.
- Polymerization was performed. This continuous polymerization was carried out in a state where the first reaction vessel 10 was filled with the reaction mixture (mixed solution) and substantially no gas phase was present (full solution state).
- the reaction mixture in the first reaction tank 10 was continuously extracted as an intermediate composition from the extraction port 11 b located at the top of the first reaction tank 10.
- the extracted intermediate composition was continuously supplied to the second reaction tank 20 through the connection line 15 from the supply port 21a located therebelow.
- the connection line 15 is provided with a jacket that surrounds the outer wall surface, and this jacket was used to adjust the intermediate composition passing through the connection line 15 to maintain a temperature of 140 ° C.
- the polymerization initiator mixed liquid 2 was continuously supplied from the polymerization initiator tank 17 to the second reaction tank 20 through another supply port 21c.
- the supply of the intermediate composition and the polymerization initiator mixed liquid 2 to the second reaction tank 20 was performed such that the flow rate ratio thereof was 9.54: 1.00.
- the average residence time ( ⁇ 2) in the second reaction tank 20 was 26.0 minutes.
- the temperature (T2) in the second reaction tank 20 is 175 ° C.
- the temperature of the jacket 23 surrounding the outer wall surface of the second reaction tank 20 is set to 175 ° C., and is continuously in an adiabatic state without substantial heat entry and exit.
- Polymerization was performed. This continuous polymerization was performed in a state where the second reaction vessel 20 was filled with the reaction mixture (mixed solution) and substantially no gas phase was present (full solution state).
- the concentration (wt%) of the chain transfer agent in the total amount of the raw material monomer mixed solution 1 and the polymerization initiator mixed solution 1 supplied to the first reaction tank and [S2] are supplied to the second reaction tank.
- [S1] and [S2] are calculated from the flow rate ratio with the concentration (wt%) of the chain transfer agent newly supplied to the second reaction tank in the total amount of the polymerization initiator mixture 2 and the intermediate composition. And 0.131% by weight and 0.286% by weight, respectively.
- the polymerization rate (x: wt%) was determined in the same manner as in Example 1. Further, in the same manner as in Example 1, GPC was measured for the obtained resin composition, a molecular weight distribution curve was calculated, and fitting was performed using the sum of two normal distribution functions. The obtained molecular weight distribution curves are shown in FIGS. 3 (a) and 3 (c). Moreover, the low molecular weight body area ratio and molecular weight distribution Mw / Mn were calculated
- Example 5 a resin composition was produced in the form of pellets in the same manner as in Example 4 except for the following points.
- a raw material monomer mixed solution 1 was prepared.
- a polymerization initiator mixed solution 1 was prepared by mixing 99.860 parts by weight of methyl methacrylate and 0.140 parts by weight of t-amylperoxy-2-ethylhexanoate as a polymerization initiator.
- the concentration (wt%) of the chain transfer agent in the total amount of the raw material monomer mixed solution 1 and the polymerization initiator mixed solution 1 supplied to the first reaction tank and [S2] are supplied to the second reaction tank. [S1] and [S2] are calculated from the flow rate ratio with the concentration (wt%) of the chain transfer agent newly supplied to the second reaction tank in the total amount of the polymerization initiator mixture 2 and the intermediate composition. And 0.089 wt% and 0.286 wt%, respectively.
- the polymerization rate (x: wt%) was determined in the same manner as in Example 1. Further, in the same manner as in Example 1, GPC was measured for the obtained resin composition, a molecular weight distribution curve was calculated, and fitting was performed using the sum of two normal distribution functions. The obtained molecular weight distribution curves are shown in FIGS. 3 (b) and 3 (c). Moreover, the low molecular weight body area ratio and molecular weight distribution Mw / Mn were calculated
- Example 6 the resin composition was produced in the form of pellets in the same manner as in Example 1 except for the following points.
- a raw material monomer mixed solution 1 was prepared.
- a polymerization initiator mixed solution 1 was prepared by mixing 99.747 parts by mass of methyl methacrylate and 0.253 parts by mass of t-amylperoxy-2-ethylhexanoate as a polymerization initiator.
- Supplying the raw material monomer mixture 1 and the polymerization initiator mixture 1 to the first reaction tank 10 has a flow rate ratio of 17.47: 1.00, and the average residence time ( ⁇ 1 in the first reaction tank 10). ) was 36.8 minutes.
- the temperature (T1) in the first reaction tank 10 is 140 ° C.
- the temperature of the jacket 13 that surrounds the outer wall surface of the first reaction tank 10 is 140 ° C.
- it is continuously insulated in a heat-insulating state substantially free of heat.
- Polymerization was performed. This continuous polymerization was carried out in a state where the first reaction vessel 10 was filled with the reaction mixture (mixed solution) and substantially no gas phase was present (full solution state).
- the reaction mixture in the first reaction tank 10 was continuously extracted as an intermediate composition from the extraction port 11 b located at the top of the first reaction tank 10.
- the extracted intermediate composition was continuously supplied to the second reaction tank 20 through the connection line 15 from the supply port 21a located therebelow.
- the connection line 15 is provided with a jacket that surrounds the outer wall surface, and this jacket was used to adjust the intermediate composition passing through the connection line 15 to maintain a temperature of 140 ° C.
- the polymerization initiator mixed liquid 2 was continuously supplied from the polymerization initiator tank 17 to the second reaction tank 20 through another supply port 21c.
- the supply of the intermediate composition and the polymerization initiator mixed solution 2 to the second reaction tank 20 was performed so that the flow rate ratio thereof was 12.08: 1.00.
- the average residence time ( ⁇ 2) in the second reaction tank 20 was 15.4 minutes.
- the temperature (T2) in the second reaction tank 20 is 175 ° C.
- the temperature of the jacket 23 surrounding the outer wall surface of the second reaction tank 20 is set to 175 ° C., and is continuously in an adiabatic state without substantial heat entry and exit.
- Polymerization was performed. This continuous polymerization was performed in a state where the second reaction vessel 20 was filled with the reaction mixture (mixed solution) and substantially no gas phase was present (full solution state).
- the concentration (wt%) of the chain transfer agent in the total amount of the raw material monomer mixed solution 1 and the polymerization initiator mixed solution 1 supplied to the first reaction tank and [S2] are supplied to the second reaction tank. [S1] and [S2] are calculated from the flow rate ratio with the concentration (wt%) of the chain transfer agent newly supplied to the second reaction tank in the total amount of the polymerization initiator mixture 2 and the intermediate composition. , 0.088 wt% and 0.240 wt%, respectively.
- Q1 is the flow rate of the intermediate composition flowing into the first reaction tank or the second reaction tank and Q2 is the flow rate of the polymerization initiator 2 supplied to the second reaction tank
- Q1 348.96 cm 3 / min.
- Q2 28.89 cm 3 / min.
- the polymerization rate (x: wt%) was determined in the same manner as in Example 1. Further, in the same manner as in Example 1, GPC was measured for the obtained resin composition, a molecular weight distribution curve was calculated, and fitting was performed using two normal distribution functions. The obtained molecular weight distribution curves are shown in FIGS. 4 (a) and (c). Moreover, the low molecular weight body area ratio and molecular weight distribution Mw / Mn were calculated
- Example 7 a resin composition was produced in the form of pellets in the same manner as in Example 6 except for the following points.
- a raw material monomer mixed solution 1 was prepared.
- a polymerization initiator mixed solution 1 was prepared by mixing 99.747 parts by mass of methyl methacrylate and 0.253 parts by mass of t-amylperoxy-2-ethylhexanoate as a polymerization initiator.
- the polymerization rate (x: wt%) was determined in the same manner as in Example 1. Further, in the same manner as in Example 1, GPC was measured for the obtained resin composition, a molecular weight distribution curve was calculated, and fitting was performed using two normal distribution functions. The obtained molecular weight distribution curves are shown in FIGS. 4 (b) and (c). Moreover, the low molecular weight body area ratio and molecular weight distribution Mw / Mn were calculated
- Comparative Example 1 In this comparative example, as shown below, by supplying a polymerization inhibitor to the second reaction tank 20 to stop the polymerization, a resin composition corresponding to the case where the polymerization was performed in one stage was obtained, The molecular weight distribution was confirmed. Mixing 98.956 parts by weight of methyl methacrylate and 0.935 parts by weight of methyl acrylate, adding 0.009 parts by weight of n-octyl mercaptan as a chain transfer agent and 0.100 parts by weight of stearyl alcohol as a release agent, A raw material monomer mixed solution 1 was prepared.
- a polymerization initiator mixed solution 1 was prepared by mixing 99.816 parts by mass of methyl methacrylate and 0.184 parts by mass of 1,1-di (t-butylperoxy) cyclohexane as a polymerization initiator.
- a polymerization inhibitor mixed solution was prepared by mixing 99.99995 parts by mass of methyl methacrylate and 0.00005 parts by mass of 2,6-bis (tert-butyl) -4-methylphenol as a polymerization inhibitor.
- the apparatus shown in FIG. 1 was used.
- a fully mixed reaction tank with a capacity of 13 L was used as the first reaction tank 10
- a fully mixed reaction tank with a capacity of 6 L was used as the second reaction tank 20.
- the raw material monomer mixed liquid 1, the polymerization initiator mixed liquid 1 and the polymerization inhibitor mixed liquid prepared above were put into the raw material monomer tank 1, the polymerization initiator tank 3 and the polymerization initiator tank 17, respectively.
- the raw material monomer mixed solution 1 and the polymerization initiator mixed solution 1 are respectively supplied from the raw material monomer tank 1 and the polymerization initiator tank 3 to the first reaction tank 10 through the raw material supply line 9 and the supply port located therebelow. It supplied continuously from 11a.
- Supplying the raw material monomer mixture 1 and the polymerization initiator mixture 1 to the first reaction tank 10 has a flow rate ratio of 17.10: 1.00, and the average residence time ( ⁇ 1 in the first reaction tank 10). ) was 63.6 minutes.
- the temperature (T1) in the first reaction tank 10 is 175 ° C.
- the temperature of the jacket 13 surrounding the outer wall surface of the first reaction tank 10 is 175 ° C.
- Polymerization was performed. This continuous polymerization was carried out in a state where the first reaction vessel 10 was filled with the reaction mixture (mixed solution) and substantially no gas phase was present (full solution state).
- the reaction mixture in the first reaction tank 10 was continuously extracted as an intermediate composition from the extraction port 11 b located at the top of the first reaction tank 10.
- the extracted intermediate composition was continuously supplied to the second reaction tank 20 through the connection line 15 from the supply port 21a located therebelow.
- the connection line 15 is provided with a jacket surrounding the outer wall surface, and the intermediate composition passing through the inside of the connection line 15 was adjusted so as to maintain a temperature of 175 ° C. by using this jacket.
- the polymerization inhibitor mixed solution was continuously supplied from the polymerization initiator tank 17 to the second reaction tank 20 through another supply port 21c.
- the supply of the intermediate composition and the polymerization inhibitor mixed solution to the second reaction tank 20 was performed so that the flow rate ratio thereof was 9.54: 1.00.
- the average residence time ( ⁇ 2) in the second reaction tank 20 was 26.0 minutes.
- the temperature (T2) in the second reaction tank 20 is 175 ° C.
- the temperature of the jacket 23 surrounding the outer wall surface of the second reaction tank 20 is set to 175 ° C., and is continuously in an adiabatic state without substantial heat entry and exit.
- Polymerization was performed. This continuous polymerization was performed in a state where the second reaction vessel 20 was filled with the reaction mixture (mixed solution) and substantially no gas phase was present (full solution state).
- [S1] is the chain transfer agent concentration (wt%) in the total amount of the raw material monomer mixed solution 1 and the polymerization initiator mixed solution 1 supplied to the first reaction tank, and [S1] is calculated from the flow rate ratio to be 0. 094% by weight.
- Q1 is the flow rate of the intermediate composition flowing into the second reaction vessel from the first reaction vessel
- Q2 is the flow rate of the polymerization inhibitor mixed solution supplied to the second reaction vessel
- Q1 201.85 cm 3 / Min
- Q2 21.15 cm 3 / min.
- the reaction mixture in the second reaction tank 20 was continuously extracted as a polymer composition from an extraction port 21b located at the top of the second reaction tank 20.
- the polymer composition thus obtained is extracted through a drawing line 25, heated to 200 ° C. by a preheater 31, and volatile such as unreacted raw material monomers at 240 ° C. by a vented devolatilizing extruder 33.
- the components were removed, and the devolatilized resin composition was extruded in a molten state. After cooling with water, the resin composition was cut and taken out from the take-out line 35 as pellets. Thereby, the resin composition was manufactured in the form of pellets.
- the polymerization rate (x: wt%) was determined in the same manner as in Example 1. Further, in the same manner as in Example 1, GPC was measured for the obtained resin composition, a molecular weight distribution curve was calculated, and fitting was performed with one normal distribution function. The obtained molecular weight distribution curves are shown in FIGS. 2 (d) and (f). Moreover, the low molecular weight body area ratio and molecular weight distribution Mw / Mn were calculated
- Comparative Example 2 the resin composition was produced in the form of pellets in the same manner as in Example 6 except for the following points.
- a raw material monomer mixed solution 1 was prepared.
- a polymerization initiator mixed solution 1 was prepared by mixing 99.719 parts by mass of methyl methacrylate and 0.281 parts by mass of t-amylperoxy-2-ethylhexanoate as a polymerization initiator.
- the concentration (wt%) of the chain transfer agent in the total amount of the raw material monomer mixed solution 1 and the polymerization initiator mixed solution 1 supplied to the first reaction tank and [S2] are supplied to the second reaction tank. [S1] and [S2] are calculated from the flow rate ratio with the concentration (wt%) of the chain transfer agent newly supplied to the second reaction tank in the total amount of the polymerization initiator mixture 2 and the intermediate composition. And 0.125 wt% and 0.080 wt%, respectively.
- Q1 is the flow rate of the intermediate composition flowing into the second reaction vessel from the first reaction vessel
- Q2 is the flow rate of the polymerization initiator mixed solution 2 supplied to the second reaction vessel
- Q1 348.96 cm 3 / Min
- Q2 28.89 cm 3 / min.
- the polymerization rate (x: wt%) was determined in the same manner as in Example 1. Further, in the same manner as in Example 1, GPC was measured for the obtained resin composition, a molecular weight distribution curve was calculated, and fitting was performed with one normal distribution function. The obtained molecular weight distribution curve is shown in FIG. Moreover, the low molecular weight body area ratio and molecular weight distribution Mw / Mn were calculated
- FIGS. 2D to 2F show that the molecular weight distribution curves of the resin compositions obtained in Comparative Examples 1 and 2 all show a unimodal distribution. Therefore, it can be seen that in Comparative Example 1 in which the polymerization inhibitor was supplied to the second reaction tank 20 and polymerization was performed in one stage, it was not possible to produce polymers having different average molecular weights.
- the temperature T2 in the second reaction tank is fixed at 175 ° C.
- the temperature T1 in the first reaction tank is changed to change the GPC.
- the area ratio of the low molecular weight component in the molecular weight distribution curve can be changed, and therefore the content of the low molecular weight component in the resin composition can be changed. Specifically, the area ratio of the low molecular weight component decreased as T1 increased.
- the molecular weight of the high molecular weight body can be increased by fixing the value of [S2] and decreasing the value of [S1].
- the distribution can be expanded. As understood from Table 1 and FIGS.
- the molecular weight of the low molecular weight substance can be decreased by fixing the value of [S1] and increasing the value of [S2].
- the distribution can be expanded. From these facts, it can be seen that the molecular weight distribution depends on the balance of the [S1] value and the [S2] value.
- a mixture of a low molecular weight polymer and a high molecular weight polymer can be prepared easily and continuously.
- a methacrylic polymer composition having a broad molecular weight distribution and a controlled proportion of low molecular weight polymer and high molecular weight polymer can be produced with high productivity.
- the methacrylic polymer composition obtained by the method of the present invention can be suitably used as a material for a molded body.
- Raw material monomer tank (Source of raw material monomer and, optionally, chain transfer agent) 3 Polymerization initiator tank (Polymerization initiator and, optionally, raw monomer and chain transfer agent supply source) 5 Pump 7 Pump 9 Raw material supply line 10 First reaction tank 11a Supply port 11b Extraction port 11c Another supply port 13 Jacket (temperature control means) 14 Stirrer 15 Connection line 17 Polymerization initiator tank (Supply source of new raw material monomer, polymerization initiator and chain transfer agent) 19 Pump 20 Second reaction tank 21a Supply port 21b Extraction port 21c Another supply port 23 Jacket (temperature control means) 24 Stirrer 25 Extraction line 31 Preheater 33 Devolatilizing extruder 35 Extraction line 37 Recovery tank T Temperature sensor (temperature detection means)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
溶液重合の場合においては一般に、溶媒により重合体の耐熱分解性が低下したり、溶媒およびモノマー回収の方法が煩雑になったりする問題が生じる。
塊状重合の場合、反応混合物の粘度が高くなるため、反応制御が難しい。溶媒を含まない、塊状重合での2段重合において反応制御を可能にした方法として、重合率1~50%まで重合した後、連鎖移動剤を追添加して重合率60%以上に重合する方法が公知である(特許文献4)。しかしながら、この手法では1段目の重合条件は130℃2時間であるが、2段目の重合条件は60℃10時間である。この方法では2段目において1段目より温和な重合条件で再重合を行っている。そのため、この方法は所要時間が長く生産性は十分でない。
[1] メタクリル酸メチルを50重量%以上含有する原料モノマーA、重合開始剤Aおよび連鎖移動剤Aを含む原料組成物Aを第1の完全混合型反応槽の供給口より供給し、第1の完全混合型反応槽において原料組成物Aを連続塊状重合に付し、得られた中間組成物を第1の完全混合型反応槽の抜き出し口より抜き出す第1の重合工程と、
メタクリル酸メチルを50重量%以上含有する原料モノマーB、重合開始剤Bおよび連鎖移動剤Bを含む原料組成物Bならびに第1の重合工程で抜き出された中間組成物を第2の完全混合型反応槽の供給口より供給し、第2の完全混合型反応槽において原料組成物Bおよび中間組成物を更に連続塊状重合に付し、得られたメタクリル系重合体組成物を第2の完全混合型反応槽の抜き出し口より抜き出す第2の重合工程と
を含み、下式(I)、(II)、(III)、(IV)および(V)
120≦T1≦160 (I)
140≦T2≦180 (II)
20≦T2−T1≦60 (III)
1.7≦[S2]/[S1] (IV)
1≦Q1/Q2≦50 (V)
(T1は第1の重合工程における第1の完全混合型反応槽内の温度(℃)、T2は第2の重合工程における第2の完全混合型反応槽内の温度(℃)、[S1]は第1の完全混合型反応槽に供給される原料組成物A中の連鎖移動剤Aの濃度(重量%)、[S2]は第2の完全混合型反応槽に供給される原料組成物Bおよび中間組成物の総量に対する連鎖移動剤Bの濃度(重量%)、Q1は第2の完全混合型反応槽に供給される中間組成物の流量(cm3/分)、Q2は第2の完全混合型反応槽に供給される原料組成物Bの流量(cm3/分))
を満たすメタクリル系重合体組成物の製造方法。
[2] さらに、下式(VI)および(VII)
40≦x≦60 (VI)
θ1+θ2≦180 (VII)
(xは、第2の完全混合型反応槽の抜き出し口より抜き出されるメタクリル系重合体組成物における重合率(重量%)、θ1は第1の重合工程における第1の完全混合型反応槽の平均滞留時間(分)、θ2は第2の重合工程における第2の完全混合型反応槽の平均滞留時間(分))
を満たす前記[1]に記載のメタクリル系重合体組成物の製造方法。
[3] 第1および第2の完全混合型反応槽の抜き出し口は、各反応槽の頂部に位置する前記[1]または[2]に記載の方法。
[4] 第1の重合工程および第2の重合工程における連続塊状重合が断熱状態で行われる前記[1]~[3]のいずれかに記載の方法。
[5] 前記[1]~[4]のいずれかに記載の方法により製造されるメタクリル系重合体組成物から得られる成形体。
これら撹拌機は、任意の適切な撹拌翼を備えていてよく、例えば、ミグ(MIG)翼、マックスブレンド翼(登録商標、住友重機械工業株式会社製)、パドル翼、ダブルヘリカルリボン翼、フルゾーン翼(登録商標、株式会社神鋼環境ソリューション製)などを備えていてよい。反応槽内での撹拌効果を増大させるためには、反応槽内にバッフルを取り付けることが望ましい。しかし、本実施形態はこれに限定されず、反応槽内を実質的に完全混合状態とし得る限り、撹拌機14および24に代えて任意の適切な構成を有し得る。
また、ジャケット13および23の温度や圧力は、熱媒排出路上に設けられた温度センサ(図示せず)などのセンサによって検知される。温度センサなどのセンサの配置箇所については、特に限定されず、例えば、熱媒供給路上や、ジャケット13および23内であってもよい。なお、接続ライン15にジャケットを備える場合、接続ライン15のジャケットは、ジャケット13および23と同様の構成を有してもよい。
上記温度調節手段(ジャケット13および23)の設定温度は、後述する供給流量制御手段に伝えられ、原料モノマー供給手段(ポンプ5)や重合開始剤供給手段(ポンプ7および19)による供給流量の制御の要否を判断するためのデータとなる。また、上記温度調節手段(ジャケット13および23)の設定温度は、上記熱媒の温度または圧力を制御することにより、調節可能である。
温度センサTで検知された反応槽10内の温度が、温度調節手段であるジャケット13の設定温度を超えるときには、上記CPUによって上記ROM内のプログラムを実行することにより、例えば、反応槽10内への重合開始剤の供給流量を減少させるように、ポンプ7を制御する。ポンプ19により反応槽20に重合開始剤を供給して重合を実施中、温度センサTで検知された反応槽20内の温度が、温度調節手段であるジャケット23の設定温度を超えるときには、上記CPUによって上記ROM内のプログラムを実行することにより、例えば、反応槽20内への重合開始剤の供給流量を減少させるように、ポンプ19を制御する。かかる制御を実行することにより、反応槽10および/または20内で発生する重合熱を減少させることができ、その結果、反応槽10および/または20内の温度を低下させることができる。
まず、原料モノマー、重合開始剤および連鎖移動剤などを準備する。
本明細書において、第1の反応槽10に供給される原料モノマーを原料モノマーAとも呼び、第2の反応槽20に新たに供給される原料モノマーを原料モノマーBとも呼ぶ。原料モノマーAおよびBは、同じ組成であってよく、または互いに異なる組成であってよい。
本発明の原料モノマーは、メタクリル酸メチルを50重量%以上含有する。
メタクリル酸メチルを50重量%以上含有することで、得られるメタクリル系樹脂組成物においてメタクリル樹脂の特徴である透明性、耐候性、耐熱性等を付与することができる。原料モノマー中のメタクリル酸メチルの含有量は、80重量%以上であることが好ましく、90重量%以上であることがより好ましい。
原料モノマーは、メタクリル酸メチルの他に、メタクリル酸メチルと共重合可能な他のモノマーを含み得る。これら他のモノマーは、単独で使用してもよく、2種以上を混合して使用してもよい。原料モノマー中の共重合可能な他のモノマーの含有量は、50重量%以下であり、好ましくは20重量%以下、より好ましくは10重量%以下である。
メタクリル酸メチルと共重合可能な他のモノマーとしては、例えば、メタクリル酸エチル、メタクリル酸n−プロピル、メタクリル酸イソプロピル、メタクリル酸n−ブチル、メタクリル酸t−ブチル、メタクリル酸sec−ブチル、メタクリル酸イソブチル、メタクリル酸2−エチルヘキシル等のメタクリル酸アルキル(アルキル基の炭素数が2~8であるメタクリル酸アルキル);メタクリル酸ベンジル等のメタクリル酸アリール;アクリル酸メチル、アクリル酸エチル、アクリル酸n−プロピル、アクリル酸イソプロピル、アクリル酸n−ブチル、アクリル酸t−ブチル、アクリル酸sec−ブチル、アクリル酸イソブチル、アクリル酸2−エチルヘキシル、アクリル酸ベンジル等のアクリル酸エステル類;アクリル酸、メタクリル酸、マレイン酸、イタコン酸、無水マレイン酸、無水イタコン酸等の不飽和カルボン酸またはこれらの酸無水物;アクリル酸2−ヒドロキシエチル、アクリル酸2−ヒドロキシプロピル、アクリル酸モノグリセロール、メタクリル酸2−ヒドロキシエチル、メタクリル酸2−ヒドロキシプロピル、メタクリル酸モノグリセロール等のヒドロキシル基含有モノマー;アクリルアミド、メタクリルアミド、アクリロニトリル、メタクリロニトリル、ジアセトンアクリルアミド、メタクリル酸ジメチルアミノエチル等の窒素含有モノマー;アリルグリシジルエーテル、アクリル酸グリシジル、メタクリル酸グリシジル等のエポキシ基含有単量体;スチレン、α−メチルスチレン、ジビニルベンゼン等のスチレン系単量体;エチレングリコールジメタクリレート、ブタンジオールジメタクリレート等のグリコール類の不飽和カルボン酸ジエステル;アクリル酸アリル、メタクリル酸アリル、ケイ皮酸アリル等の不飽和カルボン酸のアルケニルエステル;フタル酸ジアリル、マレイン酸ジアリル、トリアリルシアヌレート、トリアリルイソシアヌレート等の多塩基酸のポリアルケニルエステル;トリメチロールプロパントリアクリレート等の多価アルコールの不飽和カルボン酸エステルなどが挙げられる。
重合開始剤として、本実施形態では、例えばラジカル開始剤を用いる。
ラジカル開始剤としては、例えば、アゾビスイソブチロニトリル、アゾビスジメチルバレロニトリル、アゾビスシクロヘキサンニトリル、1,1’−アゾビス(1−アセトキシ−1−フェニルエタン)、ジメチル2,2’−アゾビスイソブチレート、4,4’−アゾビス−4−シアノバレリン酸などのアゾ化合物;ベンゾイルパーオキサイド、ラウロイルパーオキサイド、アセチルパーオキサイド、カプリリルパーオキサイド、2,4−ジクロルベンゾイルパーオキサイド、イソブチルパーオキサイド、アセチルシクロヘキシルスルホニルパーオキサイド、t−ブチルパーオキシピバレート、t−ブチルパーオキシネオデカノエート、t−ブチルパーオキシネオヘプタノエート、t−ブチルパーオキシ−2−エチルヘキサノエート、1,1−ジ(t−ブチルパーオキシ)シクロヘキサン、1,1−ジ(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、1,1−ジ(t−ヘキシルパーオキシ)−3,3,5−トリメチルシクロヘキサン、ジイソプロピルパーオキシジカーボネート、ジイソブチルパーオキシジカーボネート、ジ−sec−ブチルパーオキシジカーボネート、ジ−n−ブチルパーオキシジカーボネート、ビス(2−エチルヘキシル)パーオキシジカーボネート、ビス(4−t−ブチルシクロヘキシル)パーオキシジカーボネート、t−アミルパーオキシ−2−エチルヘキサノエート、1,1,3,3−テトラメチルブチルパーオキシ−エチルヘキサノエート、1,1,2−トリメチルプロピルパーオキシ−2−エチルヘキサノエート、t−ブチルパーオキシイソプロピルモノカーボネート、t−アミルパーオキシイソプロピルモノカーボネート、t−ブチルパーオキシ−2−エチルヘキシルカーボネート、t−ブチルパーオキシアリルカーボネート、t−ブチルパーオキシイソプロピルカーボネート、1,1,3,3−テトラメチルブチルパーオキシイソプロピルモノカーボネート、1,1,2−トリメチルプロピルパーオキシイソプロピルモノカーボネート、1,1,3,3−テトラメチルブチルパーオキシイソノナエート、1,1,2−トリメチルプロピルパーオキシ−イソノナエート、t−ブチルパーオキシベンゾエートなどの有機過酸化物が挙げられる。
これらの重合開始剤は、1種を単独で使用してもよく、2種以上を混合して使用してもよい。
連鎖移動剤は、単官能および多官能のいずれの連鎖移動剤であってもよい。連鎖移動剤としては、具体的には、例えば、n−プロピルメルカプタン、イソプロピルメルカプタン、n−ブチルメルカプタン、t−ブチルメルカプタン、n−ヘキシルメルカプタン、n−オクチルメルカプタン、2−エチルヘキシルメルカプタン、n−ドデシルメルカプタン、t−ドデシルメルカプタンなどのアルキルメルカプタン;フェニルメルカプタン、チオクレゾールなどの芳香族メルカプタン;エチレンチオグリコールなどの炭素数18以下のメルカプタン類;エチレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、ソルビトールなどの多価アルコール類;水酸基をチオグリコール酸または3−メルカプトプロピオン酸でエステル化したもの、1,4−ジヒドロナフタレン、1,4,5,8−テトラヒドロナフタレン、β−テルピネン、テルピノーレン、1,4−シクロヘキサジエン、硫化水素などが挙げられる。これらの連鎖移動剤は、単独で使用してもよく、2種以上を組み合わせて使用してもよい。
重合開始剤タンク17にて、上述のような重合開始剤を、原料モノマーおよび連鎖移動剤と(場合により他の成分と)共に適宜調合する。重合開始剤タンク17には、原料モノマー、重合開始剤および連鎖移動剤を含む混合物(場合により他の成分を更に含み得る)の形態で貯留する。
重合開始剤タンク3にポンプ7を介して供給口11cが接続される場合または重合開始剤タンク17にポンプ19を介して供給口21cが接続される場合には、重合開始剤タンク3または17に重合開始剤を単独で貯留すると、重合開始剤が単独で反応槽10または反応槽20に供給されるため、反応槽10または反応槽20において局所的に重合反応が進行するおそれがある。これに対し、原料モノマーと重合開始剤との混合物の形態で貯留すると、重合開始剤が原料モノマーの一部と予め混合されているので、かかるおそれが解消され得る。
第1の重合工程において、原料モノマー、重合開始剤および連鎖移動剤を含む原料組成物を第1の反応槽に供給する。本明細書において、第1の反応槽に供給される原料組成物を原料組成物Aとも呼ぶ。
原料モノマー、重合開始剤および連鎖移動剤の供給源である原料モノマータンク1および重合開始剤タンク3から、原料モノマー、重合開始剤および連鎖移動剤を第1の反応槽10に供給口11aより供給する。具体的には、原料モノマータンク1から原料モノマーおよび場合により連鎖移動剤をポンプ5により、ならびに重合開始剤タンク3から重合開始剤(好ましくは原料モノマー、重合開始剤および場合により連鎖移動剤の混合物)をポンプ7により、原料供給ライン9を通じて一緒にして、第1の反応槽10に供給口11aより供給する。また、重合開始剤タンク3から重合開始剤をポンプ7により、図1に点線で示すように、第1の反応槽10に供給口11cより供給してもよい。
反応槽内と反応槽外壁面との温度差は小さいほど好ましく、具体的には±5℃程度の幅で調整することが好ましい。第1の反応槽10内で発生する重合熱や撹拌熱は通常、第1の反応槽10から中間組成物を抜き出す際に持ち去られる。中間組成物が持ち去る熱量は、中間組成物の流量、比熱、重合反応の温度によって定まる。
第2の重合工程は、第1の重合工程の後に直列的に実施される。
上述のようにして得られた中間組成物は、第1の反応槽10の抜き出し口11bから抜き出された後、接続ライン15を通じて第2の反応槽20に供給口21aより供給される。そして、中間組成物は、第2の反応槽20にて更に連続塊状重合に付される。この第2の重合工程は、重合反応を所望の重合率まで進行させる。得られた重合体組成物(または重合シロップ)が、第2の反応槽20の抜き出し口21bより連続的に抜き出される。
具体的には、重合開始剤タンク17から原料モノマー、重合開始剤および連鎖移動剤を含む原料組成物をポンプ19により、第2の反応槽20に、接続ライン15を通じて供給口21aより、あるいは別の供給口21cより供給し、これにより、中間組成物に新たな重合開始剤が添加される。
また、原料組成物Bを作製する際、重合開始剤タンク17から原料モノマーおよび重合開始剤を含む原料組成物をポンプ19より接続ライン15まで送液途中に、重合開始剤タンク17とは別のタンクにて貯蔵され、ポンプ19とは別のポンプから送液された液体の連鎖移動剤と合流することによって、2つのポンプの流量を調整し所望の連鎖移動剤濃度を得ることも可能である。
重合開始剤タンク17から第2の反応槽20へと供給される原料組成物Bの温度は、特に限定されないが、反応槽内の熱バランスを崩して、重合温度を変動させる要因となることから、適宜、加熱/冷却器(図示せず)によって反応槽20に供給される前に温度調節することが好ましい。原料組成物Bに含まれる重合開始剤の割合は、0.002~10重量%であることが好ましい。
1.7≦[S2]/[S1]
を満たすように連鎖移動剤の供給量を調整し、好ましくは、下式
2.0≦[S2]/[S1]
を満たすように連鎖移動剤の供給量を調整する。
[S2]/[S1]の上限については特に限定されないが、100以下が好ましく、50以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましく、10以下が最も好ましい。
[S1]は、0.2未満であることが好ましく、0.14未満であることがより好ましい。[S1]が0.2以上であると、押出機から押し出されるストランドをペレタイザーにて引き取りペレットに成形する際、ストランドの機械強度が低くなることがある。そのため、ストランドが切れたり、微粉が増加したりすることがある。
[S1]の下限は0.05であることが好ましい。[S1]が0.05未満であると、第1の反応槽で得られる重合体の分子量が高くなるため、第1の反応槽におけるシロップ粘度が高くなることがある。その結果、第1の反応槽において、均一に撹拌することが困難になったり、送液が難しくなったりすることがある。また、シロップ粘度が高いため、第1の反応槽での暴走反応が起こる可能性がある。また、得られる重合体の平均分子量が高いため、押出機における負荷が増大することがある。
更に、[S2]は下式
0<[S2]≦1
を満たすことが好ましい。
[S2]の上限は1であることが好ましい。[S2]が1を超えると、第2の反応槽で得られる重合体の粘度がかなり低くなることがある。その結果、押出機から押し出されるストランドをペレタイザーにて引き取りペレットに成形する際、ストランドの機械強度が低くなることがある。そのため、ストランドが切れたり、微粉が増加したりすることがある。
[S2]は0より大きいことが好ましく、0.2以上であることがより好ましい。
1≦Q1/Q2≦50
を満たすように、ポンプ5、7および19を調節する。このように第2の反応槽20に供給される中間組成物および原料組成物の流量を調節し、連鎖移動剤を希釈して第2の反応槽20に供給することにより、連鎖移動剤を希釈せず直接供給するよりも、Q1および/またはQ2の変化に対する影響が緩和されるため、[S2]を安定して制御することができる。その結果、目的とする分子量分布のメタクリル系重合体組成物を安定して得ることができる。
Q1/Q2が50を超えると、低分子量重合体を作製するためには、第2の反応槽に供給される原料組成物中の連鎖移動剤濃度をかなり高くしなければならない。この場合は、Q2の微小な変化が低分子量重合体の分子量に大きな影響を与えることになるため、好ましくない。
Q1/Q2が1未満であると、第1の反応槽で作製される重合体が第2の反応槽に供給される原料組成物によって希釈される。そのため、生産効率が下がる。
この満液状態により、反応槽の内壁面にゲルが付着して成長するといった問題や、このゲルが反応混合物に混入することによって、最終的に得られる樹脂組成物の品質が低下するといった問題が発生することを、未然に防止できる。更に、この満液状態により、反応槽の容積全てを反応空間に有効利用でき、よって、高い生産効率を得ることができる。
また、重合率を高くすると、重合発熱量が大きくなり、反応系の重合反応における温度を一定に保つための除熱の際に、反応系の局所的または急激な冷却が起こりやすくなる。その結果、反応槽の内壁面におけるゲルの付着および成長がより顕著となり、得られる重合体組成物にゲル化物が不純物として混入する等の問題が起こり得る。一方、重合率が低いほど、重合体の生産性が低くなり、未反応の原料モノマーを回収するための負担が大きくなってしまう。よって、適切な重合率を目標または目安として設定することが好ましい。
第1の反応槽の温度が120℃より低いと、第1の反応槽で得られる重合率が低くなり、その結果、生産性が損なわれる。第1の反応槽の温度が160℃より高いと、高分子量重合体の割合が多くなるため、目標の低分子量重合体の割合を得られない。
第2の反応槽の温度が140℃より低いと、第2の反応槽で得られる重合率が低くなり、その結果、生産性が損なわれる。第2の反応槽の温度が180℃より高いと、解重合が起こるため、目標の低分子量重合体の割合および目標の低分子量重合体の分子量が達成できない。また、高い温度で重合することによって、副生成物である二量体が多く生成されてしまう。
T2−T1が20℃より低いと、低分子量重合体の割合が低くなりすぎるため、得られる重合体の平均分子量が高くなる。そのため、押出機における負荷が増大する。
T2−T1が60℃より高いと、低分子量重合体の割合が多くなる。その結果、押出機から出てくるストランドをペレタイザーにて引き取りペレットに成形する際、ストランドの機械強度が低いため、ストランドが切れたり、微粉が増加したりする。
第2の反応槽20の抜き出し口21bから抜き出される重合体組成物(重合シロップ)は、上述のように、生成した重合体のほか、未反応の原料モノマーおよび重合開始剤などを含み得る。かかる重合体組成物は、本実施形態を限定しないが、脱揮等に付して原料モノマーを分離回収することが好ましい。
本実施例においては、概略的には、図1を参照しながら上述した実施形態に従って、連続重合を2段で実施して、重合体組成物をペレット(樹脂組成物)の形態で製造した。より詳細には、以下の通りである。
メタクリル酸メチル99.840質量部および重合開始剤としてt−アミルパーオキシ−2−エチルヘキサノエート0.160質量部を混合して、重合開始剤混合液1を調製した。
メタクリル酸メチル96.868質量部、重合開始剤として1,1−ジ(t−ブチルパーオキシ)シクロヘキサン0.116質量部および連鎖移動剤としてn−オクチルメルカプタン3.016質量部を混合して、重合開始剤混合液2を調製した。
接続ライン15には外壁面を取り囲むジャケットが設けられており、このジャケットを用いて、接続ライン15の内部を通る中間組成物が第1の反応槽内の温度と等しい温度(本実施例では120℃)を維持するように調整した。また、重合開始剤混合液2を重合開始剤タンク17から第2の反応槽20へ、別の供給口21cより連続的に供給した。
具体的には、得られたペレット状の樹脂組成物40mgをテトラヒドロフラン(THF)溶媒20mlに溶解させ、測定試料を作製した。測定装置には、東ソー(株)製のカラムである「TSKgel SuperHM−H」2本と、「SuperH2500」1本とを直列に並べて設置し、検出器にRI検出器を採用したものを用いた。
測定された分子量分布曲線は、横軸の分子量の対数をとることにより、正規分布関数を用いてフィッティングを行った。分子量分布曲線が単峰性である場合には、下記の(式1)の正規分布関数を用いてフィッティングを行った。また、分子量分布曲線が2峰性である、平均分子量の異なる2種類の重合体の混合物については、2つの正規分布関数の和(下記の(式2))で同様にフィッティングを行った。(式2)を用いたフィッティングにより得られた2つの正規分布関数の内、yが最大となるときのxの値が小さい関数を低分子量体成分とし、全体の面積に対する低分子量体の面積(以下、低分子量体面積比とも呼ぶ)を算出することで、樹脂組成物に含まれる重合体における低分子量体成分の割合に相関する値を算出した。フィッティングには、WaveMetrics社製解析ソフトIGOR PRO6.0を用いた。
また、GPC測定結果から、低分子量体面積比および分子量分布Mw/Mnを求めた。
ここで、MwおよびMnはそれぞれ、測定した樹脂組成物の重量平均分子量および数平均分子量である。
本実施例においては、以下の点を除いて、実施例1と同様にして樹脂組成物をペレットの形態で製造した。
実施例1と同様の組成で、原料モノマー混合液1を調製した。
メタクリル酸メチル99.823質量部および重合開始剤としてt−アミルパーオキシ−2−エチルヘキサノエート0.177質量部を混合して、重合開始剤混合液1を調製した。
メタクリル酸メチル96.900質量部、重合開始剤として1,1−ジ(t−ブチルパーオキシ)シクロヘキサン0.084質量部および連鎖移動剤としてn−オクチルメルカプタン3.016質量部を混合して、重合開始剤混合液2を調製した。
第1の反応槽10内の温度(T1)は130℃とし、第1の反応槽10の外壁面を取り囲むジャケット13の温度を130℃とし、接続ライン15の内部を通る中間組成物が130℃の温度を維持するように調整した。
また、GPC測定結果から、低分子量体面積比および分子量分布Mw/Mnを求めた。
本実施例においては、以下の点を除いて、実施例1と同様にして樹脂組成物をペレットの形態で製造した。
実施例1と同様の組成で、原料モノマー混合液1を調製した。
メタクリル酸メチル99.838質量部および重合開始剤としてt−アミルパーオキシ−2−エチルヘキサノエート0.162質量部を混合して、重合開始剤混合液1を調製した。
メタクリル酸メチル96.921質量部、重合開始剤として1,1−ジ(t−ブチルパーオキシ)シクロヘキサン0.063質量部および連鎖移動剤としてn−オクチルメルカプタン3.016質量部を混合して、重合開始剤混合液2を調製した。
第1の反応槽10内の温度(T1)は150℃とし、第1の反応槽10の外壁面を取り囲むジャケット13の温度を150℃とし、接続ライン15の内部を通る中間組成物が150℃の温度を維持するように調整した。
また、GPC測定結果から、低分子量体面積比および分子量分布Mw/Mnを求めた。
本実施例においては、以下の点を除いて、実施例1と同様にして樹脂組成物をペレットの形態で製造した。
メタクリル酸メチル98.826質量部およびアクリル酸メチル0.935質量部を混合し、連鎖移動剤としてn−オクチルメルカプタン0.139質量部、および離型剤としてステアリルアルコール0.100質量部を加えて、原料モノマー混合液1を調製した。
メタクリル酸メチル99.840質量部および重合開始剤としてt−アミルパーオキシ−2−エチルヘキサノエート0.160質量部を混合して、重合開始剤混合液1を調製した。
メタクリル酸メチル96.921質量部、重合開始剤として1,1−ジ(t−ブチルパーオキシ)シクロヘキサン0.063質量部および連鎖移動剤としてn−オクチルメルカプタン3.016質量部を混合して、重合開始剤混合液2を調製した。
接続ライン15には外壁面を取り囲むジャケットが設けられており、このジャケットを用いて、接続ライン15の内部を通る中間組成物が140℃の温度を維持するように調整した。また、重合開始剤混合液2を重合開始剤タンク17から第2の反応槽20へ、別の供給口21cより連続的に供給した。
Q1を第1の反応槽から第2の反応槽に流入する中間組成物の流量、Q2を第2の反応槽に供給される重合開始剤混合液2の流量とすると、Q1=201.85cm3/分、Q2=21.15cm3/分となった。
また、GPC測定結果から、低分子量体面積比および分子量分布Mw/Mnを求めた。
本実施例においては、以下の点を除いて、実施例4と同様にして樹脂組成物をペレットの形態で製造した。
メタクリル酸メチル98.871質量部およびアクリル酸メチル0.935質量部を混合し、連鎖移動剤としてn−オクチルメルカプタン0.094質量部、および離型剤としてステアリルアルコール0.100質量部を加えて、原料モノマー混合液1を調製した。
メタクリル酸メチル99.860質量部および重合開始剤としてt−アミルパーオキシ−2−エチルヘキサノエート0.140質量部を混合して、重合開始剤混合液1を調製した。
メタクリル酸メチル96.900質量部、重合開始剤として1,1−ジ(t−ブチルパーオキシ)シクロヘキサン0.084質量部および連鎖移動剤としてn−オクチルメルカプタン3.016質量部を混合して、重合開始剤混合液2を調製した。
Q1を第1の反応槽から第2の反応槽に流入する中間組成物の流量、Q2を第2の反応槽に供給される重合開始剤混合液2の流量とすると、Q1=201.85cm3/分、Q2=21.15cm3/分となった。
また、GPC測定結果から、低分子量体面積比および分子量分布Mw/Mnを求めた。
本実施例においては、以下の点を除いて、実施例1と同様にして樹脂組成物をペレットの形態で製造した。
メタクリル酸メチル98.856質量部およびアクリル酸メチル0.951質量部を混合し、連鎖移動剤としてn−オクチルメルカプタン0.093質量部、および離型剤としてステアリルアルコール0.100質量部を加えて、原料モノマー混合液1を調製した。
メタクリル酸メチル99.747質量部および重合開始剤としてt−アミルパーオキシ−2−エチルヘキサノエート0.253質量部を混合して、重合開始剤混合液1を調製した。
メタクリル酸メチル95.775質量部、アクリル酸メチル0.915質量部、重合開始剤として1,1−ジ(t−ブチルパーオキシ)シクロヘキサン0.170質量部および連鎖移動剤としてn−オクチルメルカプタン3.140質量部を混合して、重合開始剤混合液2を調製した。
接続ライン15には外壁面を取り囲むジャケットが設けられており、このジャケットを用いて、接続ライン15の内部を通る中間組成物が140℃の温度を維持するように調整した。また、重合開始剤混合液2を重合開始剤タンク17から第2の反応槽20へ、別の供給口21cより連続的に供給した。
Q1を第1の反応槽か第2の反応槽に流入する中間組成物の流量、Q2を第2の反応槽に供給される重合開始剤2の流量とすると、Q1=348.96cm3/分、Q2=28.89cm3/分となった。
本実施例においては、以下の点を除いて、実施例6と同様にして樹脂組成物をペレットの形態で製造した。
メタクリル酸メチル98.856質量部およびアクリル酸メチル0.951質量部を混合し、連鎖移動剤としてn−オクチルメルカプタン0.093質量部、および離型剤としてステアリルアルコール0.100質量部を加えて、原料モノマー混合液1を調製した。
メタクリル酸メチル99.747質量部および重合開始剤としてt−アミルパーオキシ−2−エチルヘキサノエート0.253質量部を混合して、重合開始剤混合液1を調製した。
メタクリル酸メチル92.692質量部、アクリル酸メチル0.915質量部、重合開始剤として1,1−ジ(t−ブチルパーオキシ)シクロヘキサン0.183質量部および連鎖移動剤としてn−オクチルメルカプタン6.210質量部を混合して、重合開始剤混合液2を調製した。
Q1を第1の反応槽から第2の反応槽に流入する中間組成物の流量、Q2を第2の反応槽に供給される重合開始剤混合液2の流量とすると、Q1=348.96cm3/分、Q2=28.89cm3/分となった。
本比較例においては、以下に示す通り、第2の反応槽20に重合禁止剤を供給して重合を停止させることにより、1段で重合を行った場合に相当する樹脂組成物を得て、その分子量分布を確認した。
メタクリル酸メチル98.956質量部およびアクリル酸メチル0.935質量部を混合し、連鎖移動剤としてn−オクチルメルカプタン0.009質量部および離型剤としてステアリルアルコール0.100質量部を加えて、原料モノマー混合液1を調製した。
メタクリル酸メチル99.816質量部および重合開始剤として1,1−ジ(t−ブチルパーオキシ)シクロヘキサン0.184質量部を混合して、重合開始剤混合液1を調製した。
メタクリル酸メチル99.99995質量部および重合禁止剤として2,6−ビス(tert−ブチル)−4−メチルフェノール0.00005質量部を混合して、重合禁止剤混合液を調製した。
接続ライン15には外壁面を取り囲むジャケットが設けられており、このジャケットを用いて、接続ライン15の内部を通る中間組成物が175℃の温度を維持するように調整した。また、重合禁止剤混合液を重合開始剤タンク17から第2の反応槽20へ、別の供給口21cより連続的に供給した。
Q1を第1の反応槽から第2の反応槽に流入する中間組成物の流量、Q2を第2の反応槽に供給される重合禁止剤混合液の流量とすると、Q1=201.85cm3/分、Q2=21.15cm3/分となった。
本比較例においては、以下の点を除いて、実施例6と同様にして樹脂組成物をペレットの形態で製造した。
メタクリル酸メチル98.817質量部およびアクリル酸メチル0.951質量部を混合し、連鎖移動剤としてn−オクチルメルカプタン0.132質量部、および離型剤としてステアリルアルコール0.100質量部を加えて、原料モノマー混合液1を調製した。
メタクリル酸メチル99.719質量部および重合開始剤としてt−アミルパーオキシ−2−エチルヘキサノエート0.281質量部を混合して、重合開始剤混合液1を調製した。
メタクリル酸メチル97.930質量部、アクリル酸メチル0.915質量部、重合開始剤として1,1−ジ(t−ブチルパーオキシ)シクロヘキサン0.105質量部および連鎖移動剤としてn−オクチルメルカプタン1.050質量部を混合して、重合開始剤混合液2を調製した。
Q1を第1の反応槽から第2の反応槽に流入する中間組成物の流量、Q2を第2の反応槽に供給される重合開始剤混合液2の流量とすると、Q1=348.96cm3/分、Q2=28.89cm3/分となった。
また、表1より、実施例1~7における分子量分布Mw/Mnは3.3~5.2であり、分子量分布Mw/Mnが各々2.1および2.3である比較例1および2と比較して、分子量分布が広くなっていることがわかる。
以上より、連続塊状重合を2段で行い、[S2]/[S1]を1.7以上とすることにより、低分子量体および高分子量体を含み、かつ分子量分布の広い樹脂組成物を得ることができることがわかる。比較例2では、第2の反応槽に新たな連鎖移動剤を追加しているが、[S2]/[S1]の値が低いため、分子量分布を大きく広げることはできなかった。
表1および図3(a)~(c)から理解されるように、[S2]の値を固定し、[S1]の値を下げることによって、高分子量体の分子量を上げることができ、分子量分布を広げることができる。
表1および図4(a)~(c)から理解されるように、[S1]の値を固定し、[S2]の値を上げることによって、低分子量体の分子量を下げることができ、分子量分布を広げることができる。
これらのことより、分子量分布は、[S1]値、[S2]値のバランスに依存していることがわかる。
(原料モノマーおよび場合により連鎖移動剤の供給源)
3 重合開始剤タンク
(重合開始剤ならびに場合により原料モノマーおよび連鎖移動剤の供給源)
5 ポンプ
7 ポンプ
9 原料供給ライン
10 第1の反応槽
11a 供給口
11b 抜き出し口
11c 別の供給口
13 ジャケット(温度調節手段)
14 攪拌機
15 接続ライン
17 重合開始剤タンク
(新たな原料モノマー、重合開始剤および連鎖移動剤の供給源)
19 ポンプ
20 第2の反応槽
21a 供給口
21b 抜き出し口
21c 別の供給口
23 ジャケット(温度調節手段)
24 攪拌機
25 抜き出しライン
31 予熱器
33 脱揮押出機
35 取り出しライン
37 回収タンク
T 温度センサ(温度検知手段)
Claims (5)
- メタクリル酸メチルを50重量%以上含有する原料モノマーA、重合開始剤Aおよび連鎖移動剤Aを含む原料組成物Aを第1の完全混合型反応槽の供給口より供給し、第1の完全混合型反応槽において原料組成物Aを連続塊状重合に付し、得られた中間組成物を第1の完全混合型反応槽の抜き出し口より抜き出す第1の重合工程と、
メタクリル酸メチルを50重量%以上含有する原料モノマーB、重合開始剤Bおよび連鎖移動剤Bを含む原料組成物Bならびに第1の重合工程で抜き出された中間組成物を第2の完全混合型反応槽の供給口より供給し、第2の完全混合型反応槽において原料組成物Bおよび中間組成物を更に連続塊状重合に付し、得られたメタクリル系重合体組成物を第2の完全混合型反応槽の抜き出し口より抜き出す第2の重合工程と
を含み、下式(I)、(II)、(III)、(IV)および(V)
120≦T1≦160 (I)
140≦T2≦180 (II)
20≦T2−T1≦60 (III)
1.7≦[S2]/[S1] (IV)
1≦Q1/Q2≦50 (V)
(T1は第1の重合工程における第1の完全混合型反応槽内の温度(℃)、T2は第2の重合工程における第2の完全混合型反応槽内の温度(℃)、[S1]は第1の完全混合型反応槽に供給される原料組成物A中の連鎖移動剤Aの濃度(重量%)、[S2]は第2の完全混合型反応槽に供給される原料組成物Bおよび中間組成物の総量に対する連鎖移動剤Bの濃度(重量%)、Q1は第2の完全混合型反応槽に供給される中間組成物の流量(cm3/分)、Q2は第2の完全混合型反応槽に供給される原料組成物Bの流量(cm3/分))
を満たすメタクリル系重合体組成物の製造方法。 - さらに、下式(VI)および(VII)
40≦x≦60 (VI)
θ1+θ2≦180 (VII)
(xは、第2の完全混合型反応槽の抜き出し口より抜き出されるメタクリル系重合体組成物における重合率(重量%)、θ1は第1の重合工程における第1の完全混合型反応槽の平均滞留時間(分)、θ2は第2の重合工程における第2の完全混合型反応槽の平均滞留時間(分))
を満たす請求項1に記載の方法。 - 前記第1および第2の完全混合型反応槽の抜き出し口は、各反応槽の頂部に位置する請求項1に記載の方法。
- 第1の重合工程および第2の重合工程における連続塊状重合が断熱状態で行われる請求項1に記載の方法。
- 請求項1~4のいずれかに記載の方法により製造されるメタクリル系重合体組成物から得られる成形体。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/649,076 US9522969B2 (en) | 2012-12-03 | 2013-11-29 | Method for producing methacrylic polymer composition, and molded article |
KR1020157014598A KR102001281B1 (ko) | 2012-12-03 | 2013-11-29 | 메타크릴계 중합체 조성물의 제조 방법 및 성형체 |
EP13860754.4A EP2927249A4 (en) | 2012-12-03 | 2013-11-29 | METHOD FOR PRODUCING A METHACRYLPOLYMER COMPOSITION AND FORM BODY |
CN201380072087.7A CN104955853B (zh) | 2012-12-03 | 2013-11-29 | 生产甲基丙烯酸聚合物组合物的方法和模制品 |
SG11201504287WA SG11201504287WA (en) | 2012-12-03 | 2013-11-29 | Method for producing methacrylic polymer composition, and molded article |
SA515360508A SA515360508B1 (ar) | 2012-12-03 | 2015-06-03 | طريقة لإنتاج تركيبة بوليمر ميثاكريليك، ومنتج مقولب |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-264021 | 2012-12-03 | ||
JP2012264021A JP6002017B2 (ja) | 2012-12-03 | 2012-12-03 | メタクリル系重合体組成物の製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014088082A1 true WO2014088082A1 (ja) | 2014-06-12 |
Family
ID=50883494
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/082750 WO2014088082A1 (ja) | 2012-12-03 | 2013-11-29 | メタクリル系重合体組成物の製造方法および成形体 |
Country Status (9)
Country | Link |
---|---|
US (1) | US9522969B2 (ja) |
EP (1) | EP2927249A4 (ja) |
JP (1) | JP6002017B2 (ja) |
KR (1) | KR102001281B1 (ja) |
CN (1) | CN104955853B (ja) |
SA (1) | SA515360508B1 (ja) |
SG (1) | SG11201504287WA (ja) |
TW (1) | TWI580696B (ja) |
WO (1) | WO2014088082A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015199038A1 (ja) * | 2014-06-23 | 2015-12-30 | 住友化学株式会社 | メタクリル樹脂組成物およびその成形体 |
WO2017010323A1 (ja) * | 2015-07-14 | 2017-01-19 | 三菱レイヨン株式会社 | メタクリル系樹脂、メタクリル系樹脂の製造方法、成形体及び自動車 |
US20170298157A1 (en) * | 2014-09-30 | 2017-10-19 | Kuraray Co., Ltd. | Method for producing (meth)acrylic resin |
WO2018066393A1 (ja) * | 2016-10-04 | 2018-04-12 | 住友化学株式会社 | メタクリル樹脂組成物およびその成形体 |
EP3885371A1 (en) | 2020-03-26 | 2021-09-29 | Sumitomo Chemical Company, Limited | Methacrylic resin composition, molded article, and method of producing methacrylic resin composition |
EP3991939A1 (en) | 2020-10-30 | 2022-05-04 | Sumitomo Chemical Company Limited | Molded article and method of producing the same |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6360490B2 (ja) * | 2013-10-28 | 2018-07-18 | 株式会社クラレ | 板状成形体 |
TWI655216B (zh) * | 2014-08-06 | 2019-04-01 | Kuraray Co., Ltd. | (甲基)丙烯酸樹脂組成物之製造方法 |
JP2017132961A (ja) * | 2016-01-29 | 2017-08-03 | パナソニックIpマネジメント株式会社 | メタクリル樹脂成形材料 |
CN108350246B (zh) | 2016-02-26 | 2020-09-18 | 株式会社可乐丽 | 甲基丙烯酸类树脂组合物和注射成型品 |
CN109232787B (zh) * | 2018-09-12 | 2021-02-02 | 万华化学集团股份有限公司 | 甲基丙烯酸甲酯-苯乙烯共聚树脂、其制备方法和用途 |
CN110591059A (zh) * | 2019-08-31 | 2019-12-20 | 宁夏共享化工有限公司 | 铸造用醇酸树脂及其制备方法 |
CN110615864B (zh) * | 2019-10-10 | 2021-05-14 | 万华化学集团股份有限公司 | 一种甲基丙烯酸甲酯聚合物及其制备方法 |
JP2021109966A (ja) * | 2020-01-10 | 2021-08-02 | 住友化学株式会社 | 硬化型組成物 |
JP7482762B2 (ja) | 2020-03-26 | 2024-05-14 | 住友化学株式会社 | メタクリル樹脂組成物、成形体、および、メタクリル樹脂組成物の製造方法 |
CN113467550B (zh) * | 2020-03-30 | 2022-10-04 | 中石油吉林化工工程有限公司 | 用于mma生产装置中酰化反应的温控系统及温控方法 |
WO2023162543A1 (ja) * | 2022-02-28 | 2023-08-31 | 住友化学株式会社 | メタクリル樹脂組成物、およびその成形体 |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5129914B2 (ja) | 1973-08-15 | 1976-08-28 | ||
JPS5217555B2 (ja) | 1973-08-15 | 1977-05-16 | ||
JPS54149788A (en) | 1978-05-17 | 1979-11-24 | Asahi Chem Ind Co Ltd | Preparation of solvent-resistant acrylic resin |
JPS58101140A (ja) | 1981-12-10 | 1983-06-16 | Mitsubishi Rayon Co Ltd | 良流動性アクリル樹脂組成物 |
JPS6289710A (ja) | 1985-10-15 | 1987-04-24 | Asahi Chem Ind Co Ltd | メタクリル系樹脂の製造方法 |
JPH0153682B2 (ja) | 1982-02-26 | 1989-11-15 | Sumitomo Chemical Co | |
JPH0349925A (ja) | 1989-07-17 | 1991-03-04 | Sumitomo Chem Co Ltd | 熱可塑性重合体組成物の脱揮押出方法 |
JPH0448802B2 (ja) | 1983-05-17 | 1992-08-07 | Sumitomo Chemical Co | |
JPH06240093A (ja) | 1993-02-12 | 1994-08-30 | Sumitomo Chem Co Ltd | メタクリル系の樹脂組成物 |
JPH07206906A (ja) * | 1994-01-07 | 1995-08-08 | Mitsubishi Gas Chem Co Inc | 耐熱分解性を有するメタクリル樹脂及びその製造方法 |
JPH07206905A (ja) * | 1994-01-07 | 1995-08-08 | Mitsubishi Gas Chem Co Inc | 耐熱分解性を有するメタクリル樹脂及びその製造方法 |
JP2004211105A (ja) | 2004-04-21 | 2004-07-29 | Mitsubishi Gas Chem Co Inc | メタクリル樹脂の製造方法 |
JP2006298966A (ja) | 2005-04-15 | 2006-11-02 | Mitsubishi Rayon Co Ltd | 導光板用アクリル樹脂組成物 |
JP2008538794A (ja) | 2005-04-25 | 2008-11-06 | ルーサイト インターナショナル ユーケー リミテッド | アクリルブレンド |
JP2010059305A (ja) | 2008-09-03 | 2010-03-18 | Mitsubishi Rayon Co Ltd | メタクリル系樹脂組成物 |
WO2011049203A1 (ja) | 2009-10-22 | 2011-04-28 | 旭化成ケミカルズ株式会社 | メタクリル系樹脂、その成形体及びメタクリル系樹脂の製造方法 |
JP2012153807A (ja) * | 2011-01-26 | 2012-08-16 | Sumitomo Chemical Co Ltd | 連続重合装置および重合体組成物の製造方法 |
JP2012214618A (ja) * | 2011-03-31 | 2012-11-08 | Kuraray Co Ltd | メタクリル系樹脂の製造方法及び成形品 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3474081A (en) * | 1966-03-14 | 1969-10-21 | Du Pont | Methyl methacrylate polymer and process for making same |
US4246382A (en) | 1977-11-11 | 1981-01-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Solvent resistent acrylic resin and process for producing the same |
JP3293702B2 (ja) | 1993-11-09 | 2002-06-17 | 三菱瓦斯化学株式会社 | メチルメタクリレート系重合体の製造方法 |
JP3289627B2 (ja) | 1996-12-26 | 2002-06-10 | 住友化学工業株式会社 | メチルメタクリレート系重合体の製造法 |
JP3628518B2 (ja) * | 1998-07-14 | 2005-03-16 | 三菱レイヨン株式会社 | メタクリル系重合体およびその製造方法 |
JP5026671B2 (ja) | 2005-01-14 | 2012-09-12 | 三菱レイヨン株式会社 | アクリル系樹脂組成物および該組成物を含む車両用部材 |
DE602006020610D1 (de) | 2005-11-24 | 2011-04-21 | Asahi Kasei Chemicals Corp | Methacrylharz und herstellungsverfahren dafür |
JP5716266B2 (ja) | 2009-08-14 | 2015-05-13 | 三菱レイヨン株式会社 | メタクリル系樹脂の製造方法 |
JP5763335B2 (ja) | 2009-12-25 | 2015-08-12 | 旭化成ケミカルズ株式会社 | 射出成形体、射出成形体を成形するために用いる溶融成形用メタクリル系樹脂の製造方法、射出成形用メタクリル系樹脂組成物 |
JP5674325B2 (ja) | 2010-02-18 | 2015-02-25 | 旭化成ケミカルズ株式会社 | メタクリル樹脂組成物を用いて得られた成形体 |
JP5150708B2 (ja) * | 2010-11-08 | 2013-02-27 | 住友化学株式会社 | 連続重合装置および重合体組成物の製造方法 |
JP2012111860A (ja) | 2010-11-25 | 2012-06-14 | Sumitomo Chemical Co Ltd | 車両部材用メタクリル樹脂組成物 |
US20130333832A1 (en) * | 2011-03-03 | 2013-12-19 | Basell Polyolefine Gmbh | Process for preparing ethylene homopolymers or copolymers in a tubular reactor with at least two reaction zones having different concentrations of chain transfer agent |
JP2012207203A (ja) | 2011-03-17 | 2012-10-25 | Sumitomo Chemical Co Ltd | 重合体組成物の製造方法 |
CN102702339B (zh) | 2011-05-24 | 2013-10-30 | 华南师范大学 | 斜带石斑鱼补体c3基因、载体、重组菌株和蛋白及其应用 |
-
2012
- 2012-12-03 JP JP2012264021A patent/JP6002017B2/ja active Active
-
2013
- 2013-11-29 WO PCT/JP2013/082750 patent/WO2014088082A1/ja active Application Filing
- 2013-11-29 KR KR1020157014598A patent/KR102001281B1/ko active IP Right Grant
- 2013-11-29 US US14/649,076 patent/US9522969B2/en active Active
- 2013-11-29 CN CN201380072087.7A patent/CN104955853B/zh active Active
- 2013-11-29 SG SG11201504287WA patent/SG11201504287WA/en unknown
- 2013-11-29 TW TW102143779A patent/TWI580696B/zh not_active IP Right Cessation
- 2013-11-29 EP EP13860754.4A patent/EP2927249A4/en not_active Withdrawn
-
2015
- 2015-06-03 SA SA515360508A patent/SA515360508B1/ar unknown
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5129914B2 (ja) | 1973-08-15 | 1976-08-28 | ||
JPS5217555B2 (ja) | 1973-08-15 | 1977-05-16 | ||
JPS54149788A (en) | 1978-05-17 | 1979-11-24 | Asahi Chem Ind Co Ltd | Preparation of solvent-resistant acrylic resin |
JPS58101140A (ja) | 1981-12-10 | 1983-06-16 | Mitsubishi Rayon Co Ltd | 良流動性アクリル樹脂組成物 |
JPH0153682B2 (ja) | 1982-02-26 | 1989-11-15 | Sumitomo Chemical Co | |
JPH0448802B2 (ja) | 1983-05-17 | 1992-08-07 | Sumitomo Chemical Co | |
JPS6289710A (ja) | 1985-10-15 | 1987-04-24 | Asahi Chem Ind Co Ltd | メタクリル系樹脂の製造方法 |
JPH0349925A (ja) | 1989-07-17 | 1991-03-04 | Sumitomo Chem Co Ltd | 熱可塑性重合体組成物の脱揮押出方法 |
JPH06240093A (ja) | 1993-02-12 | 1994-08-30 | Sumitomo Chem Co Ltd | メタクリル系の樹脂組成物 |
JPH07206906A (ja) * | 1994-01-07 | 1995-08-08 | Mitsubishi Gas Chem Co Inc | 耐熱分解性を有するメタクリル樹脂及びその製造方法 |
JPH07206905A (ja) * | 1994-01-07 | 1995-08-08 | Mitsubishi Gas Chem Co Inc | 耐熱分解性を有するメタクリル樹脂及びその製造方法 |
JP2004211105A (ja) | 2004-04-21 | 2004-07-29 | Mitsubishi Gas Chem Co Inc | メタクリル樹脂の製造方法 |
JP2006298966A (ja) | 2005-04-15 | 2006-11-02 | Mitsubishi Rayon Co Ltd | 導光板用アクリル樹脂組成物 |
JP2008538794A (ja) | 2005-04-25 | 2008-11-06 | ルーサイト インターナショナル ユーケー リミテッド | アクリルブレンド |
JP2010059305A (ja) | 2008-09-03 | 2010-03-18 | Mitsubishi Rayon Co Ltd | メタクリル系樹脂組成物 |
WO2011049203A1 (ja) | 2009-10-22 | 2011-04-28 | 旭化成ケミカルズ株式会社 | メタクリル系樹脂、その成形体及びメタクリル系樹脂の製造方法 |
JP2012153807A (ja) * | 2011-01-26 | 2012-08-16 | Sumitomo Chemical Co Ltd | 連続重合装置および重合体組成物の製造方法 |
JP2012214618A (ja) * | 2011-03-31 | 2012-11-08 | Kuraray Co Ltd | メタクリル系樹脂の製造方法及び成形品 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2927249A4 |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015199038A1 (ja) * | 2014-06-23 | 2015-12-30 | 住友化学株式会社 | メタクリル樹脂組成物およびその成形体 |
JP2016008237A (ja) * | 2014-06-23 | 2016-01-18 | 住友化学株式会社 | メタクリル樹脂組成物およびその成形体 |
TWI671349B (zh) * | 2014-06-23 | 2019-09-11 | 日商住友化學股份有限公司 | 甲基丙烯酸樹脂組成物及其成形體 |
CN106459267A (zh) * | 2014-06-23 | 2017-02-22 | 住友化学株式会社 | 甲基丙烯酸树脂组合物及其成型体 |
US20170190896A1 (en) * | 2014-06-23 | 2017-07-06 | Sumitomo Chemical Company, Limited | Methacrylic resin composition and molded article of same |
US20170298157A1 (en) * | 2014-09-30 | 2017-10-19 | Kuraray Co., Ltd. | Method for producing (meth)acrylic resin |
JPWO2017010323A1 (ja) * | 2015-07-14 | 2018-06-14 | 三菱ケミカル株式会社 | メタクリル系樹脂、メタクリル系樹脂の製造方法、成形体及び自動車 |
CN107849188A (zh) * | 2015-07-14 | 2018-03-27 | 三菱化学株式会社 | 甲基丙烯酸系树脂、甲基丙烯酸系树脂的制造方法、成型体及汽车 |
WO2017010323A1 (ja) * | 2015-07-14 | 2017-01-19 | 三菱レイヨン株式会社 | メタクリル系樹脂、メタクリル系樹脂の製造方法、成形体及び自動車 |
US11072673B2 (en) | 2015-07-14 | 2021-07-27 | Mitsubishi Chemical Corporation | Methacrylic resin, method for producing methacrylic resin, shaped article and automobile |
WO2018066393A1 (ja) * | 2016-10-04 | 2018-04-12 | 住友化学株式会社 | メタクリル樹脂組成物およびその成形体 |
JPWO2018066393A1 (ja) * | 2016-10-04 | 2019-07-25 | 住友化学株式会社 | メタクリル樹脂組成物およびその成形体 |
EP3524872A4 (en) * | 2016-10-04 | 2020-05-06 | Sumitomo Chemical Company, Limited | METHACRYLIC RESIN COMPOSITION AND MOLDED OBJECT THEREOF |
US11155704B2 (en) | 2016-10-04 | 2021-10-26 | Sumitomo Chemical Company, Limited | Methacrylic resin composition and molded object thereof |
EP3885371A1 (en) | 2020-03-26 | 2021-09-29 | Sumitomo Chemical Company, Limited | Methacrylic resin composition, molded article, and method of producing methacrylic resin composition |
US11851558B2 (en) | 2020-03-26 | 2023-12-26 | Sumitomo Chemical Company, Limited | Methacrylic resin composition, molded article, and method of producing methacrylic resin composition |
EP3991939A1 (en) | 2020-10-30 | 2022-05-04 | Sumitomo Chemical Company Limited | Molded article and method of producing the same |
Also Published As
Publication number | Publication date |
---|---|
KR102001281B1 (ko) | 2019-07-17 |
SA515360508B1 (ar) | 2017-11-08 |
SG11201504287WA (en) | 2015-07-30 |
EP2927249A1 (en) | 2015-10-07 |
KR20150091070A (ko) | 2015-08-07 |
CN104955853B (zh) | 2016-12-14 |
JP2014108988A (ja) | 2014-06-12 |
EP2927249A4 (en) | 2016-05-11 |
US9522969B2 (en) | 2016-12-20 |
CN104955853A (zh) | 2015-09-30 |
US20160185884A1 (en) | 2016-06-30 |
TWI580696B (zh) | 2017-05-01 |
JP6002017B2 (ja) | 2016-10-05 |
TW201434861A (zh) | 2014-09-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6002017B2 (ja) | メタクリル系重合体組成物の製造方法 | |
KR101899630B1 (ko) | 연속 중합 장치 및 중합체 조성물을 제조하는 방법 | |
JP2012207203A (ja) | 重合体組成物の製造方法 | |
TWI597294B (zh) | 製備甲基丙烯酸系聚合物組成物之方法 | |
US9403922B2 (en) | Continuous polymerization device, method for producing polymer composition, and injection valve | |
US9114374B2 (en) | Continuous polymerization apparatus and process for producing polymer composition | |
WO2014136699A1 (ja) | メタクリル酸エステル系モノマーを含む反応液の冷却方法 | |
JP2013203840A (ja) | 連続重合装置の操作方法 | |
JP5984702B2 (ja) | 連続重合装置および重合体組成物の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13860754 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013860754 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20157014598 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14649076 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |