WO2009113609A1 - エポキシ(メタ)アクリレートの製造方法 - Google Patents
エポキシ(メタ)アクリレートの製造方法 Download PDFInfo
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- WO2009113609A1 WO2009113609A1 PCT/JP2009/054733 JP2009054733W WO2009113609A1 WO 2009113609 A1 WO2009113609 A1 WO 2009113609A1 JP 2009054733 W JP2009054733 W JP 2009054733W WO 2009113609 A1 WO2009113609 A1 WO 2009113609A1
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- reaction
- compound
- epoxy
- meth
- acrylate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
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- the present invention relates to a production method capable of continuously producing epoxy (meth) acrylate safely and with high productivity.
- epoxy (meth) acrylate has been produced by a batch method using a reaction kettle.
- an epoxy (meth) acrylate is produced by reacting a carboxyl group of a compound having a carboxyl group and a (meth) acryloyl group with an epoxy group of a compound having an epoxy group.
- the reaction between the carboxyl group and the epoxy group is an exothermic reaction.
- (meth) acryloyl groups are bonded to each other and a runaway reaction occurs in which the reaction product gels. Therefore, precise temperature control and effective heat removal operation are required to suppress excessive generation and accumulation of reaction heat that causes runaway reaction, but the larger the reaction system, for example, the scale of industrial production This is difficult due to the efficiency of stirring and the ability to remove heat.
- a method of adding a polymerization inhibitor is known as a means for stopping the runaway reaction that occurred during the production of epoxy (meth) acrylate. In this method, it is necessary to disperse and dissolve the polymerization inhibitor in the reaction system in a very short time.
- the cross-sectional area of the channel is 300 to 1,000,000 ⁇ m 2 [3 ⁇ 10 ⁇ 4 to 1 (mm) 2 ] is disclosed in which an epoxy compound and a compound having a hydroxyl group are circulated and both compounds are brought into contact with each other to perform a ring-opening addition reaction.
- an epoxy compound and a compound having a hydroxyl group are circulated and both compounds are brought into contact with each other to perform a ring-opening addition reaction.
- Patent Document 2 has a (meth) acryloyl group that causes a runaway reaction, for example, in Example 1, producing a ring-opening reaction product of ethylhexyl alcohol and epichlorohydrin.
- Patent Document 2 does not disclose any measures for preventing runaway reaction due to polymerization of (meth) acryloyl groups, which is a problem in the production of the epoxy (meth) acrylate. Moreover, it takes 160 minutes to sufficiently react the epoxy compound and the compound having a hydroxyl group in the flow path (for example, the reaction rate is 98%), and the production efficiency is very poor.
- An object of the present invention is to provide a production method capable of producing epoxy (meth) acrylate safely and with high productivity.
- the present inventors have used a heat transfer reaction vessel in which a microtubular channel is formed, and a compound (A) having a carboxyl group and a (meth) acryloyl group in the microtubular channel; When the liquid mixture with the compound (B) having an epoxy group is allowed to continuously and liquid-tightly react with the carboxyl group in the compound (A) and the epoxy group in the compound (B).
- the reaction vessel is a container having a microtubular channel having a void size with a fluid cross-sectional area of 0.1 to 4.0 mm 2 flowing in a liquid-tight manner in the microtubular channel, and
- a fluid cross-sectional area of 0.1 to 4.0 mm 2 flowing in a liquid-tight manner in the microtubular channel
- the epoxy (meth) acrylate flowing out from the microchannel after the reaction has a smaller capacity than the batch type, and can be easily temperature controlled by continuous cooling.
- the inventors have found that the runaway reaction of the (meth) acryloyl group is less likely to occur, and that the reaction occurs in a short time, so that an epoxy (meth) acrylate can be produced with high productivity, and the present invention has been completed.
- the present invention has a compound (A) having a carboxyl group and a (meth) acryloyl group and an epoxy group in the microtubular channel of the heat transfer reaction vessel in which the microtubular channel is formed.
- a mixture of the compound (B) is continuously and in a liquid-tight manner, and a continuous epoxy (meth) acrylate is reacted with the carboxyl group in the compound (A) and the epoxy group in the compound (B).
- a manufacturing method comprising:
- the reaction vessel has a microtubular channel having a void size with a fluid cross-sectional area of 0.1 to 4.0 mm 2 flowing in a liquid-tight manner in the microtubular channel, and the transmission
- the thermal reaction vessel is heated to 150 to 260 ° C.
- the present invention provides a method for producing an epoxy (meth) acrylate characterized by continuously cooling a reaction product discharged from a thermal reaction vessel.
- the production method of the present invention it is possible to provide a production method capable of producing epoxy (meth) acrylate safely and with high productivity. Moreover, it is not necessary to introduce large-scale equipment, and it can be expected to reduce investment costs and manufacturing costs.
- the compound (A) used in the present invention has a carboxyl group and a (meth) acryloyl group.
- the compound (A) is not particularly limited as long as it can be supplied without clogging the flow path by means of heating, melting, dissolving, dispersing, etc. Can be used.
- Examples of the compound (A) used in the present invention include acrylic acid, methacrylic acid, dimers and trimer acids thereof, or hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
- Examples thereof include half ester compounds of an isohydroxy (meth) acrylate compound and an acid anhydride, a reaction product of (meth) acrylic acid and epsilon caprolactone, or a mixture thereof. These may be used alone or in combination of two or more.
- the production method using acrylic acid or methacrylic acid having a large calorific value in the reaction with the compound (B) as the compound (A) has the effect of the present invention, that is, the effect that it can be produced safely. It is preferable because it is sufficiently exerted, and since the acryloyl group concentration is high, the polymerization is easy.
- the compound (B) used in the present invention has an epoxy group.
- the compound (B) is not particularly limited as long as it can be supplied without clogging the flow path by means of heating, melting, dissolving, dispersing, etc., even if it is a solid at room temperature or a liquid with high viscosity, and is publicly known. These compounds can be used.
- Examples of the compound (B) used in the present invention include epoxy resins.
- Examples of the epoxy resin include bisphenol-type epoxy resins, naphthalene-type epoxy resins, cresol novolak-type and phenol novolak-type epoxy resins; halogenated bisphenol-type epoxy resins, halogenated novolak-type epoxy resins, and polyvalent carboxylic acids.
- Acid glycidyl ester resins aliphatic epoxy resins, and alicyclic epoxy resins, polyalkylene glycol diglycidyl ethers, allyl glycidyl ethers, phenyl glycidyl ethers, triglycidyl isocyanurates and their derivatives, polyglycidyl (meth) acrylates and glycidyl Examples thereof include copolymers of glycidyl group-containing unsaturated monomers such as (meth) acrylates and other unsaturated monomers. These may be used alone or in combination of two or more.
- the production method using an epoxy resin having an epoxy equivalent having a large calorific value at the time of reaction with the compound (A) as the compound (B) of 200 or less is the effect of the present invention, that is, safely produced. It is preferable because the effect that it is possible can be sufficiently exhibited.
- a bisphenol type epoxy resin or a naphthalene type epoxy resin, which is an aromatic epoxy resin is used as the compound (B)
- these compounds are likely to cause polymerization and have a large calorific value, so that they can be used in the production method of the present invention. It is preferable because the effects of the production method of the present invention can be sufficiently exhibited.
- the heat transfer reaction vessel used in the method for producing an epoxy (meth) acrylate of the present invention has a microtubular channel formed therein. Then, a mixed liquid of the compound (A) having a carboxyl group and a (meth) acryloyl group and the compound (B) having an epoxy group is continuously and liquid-tightly passed through this microchannel to obtain the compound (A). An epoxy (meth) acrylate is continuously produced by reacting a carboxyl group having an epoxy group with a compound (B).
- the heat transfer reaction vessel used in the present invention preferably has a microtubular channel having a void size with a fluid cross-sectional area of 0.3 to 1.0 mm 2 flowing in a liquid-tight manner in the microtubular channel.
- the “cross section” used in the present invention means a cross section perpendicular to the flow direction in the reaction channel, and the “cross sectional area” means the area of the cross section.
- the Reynolds number of the reaction solution flowing through the microtubular channel is in the range of 0.4 to 100.
- the flowing fluid becomes a laminar flow.
- the compound (A) and the compound (B) Since far-away compounds have very few opportunities to contact each other, they are difficult to react. For this reason, the compound (A) and the compound (B) mainly react with each other in the vicinity, and the reaction does not proceed any further even if they move further in the flow path.
- the inventors have applied a compound (A) and a compound within a range in which the Reynolds number is 0.4 to 100 in a microtubular flow channel having a void size with a fluid cross-sectional area of 0.1 to 4.0 mm 2 .
- the Reynolds number is preferably 1 to 50. If the Reynolds number is less than 0.4, the reaction proceeds slowly and stays for a long time, which may cause gelation. If the Reynolds number exceeds 100, the reaction efficiency is limited, and the reactor becomes longer.
- the Reynolds number as used in the present invention is calculated according to the following formula (1).
- Reynolds number (D ⁇ u ⁇ ⁇ ) / ⁇ (1)
- D inner diameter of the flow path
- u average flow velocity
- ⁇ fluid density
- ⁇ fluid viscosity
- D inner diameter of the channel: equivalent diameter (m) of the microtubular channel.
- u average flow rate: the flow rate (m / sec) of the mixture of the compound (A) and the compound (B).
- ⁇ fluid density: The density of water at 20 ° C. is 998.2 kg / m 3 .
- ⁇ fluid viscosity: The viscosity of water at 20 ° C. is 1.002 mPa ⁇ s.
- the heat transfer reaction vessel needs to be heated to 150 to 260 ° C. By selecting such a temperature, the reaction between the carboxyl group and the epoxy group occurs efficiently, but the runaway reaction that is the polymerization of the (meth) acryloyl group does not occur.
- the temperature of the heat transfer reaction vessel is preferably from 160 to 240 ° C., more preferably from 170 to 220 ° C. because runaway reaction hardly occurs and production efficiency is good.
- the cross-sectional area of the mixed fluid flowing through the microchannel included in the reaction apparatus used in the present invention By selecting the temperature of the reaction vessel as described above, an efficient reaction between the carboxyl group and the epoxy group occurs, and as a result, the epoxy (meth) acrylate generated before the polymerization reaction between the (meth) acryloyl groups occurs. It can be cooled.
- the flow rate when the mixed fluid flows through the micro flow path is preferably 1.8 ⁇ 10 ⁇ 4 to 0.28 m / sec, more preferably 4.5 ⁇ 10 ⁇ 4 to 0.14 m / sec. preferable.
- the heat transfer reaction vessel used in the production method of the present invention has a heat exchange function, and has a void size in which a fluid cross-sectional area flowing in a liquid-tight manner in a microtubular channel is 0.1 to 4 mm 2.
- a microtubular channel should just be used, and there is no restriction
- Examples of such an apparatus include an apparatus in which the channel (hereinafter, simply referred to as “microchannel”) is provided in a member used as a chemical reaction device.
- the cross-sectional shape obtained by cutting the microtubular channel perpendicular to the flow of the mixed fluid containing the compound (A) and the compound (B) is a square, a rectangle including a rectangle, a trapezoid or a parallelogram, It may be a polygonal shape including a triangle, a pentagon, etc. (a shape in which these corners are rounded, a high aspect ratio, that is, including a slit shape), a star shape, a semicircle, a circle including an ellipse, or the like.
- the cross-sectional shape of the microchannel does not need to be constant.
- the method for forming the microtubular channel is not particularly limited, but in general, the member (X) having a groove on the surface thereof is laminated with another member (Y) on the surface having the groove, bonded, or the like. To form a space between the member (X) and the member (Y).
- the member (X) can be provided with a heat exchange function.
- a groove for allowing the temperature adjusting fluid to flow may be provided on the surface of the member (X), and another member may be bonded or laminated to the surface provided with the groove for allowing the temperature adjusting fluid to flow.
- a member (X) having a groove on the surface and a member (Y) provided with a groove for flowing a temperature-controlled fluid include a surface provided with a groove, and a surface provided with a groove of another member.
- a flow path may be formed by fixing the opposite surface, and a plurality of these members (X) and members (Y) may be fixed alternately.
- the groove formed on the surface of the member may be formed as a so-called groove lower than the peripheral portion thereof, or may be formed between the walls standing on the surface of the member.
- the method of providing the groove on the surface of the member is arbitrary, and for example, methods such as injection molding, solvent casting method, melt replica method, cutting, etching, photolithography (including energy beam lithography), and laser ablation can be used.
- the layout of the flow paths in the member may be in the form of a straight line, a branch, a comb, a curve, a spiral, a zigzag, or any other arrangement according to the purpose of use.
- the flow path is, for example, a mixing field, an extraction field, a separation field, a flow rate measurement unit, a detection unit, a liquid storage tank, a membrane separation mechanism, a connection port to the inside or outside of the device, a tangential line, a development path for chromatography or electrophoresis Further, it may be connected to a part of the valve structure (portion surrounding part), a pressurizing mechanism, a depressurizing mechanism or the like.
- the outer shape of the member does not need to be particularly limited, and can take a shape according to the purpose of use.
- the shape of the member may be, for example, a plate shape, a sheet shape (including a film shape, a ribbon shape, etc.), a coating film shape, a rod shape, a tube shape, and other complicated shapes. External dimensions such as thickness are preferably constant.
- the material of the member is arbitrary, and may be, for example, a polymer, glass, ceramic, metal, semiconductor, or the like.
- the member (X) having a groove on the surface as described above, another member (Y) is fixed to the surface having the groove by lamination, bonding or the like, and the member (X) What formed the microtubular flow path by forming as a space between a member and a member (Y) can be used preferably.
- a heat transfer reaction vessel include those having a structure in which a plurality of heat transfer plate-like structures having a plurality of grooves formed on the surface are stacked.
- the flow path described in the above formation method is a combination of at least two members and a space formed between the members is used as the flow path. It may be used as a road.
- the length of the flow path may be appropriately set so as to obtain a desired reaction rate, but is usually 0.5 to 100 m, preferably 3 to 70 m.
- the heat transfer reaction vessel used in the production method of the present invention for example, a heat transfer plate-like structure provided with a microtubular flow channel and a flow channel for flowing a fluid for heat exchange between the mixed solution are arranged.
- Examples include an apparatus in which the provided heat conductive plate-like structures are alternately stacked.
- the mixing space which mixes the compound (A) and the compound (B) which were supplied separately in front of this heat-transfer reaction container or in this apparatus can also be provided.
- it is preferable that the compound (A) and the compound (B) are continuously introduced into the heat transfer reaction vessel as a mixed solution obtained by mixing them in advance.
- FIG. 1 shows a reaction apparatus in which a plate provided with a microtubular channel for flowing a mixed liquid and a plate provided with a flow path for flowing a fluid that exchanges heat with the mixed liquid are alternately stacked.
- 1 is a schematic configuration example of a chemical reaction device 1 having a microtubular channel having a void size with a fluid cross-sectional area of 0.1 to 4 mm 2 flowing in a liquid-tight manner in the microtubular channel.
- Each of the first plates is provided with a channel (hereinafter referred to as a reaction channel) having a cross-sectional area of 0.1 to 4.0 (mm 2 ) (hereinafter referred to as a reaction channel).
- a reaction channel having a cross-sectional area of 0.1 to 4.0 (mm 2 )
- mm 2 mm 2
- the second plate is provided with a flow channel for temperature control fluid (hereinafter referred to as a temperature control channel) (hereinafter, the plate provided with the temperature control channel is referred to as a temperature control plate).
- the supply ports and the discharge ports are dispersed and arranged in each region of the end surface 1b, 1c, side surface 1d, 1e of the chemical reaction device 1, and the compound (A) and
- the joint part 32 which consists of the connector 30 and the joint part 31 for flowing a compound (B), and a temperature control fluid is each connected.
- a fluid ⁇ (mixed liquid) containing the compound (A) and the compound (B) is supplied from the end face 1b through these joint portions, and contains a reaction product of the compound (A) and the compound (B).
- the fluid ⁇ to be discharged is discharged to the end surface 1c, and the temperature control fluid ⁇ is supplied from the side surface 1e and discharged to the side surface 1d.
- the shape in plan view of the device for chemical reaction 1 is not limited to the rectangular shape shown in the figure, and may be a square shape or a rectangular shape in which the distance between the side surfaces 1d and 1e is longer than between the end surfaces 1b and 1c. Therefore, in accordance with the illustrated shape, the direction from the end surface 1b to the end surface 1c is referred to as the longitudinal direction of the process plate and temperature control plate of the chemical reaction device 1, and the direction from the side surface 1d to the side surface 1e is referred to as the chemical reaction device. This is referred to as the short direction of the process plate 1 and the temperature control plate.
- the process plate extends on one surface 2 a by passing through a channel 4 having a concave groove shape in the longitudinal direction of the process plate, and a plurality of process plates are arranged at a predetermined interval p 0 in the short direction.
- L be the length of the flow path 4.
- the cross-sectional shape is a width w 0 and a depth d 0 .
- the cross-sectional shape of the flow path 4 can be appropriately set according to the type, flow rate, and flow path length L of the fluid ⁇ containing the compound (A) and the compound (B).
- the width w 0 and the depth d 0 are set in the range of 0.1 to 16 [mm] and 0.1 to 2 [mm], respectively.
- variety and a depth is a case where a drawing is referred, Comprising: This value can be interpreted suitably so that it may become a wide value with respect to a heat transfer surface.
- the number is, for example, 1 to 1000, preferably 10 to 100 per plate.
- the fluid ⁇ is flowed into each flow path 4 and is supplied from one end face 2b side and discharged to the other end face 2c side as shown by arrows in FIGS.
- the temperature control plate is provided with a temperature control flow path 6 having a concave groove shape on one surface 3 a at a predetermined interval.
- the cross-sectional area of the temperature control channel 6 is not particularly limited as long as heat can be transferred to the reaction channel, but is generally in the range of 0.1 to 4.0 (mm 2 ). More preferably, it is 0.3 to 1.0 (mm 2 ).
- the number of the temperature control channels 6 may be an appropriate number in consideration of the heat exchange efficiency, and is not particularly limited. For example, 1 to 1000, preferably 10 to 100 per plate is used. It is.
- the temperature control channel 6 flows in a plurality of main channels 6a arranged in the longitudinal direction of the temperature control plate and upstream and downstream ends of the main channel 6a.
- the supply-side flow path 6b and the discharge-side flow path 6c are bent at right angles twice and open to the outside from the side surfaces 3d and 3e of the temperature control plate.
- the supply side channel 6 b and the discharge side channel 6 c are each composed of one. .
- each main flow path 6a of the temperature control flow path 6 is provided in a range in which the range in which the flow paths 4 are distributed overlaps the stack direction in the short direction of the temperature control plate.
- the main flow paths 6a are arranged in the stacking direction so as to be positioned between two adjacent flow paths 4, 4. More preferably, each main flow path 6a overlaps each flow path 4 in the stacking direction. Arrange as follows.
- the plurality of process plates and temperature control plates are stacked by alternately stacking process plates and temperature control plates in the same direction, and are fixed and stacked on each other.
- each flow path 4 and the temperature control flow path 6 are covered with a lower surface of a plate on which a groove is opened and a tunnel shape having a rectangular cross section with both ends open. It is said.
- Each process plate and temperature control plate can be made of an appropriate metal material.
- a flow path 4 and a temperature control path 6 are formed by etching a stainless steel plate, and the flow path surface is changed. It can be manufactured by electrolytic polishing finish.
- a manufacturing apparatus shown in FIG. 4 can be exemplified.
- a production apparatus having the following chemical reaction device can be exemplified.
- the chemical reaction device has a structure shown in FIG. 1, and as a structure, process plates and temperature control plates are alternately stacked. A flow path 4 is formed in the process plate, and a temperature control flow path 6 is formed in the temperature control plate.
- the chemical reaction device 40 used in the manufacturing apparatus shown in FIG. 4 has 20 temperature control channels 6 formed by etching as well as three process plates having 20 reaction channels 4 formed by dry etching. Four temperature control plates are alternately stacked.
- the material of the process plate 2 and the temperature control plate 3 is SUS304, and the plate thickness is 1 mm.
- the cross-sectional dimensions of the reaction channel 4 and the temperature control channel 6 are both width 1.2 mm ⁇ depth 0.5 mm.
- the chemical reaction device 50 used in the manufacturing apparatus shown in FIG. 4 has five temperature control channels 6 formed by etching as well as two process plates having five reaction channels 4 formed by dry etching. Three temperature control plates are alternately stacked.
- the material of the process plate 2 and the temperature control plate 3 is SUS304, and the plate thickness is 1 mm.
- the cross-sectional dimensions of the reaction channel 4 and the temperature control channel 6 are both width 1.2 mm ⁇ depth 0.5 mm.
- These pipes are connected to the inlet of a mixer [mixing space for mixing the compound (A) and the compound (B)] 65.
- the compound (A) (61) and the compound (B) (62) are mixed to form a mixed fluid containing the compound (A) (61) and the compound (B) (62).
- This fluid moves to the inlet 1 b of the chemical reaction device 40, 50, or 60 through a pipe connected to the outlet of the mixer 65.
- a temperature control device 66 is connected to the chemical reaction device 40, 50, or 60.
- the compound (A) and the compound (B) in the mixed fluid react with each other by moving through the micro flow path in the chemical reaction device 40, 50 or 60. It moves through the microchannel in the chemical reaction device 40, 50 or 60 and reaches the outlet 1 c of the chemical reaction device 40, 50 or 60. Then, it moves to the inflow port of the cooling heat exchanger 67 through the pipe connected to the outflow port.
- the Reynolds number and temperature can be changed, so that the heat transfer reaction vessel is formed with a microtubular channel such as the chemical reaction devices 40 and 50 described above.
- the reaction is preferably carried out using a reaction apparatus in which a plurality of thermal reaction vessels are arranged in series.
- compound (A) and compound (B) may be placed in separate syringe pumps as described above and stirred with a mixer to form a mixed solution, but compound (A) and compound (B) are mixed in advance. It is also possible to prepare a mixed solution, put it in one syringe pump, and supply it to the chemical reaction device.
- the obtained reactive organism is discharged from the heat transfer reaction vessel. And this reaction product is cooled continuously.
- the runaway reaction of the (meth) acryloyl group can be prevented by cooling the reaction product promptly and continuously.
- This cooling may be, for example, natural air cooling as it is in the air as it is, or it may be discharged immediately after being discharged into the solvent for cooling, or distributed to a cooling device having a heat exchange function. May be cooled.
- this cooler a cooling heat transfer device in which a micro tubular channel is formed is preferable.
- a cooling heat transfer device in which a microtubular channel is formed which communicates with the reaction solution outlet (outflow port) of the heat transfer reaction vessel. It can be preferably carried out by continuously circulating the reaction product.
- a fluid ⁇ [epoxy (meta) containing a reaction product of the compound (A) (61) and the compound (B) (62) moved to the inlet of the cooling heat transfer device (cooling device) 67. ) Acrylate] is cooled while moving in the cooling heat exchanger 67 and reaches the outlet of the cooling heat exchanger 67.
- the fluid ⁇ is discharged from the cooling heat exchanger 67 through the pipe connected to the outlet, and is discharged to the receiving container 70 through the exhaust pressure valve 69.
- a heat transfer reaction vessel having a microtubular channel formed therein which can be preferably used as the heat transfer reaction vessel, has a heat transfer property in which a plurality of grooves are formed on the surface.
- Those having a structure in which a plurality of plate-like structures are laminated can be preferably used.
- the apparatus which has an above described chemical reaction device can be illustrated.
- the reaction between the compound (A) and the compound (B) in the microtubular channel can be stopped at an arbitrary yield, and the reactants or unreacted materials may be discharged out of the reaction channel system.
- the viscosity of the reaction product increases as the reaction proceeds. Therefore, in consideration of pressure loss, for example, the reaction from the initial reaction stage to the intermediate reaction stage is carried out by the production method of the present invention, and then the unreacted substance is removed. It is also possible to transfer the composition to be contained in a batch-type reactor or storage tank, or a flow path having a larger cross-sectional area, and react the remaining unreacted materials.
- the compound (A) or compound (B) used in the production method of the present invention may be a liquid having a supplyable viscosity, and may be heated to enable supply, or diluted and dissolved in a solvent. May be.
- an additive such as a catalyst (initiator) or a polymerization inhibitor may be added to the compound (A) or the compound (B) as long as the flow path is not blocked.
- the compound (A) and compound (B) used in the present invention may be supplied alone or in a mixed state in the flow path as long as they do not adversely affect the reaction. Moreover, you may dilute and use for a solvent as needed, and additives, such as a catalyst (initiator) and a polymerization inhibitor, may be added.
- the catalyst (initiator) is not particularly limited as long as it can be dissolved in the compound (A) and the compound (B) or dispersed within a range that does not block the flow path, or can be used together by dissolving in a solvent.
- phosphines such as triphenylphosphine, amines such as triethylamine, quaternary ammonium salts such as tetramethylammonium salt and benzyltrimethylammonium salt, quaternary phosphonium salts,
- imidazoles such as -methylimidazole and 2-methyl-4-methylimidazole.
- the polymerization inhibitor is not particularly limited as long as it can be dissolved in the compound (A) and the compound (B) or can be dispersed within a range that does not block the flow path, or can be used together by dissolving in a solvent.
- Inhibitors can be used, and examples include methoquinone, hydroquinone, 1,4 naphthoquinone, phenothiazine, t-butylhydroquinone, aluminum N-nitrophenylhydroxyamine and the like.
- ⁇ Chemical reaction device used in Examples and Comparative Examples> a chemical reaction device having the structure shown in FIG. 1 was used.
- the process plate 2 and the temperature control plate 3 are alternately stacked.
- a flow path 4 is formed in the process plate, and a temperature control flow path 6 is formed in the temperature control plate.
- chemical reaction devices 40 and 50 shown in FIG. 4 having different Reynolds numbers were used when the same flow rate was applied (when the flow rate was the same).
- the chemical reaction device 40 is formed by alternately stacking four temperature control plates having 20 temperature control channels 6 formed by etching as well as three process plates having 20 reaction channels 4 formed by dry etching. Yes.
- the material of the process plate 2 and the temperature control plate 3 is SUS304, and the plate thickness is 1 mm.
- the cross-sectional dimensions of the reaction channel 4 and the temperature control channel 6 are both width 1.2 mm ⁇ depth 0.5 mm.
- the length of the reaction channel 4 is 80 mm.
- the chemical reaction device 50 is formed by alternately laminating three temperature control plates having five temperature control channels 6 formed by etching as well as two process plates having five reaction channels 4 formed by dry etching. Yes.
- the material of the process plate 2 and the temperature control plate 3 is SUS304, and the plate thickness is 1 mm.
- the cross-sectional dimensions of the reaction channel 4 and the temperature control channel 6 are both width 1.2 mm ⁇ depth 0.5 mm.
- the length of the reaction channel 4 is 40 mm.
- the chemical reaction device 50 was used for the cooling heat exchanger 67.
- Example 1 In the manufacturing apparatus 80 shown in FIG. 4, an apparatus in which one chemical reaction device 40 is connected is used.
- a mixed solution 61 was prepared by mixing and dissolving 737 g of a bisphenol A type epoxy resin (epoxy equivalent 189), 277 g of acrylic acid, 5.1 g of triphenylphosphine as a catalyst, and 0.5 g of methoquinone as a polymerization inhibitor.
- reaction time means the total time for which the mixed fluid of the compound (A) and the compound (B) stays in the chemical reaction device. (The same applies hereinafter).
- Example 2 In the manufacturing apparatus 80 shown in FIG. 4, an apparatus in which six chemical reaction devices 50 are connected is used.
- a mixed solution 61 was prepared by mixing and dissolving 737 g of a bisphenol A type epoxy resin (epoxy equivalent 189), 277 g of acrylic acid, 5.1 g of triphenylphosphine as a catalyst, and 0.5 g of methoquinone as a polymerization inhibitor.
- epoxy acrylate was produced at a reaction rate of 86.4% in a reaction time of 135 seconds. Also, no runaway reaction occurred.
- Example 3 A reaction mixture was obtained in the same manner as in Example 2 except that the Reynolds number was 3.72. From the quantification result of unreacted acrylic acid in the reaction mixture, epoxy acrylate was produced at a reaction rate of 92.3% in a reaction time of 63 seconds. Also, no runaway reaction occurred.
- Example 4 A reaction mixture was obtained in the same manner as in Example 2 except that the Reynolds number was 7.44. From the quantification result of unreacted acrylic acid in the reaction mixture, epoxy acrylate was produced at a reaction rate of 86% in a reaction time of 32 seconds. Also, no runaway reaction occurred.
- Example 5 A reaction mixture was obtained in the same manner as in Example 2 except that the Reynolds number was 2.62. From the quantification result of unreacted acrylic acid in the reaction mixture, epoxy acrylate was produced at a reaction rate of 99% in a reaction time of 90 seconds. Also, no runaway reaction occurred
- the reaction rate is 99% after passing time of 90 seconds, and the reaction is almost complete.
- a runaway reaction has not been achieved even at a reaction temperature that could not be achieved with a conventional reaction kettle, and the reaction time could be shortened to a level that could not be achieved with a conventional reaction kettle.
- the weight average molecular weight of the epoxy (meth) acrylate compound was 733.
- a refractive index detector (RI) was used as a detector, and an HLC-8120GPC manufactured by Tosoh Corporation equipped with TSKgel G1000HXL + G2000HXL + G3000HXL + G4000HXL as a measuring column was used.
- tetrahydrofuran (THF) was used as a solvent, the sample was adjusted to a concentration of 0.2 to 0.3%, and measurement was performed under the conditions of a column temperature of 40 ° C. and a flow rate of 1.0 ml / min.
- Comparative Example 1 A reaction mixture was obtained in the same manner as in Example 1 except that the Reynolds number was 0.26. From the quantification result of unreacted acrylic acid in the reaction mixture, epoxy acrylate was produced at a reaction rate of 67.4% in a reaction time of 296 seconds. Also, no runaway reaction occurred.
- Comparative Example 2 In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, nitrogen inlet, and air inlet, 737 g of bisphenol A type epoxy resin (epoxy equivalent 189), 277 g of acrylic acid, 5.1 g of triphenylphosphine as a catalyst, polymerization prohibited As an agent, 0.5 g of methoquinone was added, the temperature was raised to 100 ° C. over 3 hours while paying attention to heat generation, and the reaction was continued at 100 ° C. for 12 hours. The reaction was terminated when the acid value became 2 or less, and a comparative epoxy acrylate was obtained.
- the weight average molecular weight of this epoxy (meth) acrylate compound measured under the same measurement conditions was 793.
- Comparative Example 3 In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, nitrogen inlet, and air inlet, 737 g of bisphenol A type epoxy resin (epoxy equivalent 189), 277 g of acrylic acid, 5.1 g of triphenylphosphine as a catalyst, polymerization prohibited As an agent, 0.5 g of methoquinone was charged and heated to 100 ° C. over 30 minutes. Immediate heat generation occurred and control became impossible. The flask gelled and a large amount of gas was generated from the flask.
- Table 1 shows the temperature-controlled fluid temperature, Reynolds number, reaction time, and reaction rate of the resulting epoxy acrylate obtained by heating the chemical reaction devices of Examples 1 to 5 and Comparative Example 1.
- the reaction rate increases as the Reynolds number increases, and epoxy acrylate can be produced efficiently.
- Example 5 it can be seen that the reaction is almost completed in a very short time without the occurrence of a runaway reaction. This is because the compound (A) and the compound (B) are mixedly supplied at a flow rate corresponding to a specific Reynolds number (0.4 or more) in a microchannel that satisfies a specific condition, and a batch type reaction mode such as a reaction kettle. This is a result achieved by reacting in a micro flow path at a reaction temperature (180 ° C.) that cannot normally be taken due to the risk of runaway reaction.
- Comparative Example 1 a mixed solution of a bisphenol A type epoxy resin and acrylic acid is supplied into a specific microchannel at a flow rate corresponding to a specific Reynolds number (less than 0.4), and a batch type reaction mode such as a reaction kettle Shows the results of reaction in a microchannel at a reaction temperature (180 ° C.) that cannot normally be taken due to the risk of runaway reaction.
- a reaction temperature 180 ° C.
- the Reynolds number is less than 0.4, even if the reaction is carried out for a long time at a very high reaction temperature, the viscosity of the reaction product increases with the progress of the reaction, and the mixing property due to molecular diffusion decreases significantly. It can be seen that the reaction does not proceed in a short time.
- Comparative Example 2 shows the results of a batch system that is usually performed in a reaction kettle. In order to suppress the runaway reaction and sufficiently control the temperature in the system, the temperature is gradually raised over 3 hours and charged at a low temperature of 100 ° C. for 15 hours. I need it. From this result, it can be seen that the result of Example 5 is a safe and efficient method for producing an epoxy (meth) acrylate compound.
- Comparative Example 3 shows the result of performing the reaction in a batch mode by rapidly raising the temperature to 100 ° C. in 30 minutes after the raw materials were charged in order to shorten the reaction time. After reaching 100 ° C., rapid heat generation occurred, and gelation occurred with intense gas generation. This resulted in a so-called runaway reaction. This result also shows that the result of Example 5 is a safe and efficient method for producing an epoxy (meth) acrylate compound.
- FIG. 3 is an exploded perspective view showing two types of plate structures in FIG. 2. It is a schematic block diagram which shows typically the manufacturing apparatus used by the Example and the comparative example. It is a graph which shows the reaction rate with respect to the passage time in an Example and a comparative example.
- Manufacturing equipment 61 ... Compound (A) 62... Compound (B) 63 ... Syringe pump 64 ... Syringe pump 65 ... Mixer 66 ... Temperature control device 67 ... Heat exchanger for cooling 68 ... Temperature Control device 69... Exhaust pressure valve 70... Receiving container 80... Schematic configuration diagram schematically showing a resin manufacturing apparatus used in Examples and Comparative Examples
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Abstract
Description
前記反応容器が、前記微小管状流路内を液密状に流通する流体断面積が0.1~4.0mm2となる空隙サイズを有する微小管状流路を有するものであり、かつ、前記伝熱性反応容器を150~260℃に加熱すると共に、前記微小管状流路内を流通する反応液のレイノルズ数が0.4~100の範囲となるように反応させ、次いで、反応終了後、前記伝熱性反応容器から吐出された反応生成物を連続的に冷却することを特徴とするエポキシ(メタ)アクリレートの製造方法を提供するものである。
レイノルズ数=(D×u×ρ)/μ・・・式(1)
ここで、D(流路の内径)、u(平均流速)、ρ(流体密度)、μ(流体粘度)である。本発明において、レイノルズ数は上記式(1)の各要素を以下のように定義し、求めた。
u(平均流速):化合物(A)と化合物(B)との混合液の流速(m/秒)である。
ρ(流体密度):20℃における水の密度998.2kg/m3である。
μ(流体粘度):20℃における水の粘度1.002mPa・sである。
化学反応デバイスは図1に示す構造であり、構造としては、プロセスプレートと温調プレートと交互に積層している。プロセスプレートには流路4が形成されおり、また、温調プレートには温調流路6が形成されている。
本実施例では図1に示す構造の化学反応デバイスを用いた。プロセスプレート2と温調プレート3とを交互に積層した構造である。プロセスプレートには流路4が形成されおり、また、温調プレートには温調流路6が形成されている。化学反応デバイスとしては、同じ流量を流したとき(同じ流速で流したとき)レイノルズ数が異なる図4に示す化学反応デバイス40、50を用いた。
図4に示す製造装置80において化学反応デバイス40を一つ繋いだ装置を用いた。先立って、ビスフェノールA型エポキシ樹脂(エポキシ当量189)737g、アクリル酸277g、触媒としてトリフェニルホスフィン5.1g、重合禁止剤としてメトキノン0.5gを混合溶解した混合溶液61を作製した。
図4に示す製造装置80において化学反応デバイス50を6個繋いだ装置を用いた。先立って、ビスフェノールA型エポキシ樹脂(エポキシ当量189)737g、アクリル酸277g、触媒としてトリフェニルホスフィン5.1g、重合禁止剤としてメトキノン0.5gを混合溶解した混合溶液61を作製した。
レイノルズ数を3.72とする以外は、実施例2と同様にして反応混合物を得た。反応混合物中の未反応のアクリル酸の定量結果から、反応時間63秒で反応率92.3%の割合でエポキシアクリレートが生成されていた。又、暴走反応は起こらなかった。
レイノルズ数を7.44とする以外は、実施例2と同様にして反応混合物を得た。反応混合物中の未反応のアクリル酸の定量結果から、反応時間32秒で反応率86%の割合でエポキシアクリレートが生成されていた。又、暴走反応は起こらなかった。
レイノルズ数を2.62とする以外は、実施例2と同様にして反応混合物を得た。反応混合物中の未反応のアクリル酸の定量結果から、反応時間90秒で反応率99%の割合でエポキシアクリレートが生成されていた。又、暴走反応は起こらなかった
レイノルズ数を0.26とする以外は、実施例1と同様にして反応混合物を得た。反応混合物中の未反応のアクリル酸の定量結果から、反応時間296秒で反応率67.4%の割合でエポキシアクリレートが生成されていた。又、暴走反応は起こらなかった。
温度計、攪拌機、水冷コンデンサー、窒素吹き込み口、エアー吹き込み口を備えた4つ口フラスコにビスフェノールA型エポキシ樹脂(エポキシ当量189)737g、アクリル酸277g、触媒としてトリフェニルホスフィン5.1g、重合禁止剤としてメトキノン0.5gを仕込み、発熱に注意しながら3時間かけて100℃まで昇温し、100℃で12時間反応を継続した。酸価が2以下になった時点で反応を終了し、比較対照用エポキシアクリレートを得た。
温度計、攪拌機、水冷コンデンサー、窒素吹き込み口、エアー吹き込み口を備えた4つ口フラスコにビスフェノールA型エポキシ樹脂(エポキシ当量189)737g、アクリル酸277g、触媒としてトリフェニルホスフィン5.1g、重合禁止剤としてメトキノン0.5gを仕込み、30分かけて100℃まで昇温した。直ちに激しい発熱が生じ制御不能となり、フラスコ内がゲル化してフラスコ内より大量のガスが発生した。
β・・・・・化合物(A)と化合物(B)との反応物を含有する流体
γ・・・・・温調流体
1・・・・・化学反応用デバイス
1b・・・・化学反応用デバイスの端面
1c・・・・化学反応用デバイスの端面
1d・・・・化学反応用デバイスの側面
1e・・・・化学反応用デバイスの側面
2・・・・・第1プレート(プロセスプレート)
2a・・・・第1プレートの面
2b・・・・第1プレートの端面
2c・・・・第1プレートの端面
2d・・・・第1プレートの側面
2e・・・・第1プレートの側面
3・・・・・第2プレート(温調プレート)
3a・・・・第2プレートの面
3b・・・・第2プレートの端面
3c・・・・第2プレートの端面
3d・・・・第2プレートの側面
3e・・・・第2プレートの側面
4・・・・・断面凹溝形状の流路
6・・・・・断面凹溝形状の温調流路
6a・・・・断面凹溝形状の主流路
6b・・・・断面凹溝形状の供給側流路
6c・・・・断面凹溝形状の排出側流路
p0・・・・所定間隔
w0・・・・・幅
d0・・・・・深さ
L・・・・・・流路長さ
30・・・・・コネクタ
31・・・・・ジョイント部
32・・・・・継手部
40・・・・・化学反応デバイス
50・・・・・化学反応デバイス
60・・・・・化学反応デバイス
80・・・・・製造装置
61・・・・・化合物(A)
62・・・・・化合物(B)
63・・・・・シリンジポンプ
64・・・・・シリンジポンプ
65・・・・・ミキサー
66・・・・・温調装置
67・・・・・冷却用熱交換器
68・・・・・温調装置
69・・・・・排圧弁
70・・・・・受け容器
80・・・・・実施例及び比較例で用いた樹脂の製造装置を模式的に示す概略構成図
Claims (8)
- 内部に微小管状流路が形成された伝熱性反応容器の該微小管状流路内に、カルボキシル基と(メタ)アクリロイル基とを有する化合物(A)と、エポキシ基を有する化合物(B)との混合液を、連続的かつ液密状に流通させ、前記化合物(A)中のカルボキシル基と前記化合物(B)中のエポキシ基とを反応させるエポキシ(メタ)アクリレートの連続製造方法であって、
前記反応容器が、前記微小管状流路内を液密状に流通する流体断面積が0.1~4.0mm2となる空隙サイズを有する微小管状流路を有するものであり、かつ、前記伝熱性反応容器を150~260℃に加熱すると共に、前記微小管状流路内を流通する反応液のレイノルズ数が0.4~100の範囲となるように反応させ、次いで、反応終了後、前記伝熱性反応容器から吐出された反応生成物を連続的に冷却することを特徴とするエポキシ(メタ)アクリレートの製造方法。 - 反応終了後の反応生成物の冷却を50~90℃の温度条件で行う請求項1記載のエポキシ(メタ)アクリレートの製造方法。
- 前記カルボキシル基と(メタ)アクリロイル基とを有する化合物(A)と、前記エポキシ基を有する化合物(B)とを、これらを予め混合した混合液として連続的に前記伝熱性反応容器に導入する請求項1又は2記載のエポキシ(メタ)アクリレートの製造方法。
- 内部に微小管状流路が形成された伝熱性反応容器を複数直列状に配設してなる反応装置を用いて反応を行う請求項3記載のエポキシ(メタ)アクリレートの製造方法。
- 内部に微小管状流路が形成された伝熱性反応容器が、表面に複数の溝部が形成された伝熱性プレート状構造体を複数枚積層してなる構造を有するものである請求項3記載のエポキシ(メタ)アクリレートの製造方法。
- 前混混合流体を、1.8×10-4~0.28m/秒の流速で微小管状流路に流通させる請求項1記載のエポキシ(メタ)アクリレートの製造方法。
- 前記化合物(A)が(メタ)アクリル酸で、前記化合物(B)がビスフェノール型エポキシ樹脂またはナフタレン型エポキシ樹脂である請求項1記載のエポキシ(メタ)アクリレートの製造方法。
- 連続的な冷却を、前記伝熱性反応容器の反応液出口に連通する、微小管状流路が形成された冷却用伝熱器に連続的に反応生成物を流通させることにより行う請求項1又は2記載のエポキシ(メタ)アクリレートの製造方法。
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US12/922,193 US8759551B2 (en) | 2008-03-14 | 2009-03-12 | Process for producing epoxy (metha)acrylate |
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- 2009-03-12 EP EP09719026A patent/EP2258678B1/en not_active Not-in-force
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011057603A (ja) * | 2009-09-09 | 2011-03-24 | Dic Corp | ウレタン(メタ)アクリレートの製造方法 |
JP2020179395A (ja) * | 2014-09-15 | 2020-11-05 | アルキマル, アクティーゼルスカブ | 酵素処理プラントおよび酵素処理方法 |
JP7050120B2 (ja) | 2014-09-15 | 2022-04-07 | アルキマル, アクティーゼルスカブ | 酵素処理プラントおよび酵素処理方法 |
Also Published As
Publication number | Publication date |
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KR101502647B1 (ko) | 2015-03-13 |
US8148567B2 (en) | 2012-04-03 |
US20110071307A1 (en) | 2011-03-24 |
EP2258740A1 (en) | 2010-12-08 |
EP2258678B1 (en) | 2012-07-11 |
KR20100135717A (ko) | 2010-12-27 |
JP4457329B2 (ja) | 2010-04-28 |
JPWO2009113608A1 (ja) | 2011-07-21 |
EP2258740B1 (en) | 2012-07-11 |
CN101970524B (zh) | 2013-02-27 |
EP2258678A4 (en) | 2011-02-23 |
CN101970398A (zh) | 2011-02-09 |
US20110087041A1 (en) | 2011-04-14 |
KR20100138881A (ko) | 2010-12-31 |
WO2009113608A1 (ja) | 2009-09-17 |
CN101970524A (zh) | 2011-02-09 |
EP2258678A1 (en) | 2010-12-08 |
KR101479370B1 (ko) | 2015-01-05 |
US8759551B2 (en) | 2014-06-24 |
EP2258740A4 (en) | 2011-03-02 |
JP4390020B2 (ja) | 2009-12-24 |
JPWO2009113609A1 (ja) | 2011-07-21 |
CN101970398B (zh) | 2013-06-05 |
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