JP2011057603A - Method for producing urethane (meth)acrylate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for safely producing urethane (meth)acrylate in excellent productivity. <P>SOLUTION: The method for producing urethane (meth)acrylate includes continuously and liquid-tightly circulating a mixed liquid of a hydroxy group-containing compound (A) and a compound (B) containing an isocyanate group and a (meth)acryloyl group through a very small tubular channel of a thermally-conductive reaction vessel having formed the very small tubular channel inside in which the reaction vessel has the very small tubular channel having a void size forming a fluid sectional area of 0.1-4.0 mm<SP>2</SP>for circulation in a liquid tight state in the very small tubular channel, the reaction vessel is heated to 80-250°C, the reaction is carried out so that a Reynolds number of the reaction solution circulating in the very small tubular channel is 0.05-300 and then, after completion of the reaction, the reaction product discharged from the thermally-conductive reaction vessel is continuously cooled. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a production method capable of continuously producing urethane (meth) acrylate safely and with high productivity.

  Conventionally, urethane (meth) acrylate has been produced by a batch method using a reaction kettle. In general, urethane (meth) acrylate is produced by reacting a hydroxyl group of a compound having a hydroxyl group and a (meth) acryloyl group with an isocyanate group of a compound having an isocyanate group. It may be produced by reacting a hydroxyl group of a compound having a hydroxyl group with an isocyanate group of a compound having a (meth) acryloyl group. The reaction between the hydroxyl group and the isocyanate group is an exothermic reaction. In the course of this exothermic reaction, when the heat of reaction is accumulated and the temperature of the reaction system rises abnormally, (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.

  When a runaway reaction occurs, the unreacted raw material is gasified due to heat generated during the runaway reaction, and gasification occurs due to decomposition of the generated urethane (meth) acrylate. As a result, the pressure in the reaction system suddenly increases, and the reactor itself may be fatally destroyed. To prevent the reactor from being destroyed, when a runaway reaction occurs, measures such as opening the manhole, safety valve, rupture disk, explosion vent, etc. attached to the reaction kettle to release the pressure accumulated in the system Although measures are taken to discharge itself out of the system, the equipment itself for taking these measures becomes very large, the investment cost is high, and the occupied area is large, so the productivity is not good.

  A method of adding a polymerization inhibitor is known as means for stopping the runaway reaction that occurred during the production of urethane (meth) acrylate. In this method, it is necessary to disperse and dissolve the polymerization inhibitor in the reaction system in a very short time.

  However, when gelation occurs, there is a problem that the reaction system tends to increase in viscosity, and it becomes very difficult to disperse and dissolve the polymerization inhibitor in the reaction system in a very short time. In addition, the stirrer impeller that stirs the reaction system due to a sudden increase in viscosity due to a runaway reaction cannot be followed, and the polymerization inhibitor cannot be sufficiently dispersed and dissolved in the reaction system. There is also a problem that causes fatal damage to the device itself. Such a problem is particularly serious when a diluting solvent or the like is not used during the production of urethane (meth) acrylate.

  As a means to make the polymerization inhibitor easily dispersed and dissolved in the reaction system, there is a method in which the polymerization inhibitor is dissolved in a solvent or the like, but in order to respond quickly to the occurrence of a runaway reaction, a polymerization inhibitor is used. A large amount of the dissolved solution must be prepared in advance. Therefore, the cost at the time of manufacture of urethane (meth) acrylate increases. In addition, since a polymerization inhibitor contains a mutagenic substance, it is necessary to pay careful attention to handling.

  As a means to prevent runaway reaction during the production of urethane (meth) acrylate, a solvent coexists in the reaction system, lowering the concentration of the polymerizable compound present in the system and increasing the fluid as the reaction proceeds A method for improving the controllability of the reaction by lowering the viscosity is also known. However, this method must recover the solvent in the reaction system after the completion of the reaction, and is not a method with good productivity because the amount of the kettle is reduced because the solvent is used. Furthermore, there is a concern about the influence of the solvent remaining in a trace amount in the obtained resin composition in terms of quality.

  Thus, when manufacturing urethane (meth) acrylate, it is necessary to take the above countermeasures against the runaway reaction, and the productivity is not good. And although measures against runaway reaction are taken, after all, conditions that do not cause runaway reaction, for example, 100 ° C or lower, preferably 80 ° C or lower, 5-7 hours, and low temperature for a long time. Currently, urethane (meth) acrylate is produced inefficiently (see, for example, Patent Document 1).

As a production method that can prevent heating due to reaction heat, suppress side reactions such as mass increase, and obtain a high reaction rate, the cross-sectional area of the channel is 300 to 1,000,000 μm 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. (For example, refer to Patent Document 2). However, the production method described in Patent Document 2 is a production method specialized only for a ring-opening reaction product of an epoxy compound, and a (meth) acryloyl group which becomes a problem in the production of the urethane (meth) acrylate. There is no disclosure of a measure for preventing a runaway reaction due to polymerization of. 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.

Japanese Patent Laid-Open No. 08-109230 JP 2006-111574 A

  The subject of this invention is providing the manufacturing method which can manufacture urethane (meth) acrylate safely with sufficient productivity.

  As a result of intensive studies, the inventors of the present invention have used a heat transfer reaction vessel having a microtubular channel formed therein, a compound (A) having a hydroxyl group in the microtubular channel, an isocyanate group, and (meth) acryloyl. When the mixed liquid with the compound (B) having a group is continuously and liquid-tightly reacted to react the hydroxyl group in the compound (A) with the isocyanate group in the compound (B), A reaction vessel having a microtubular channel having a void size in which a fluid cross-sectional area flowing in a liquid-tight manner in the microtubular channel has a specific area and flowing in the microtubular channel is used. By mixing the reaction liquid so that the Reynolds number falls within a specific range, mixing by molecular diffusion proceeds in a state where micro turbulence is caused in a microchannel considered to be a normal laminar flow, and the compound (A) and Contact with compound (B) is active In addition, by setting the heat transfer reaction vessel to a high temperature that cannot be obtained by a normal batch method, the efficiency of the urethane reaction between the hydroxyl group and the isocyanate group is improved. The urethane (meth) acrylate flowing out of the flow path has a smaller capacity than the batch type and can be easily temperature controlled by continuous cooling, resulting in runaway reaction of the (meth) acryloyl group The inventors have found that urethane (meth) acrylate can be produced with high productivity because it is difficult to occur and a urethanization reaction occurs in a short time, and the present invention has been completed.

That is, the present invention relates to a compound having a hydroxyl group-containing compound (A), an isocyanate group, and a (meth) acryloyl group in the microtubular channel of a heat transfer reaction vessel in which a microtubular channel is formed. A continuous production method of urethane (meth) acrylate in which the mixed solution with (B) is continuously and liquid-tightly passed and the hydroxyl group in the compound (A) is reacted with the isocyanate group in the compound (B). Because
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 80 to 250 ° C., and reacted so that the Reynolds number of the reaction solution flowing in the microtubular channel is in the range of 0.05 to 300. The present invention provides a method for producing a urethane (meth) acrylate characterized by continuously cooling a reaction product discharged from a thermal reaction vessel.

  According to the production method of the present invention, a production method capable of producing urethane (meth) acrylate safely and with high productivity can be provided. Moreover, it is not necessary to introduce large-scale equipment, and it can be expected to reduce investment costs and manufacturing costs.

It is a perspective view which shows the schematic diagram whole structure including the coupling | bond part of the chemical reaction device used for the manufacturing method of this invention. It is a horizontal sectional view showing the whole schematic diagram composition including the joint part of the chemical reaction device used for the manufacturing method of the present invention. 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.

  The compound (A) used in the present invention is a compound having a hydroxyl group. The compound (A) is not particularly limited as long as it can be supplied without clogging the flow path by means of heat melting, dissolution, dispersion, etc. Can be used.

  The hydroxyl group of the compound (A) used in the present invention may be an alcoholic hydroxyl group or a phenolic hydroxyl group.

  Examples of the compound (A) used in the production method of the present invention include ethanol, methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 1-pentanol, 2-pentanol, Aliphatic alcohols such as 1-hexanol, 2-hexanol, 1-heptanol, 2-heptanol, 1-octanol, 2-octanol, 1-decanol, 2-decanol; cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol , Alicyclic alcohols such as 2-cyclopenten-1-ol and 2-cyclohexen-1-ol; phenethyl alcohol, α-methylbenzyl alcohol, benzyl alcohol, 4-methylbenzyl alcohol, 4-nitrobenzyl alcohol, 4- Aromatic alcohols such as lomobenzyl alcohol; alcohols having a fluorinated alkyl group such as perfluorobutyl alcohol, perfluorobutylethyl alcohol, perfluorobutylsulfonylaminoethyl alcohol, perfluorohexylethyl alcohol, perfluorooctylethyl alcohol, etc. Of the monohydric alcohol.

  Further, as the compound (A), ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butanediol, polybutylene glycol, polyethylene glycol-polypropylene glycol, trimethylolethane, trimethylolpropane, ditrimethylol. Polyhydric alcohols such as propane, glycerin, pentaerythritol, dipentaerythritol, tripentaerythritol, tris (2-hydroxyethyl) isocyanurate, monosaccharides, polysaccharides; fluorine-based polyhydric alcohols such as perfluoropolyether, etc. Polyhydric alcohols can also be used.

  Furthermore, an alcohol having two fluorinated alkyl groups (including those having an etheric oxygen atom) having a branched structure as shown below may be used.

  The compound (A) used in the present invention may be a compound having a (meth) acryloyl group. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy (meth) butyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl acryloyl phosphate, 2- (meta ) Hydroxyl-containing (meth) acrylate compounds having one (meth) acryloyl group such as acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate; 2-hydroxy-3- (meth) Acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate , Caprolactone-modified dipentaerythritol penta (meth) acrylate, hydroxyl group-containing having two or more (meth) acryloyl group such as ethylene oxide-modified pentaerythritol tri (meth) acrylate (meth) acrylate compounds, and the like. These may be used alone or in combination of two or more.

  In the present invention, “(meth) acryloyl” refers to one or both of methacryloyl and acryloyl, and “(meth) acrylate” refers to one or both of methacrylate and acrylate.

  As the production method of the present invention, the production method using a compound having a large calorific value of the urethanization reaction as the compound (A) and having a hydroxyl value of 50 to 500 is sufficient for the effect of the present invention, that is, the effect that it can be produced safely. It is preferable because it can be exhibited.

  The compound (B) used in the present invention is a compound having an isocyanate group and a (meth) acryloyl 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, dissolution, dispersion, etc. These compounds can be used.

  The compound (B) used in the present invention includes (meth) acryloyloxyalkyl isocyanate, acryloyloxyethoxyethyl isocyanate, methacryloyloxyethoxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 1,1-bis ( And methacryloyloxymethyl) ethyl isocyanate. These may be used alone or in combination of two or more.

  Specific examples of (meth) acryloyloxyalkyl isocyanate include compounds represented by the following formulas (B) -1 to 8.

The heat transfer reaction vessel used in the urethane (meth) acrylate production method of the present invention has a microtubular channel formed therein. A compound (A) is obtained by continuously and liquid-circulating a mixed solution of the compound (A) having a hydroxyl group and the compound (B) having an isocyanate group and a (meth) acryloyl group in the microchannel. Urethane (meth) acrylate is continuously produced by reacting the hydroxyl group with the isocyanate group of the compound (B). Pressure loss due to the use of a heat transfer reaction vessel having a microtubular channel having a void cross-sectional area of 0.1 to 4.0 mm ² flowing in a liquid-tight manner in the microtubular channel Therefore, there are excellent effects such as that the flow rate is not excessively increased, the productivity is good, the flow channel is not easily blocked, and the heating and cooling of the flow channel can be quickly controlled. As the heat transfer reaction vessel used in the present invention, one having 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 is more used. preferable. The “cross section” used in the present invention refers to a cross section perpendicular to the flow direction in the reaction channel, and “cross sectional area” refers to the area of the cross section.

Moreover, in the manufacturing method of the urethane (meth) acrylate of this invention, it is necessary to make it react so that the Reynolds number of the reaction liquid which distribute | circulates the said inside of a microtubular channel may be in the range of 0.05-300. In general, when a fluid is passed through 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, the flowing fluid is a laminar flow. Become. Therefore, for example, when a mixed liquid of the compound (A) having a hydroxyl group and the compound (B) having an isocyanate group and a (meth) acryloyl group is circulated through the channel, the compound (A) and the compound (B) Are far less likely to react with each other because they have very few opportunities to contact each other. 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. Now, the inventors have added a compound (A) and an isocyanate in a microtubular channel having a void size of 0.1 to 4.0 mm ^{2 in} a range where the Reynolds number is 0.05 to 300. When the mixed liquid of the compound (B) having a group is circulated, the mixing in the flow path proceeds with a slight turbulence, and the contact between the compound (A) and the compound (B) is activated. The inventors were able to complete the present invention. The Reynolds number is preferably from 0.1 to 200, more preferably from 1 to 100. If the Reynolds number is less than 0.05, the reaction proceeds slowly and stays for a long time, which may cause gelation. If the Reynolds number exceeds 300, the reaction efficiency is limited and the reactor becomes longer, which is not preferable.

The Reynolds number in the present invention is calculated according to the following formula (1).
Reynolds number = (D × u × ρ) / μ (1)
Here, D (inner diameter of the flow path), u (average flow velocity), ρ (fluid density), and μ (fluid viscosity). In the present invention, the Reynolds number was determined by defining each element of the above formula (1) as follows.

D (inner diameter of channel): equivalent diameter (m) of microtubular channel. Here, the equivalent diameter is [(4 × cross-sectional area of microtubular channel (m ² )) / perimeter (m)].
u (average flow rate): the flow rate (m / sec) of the mixture of the compound (A) and the compound (B).
ρ (fluid density): the density (kg / m ³ ) of compound (A) at 20 ° C.
μ (fluid viscosity): the viscosity (Pa · s) of the compound (A) at 20 ° C.

  Furthermore, in the method for producing urethane (meth) acrylate according to the present invention, the heat transfer reaction vessel needs to be heated to 80 to 250 ° C. By setting it within this temperature range, the reaction between the hydroxyl group and the isocyanate group can be efficiently advanced, and an excellent effect is achieved that 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 100 to 210 ° C., more preferably 120 to 180 ° C. because runaway reaction is unlikely to occur and production efficiency is good.

In the method for producing urethane (meth) acrylate according to the present invention, the cross-sectional area of the mixed liquid flowing through the micro flow path of the reaction apparatus used in the present invention, the Reynolds number when the mixed liquid flows through the micro flow path, and the heat conductivity By setting the temperature of the reaction vessel within the above range, an efficient reaction between the hydroxyl group and the isocyanate group occurs, and as a result, the urethane (meth) acrylate produced before the condensation reaction between (meth) acryloyl groups occurs is cooled. It is possible to do it. Moreover, as a flow rate at the time of distribute | circulating the liquid mixture to a microchannel, 0.9 * 10 < ^-4 > -4.2m / sec is preferable, and 1.5 * 10 ^<-2 > -1.5m / sec is more. preferable.

  In the present invention, urethane (meth) acrylate can also be produced without using a catalyst. By not using a catalyst, for example, a heavy metal-free urethane (meth) acrylate or the like can be produced, and for example, a problem that the urethane (meth) acrylate obtained by the catalyst is colored can be avoided.

The heat transfer reaction vessel used in the production method of the present invention has a heat exchange function, and a void size in which a fluid cross-sectional area flowing in a liquid-tight manner in a microtubular channel is 0.1 to 4.0 mm ² What has only to be used is a microtubular channel having the above, and there are no particular restrictions on other requirements. 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 perpendicularly to the flow of the mixed solution 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).

  When a microtubular channel is formed between the member (X) and the member (Y), the member (Y) can be provided with a heat exchange function. For example, a groove for allowing the temperature control fluid to flow may be provided on the surface of the member (Y), and another member may be bonded or laminated to the surface provided with the groove for the temperature control fluid to flow. In general, 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.

  At this time, the groove formed on the member surface may be formed as a so-called groove lower than the peripheral portion thereof, or may be formed between the walls standing on the member surface. 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 need not 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.

  As the heat transfer reaction vessel used in the present invention, 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. Examples of such 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.

  As 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.

  Moreover, when supplying a compound (A) and a compound (B) separately in an apparatus, it is preferable to provide the mixing space which mixes in the front of the said heat-transfer reaction container or this apparatus. Further, the compound (A) and the compound (B) may be mixed in advance and mixed and introduced continuously into the heat transfer reaction vessel.

Hereinafter, the heat transfer reaction container having a microtubular channel formed therein will be specifically described. 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 in which a fluid cross-sectional area flowing in a liquid-tight manner in the microtubular channel is 0.1 to 4.0 mm ² .

In the chemical reaction device 1, a plurality of first plates (2 in FIG. 1) and second plates (3 in FIG. 1) having the same rectangular plate shape in FIG. Configured. Each one first plate is provided with a flow path (hereinafter referred to as a reaction flow path) having a cross-sectional area of 0.1 to 4.0 (mm ² ) (hereinafter referred to as a reaction flow path). Plate is called process plate). 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). And as shown in FIG. 2, those supply ports and discharge ports are distributed 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 α (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 β to be discharged is discharged to the end surface 1c, and the temperature control fluid γ is supplied from the side surface 1e and discharged to the side surface 1d.

  The planar view shape of the device for chemical reaction 1 is not limited to the rectangular shape as shown in the figure, and may be a square shape or a rectangular shape with the side surfaces 1d and 1e 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.

As shown in FIG. 3, 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. Is. Let 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 α containing the compound (A) and the compound (B). In order to ensure uniformity, 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. In addition, description of a width | 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. Although it does not specifically limit, For example, 1-1000 pieces per plate, Preferably it is 5-100 pieces.

  The fluid α flows in 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.

As shown in FIG. 1, 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 approximately in the range of 0.1 to 4.0 (mm ² ). More preferably, it is 0.3-1.0 (mm < ² >). The number of the temperature control flow paths 6 can adopt an appropriate number in consideration of heat exchange efficiency, and is not particularly limited, but is, for example, 1 to 1000, preferably 5 to 100 per plate. It is.

  As shown in FIGS. 1 and 3, 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. You may provide the supply side flow path 6b and the discharge side flow path 6c which are arrange | positioned substantially orthogonally to the path | route 4, and are connected to each main flow path 6a. In FIGS. 1 and 3, 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. As for the number of each temperature control channel 6, only the main channel 6a portion of the temperature control channel 6 is arranged, and the supply side channel 6b and the discharge side channel 6c are each composed of one. .

  In addition, 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 with respect to the flow path 4.

  Preferably, 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 to each other and stacked.

  Therefore, in the form of the chemical reaction device 1, 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 rectangular cross-section with both ends opened. It is said.

  Each process plate and temperature control plate can be made of an appropriate metal material. For example, 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.

  As an apparatus having a chemical reaction device provided with a flow path used in the manufacturing method of the present invention, for example, a manufacturing apparatus shown in FIG. 4 can be exemplified. Specifically, for example, a production apparatus having the following chemical reaction device can be exemplified.

<Chemical reaction device>
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 21 temperature control channels 6 formed by etching as well as 20 process plates having 21 reaction channels 4 formed by dry etching. 21 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.

  The chemical reaction device 60 used in the manufacturing apparatus shown in FIG. 4 has five temperature control channels 6 formed by etching as well as four process plates having five reaction channels 4 formed by dry etching. Five 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.

  In FIG. 4, the outlet of the tank 62 (first tank) for containing the compound (A) (61) and the inlet of the plunger pump 65 are connected via a pipe through which the compound (A) passes. Further, the outlet of the tank 64 (second tank) for containing the compound (B) and the inlet of the plunger pump 66 are connected via a pipe through which the compound (B) (63) passes. From the outlet of the plunger pump 65 and the outlet of the plunger pump 66, pipes through which the compound (A) or the compound (B) passes through the plunger pump 65 or the plunger pump 66 respectively extend. A mixer [mixing space for mixing the compound (A) and the compound (B)] 67 is connected to the inlet of the mixer 67.

  Compound (A) (61) and compound (B) (63) are mixed by this mixer 67, and the liquid mixture containing compound (A) (61) and compound (B) (63) is formed. 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 67. A temperature control device 68 is connected to the chemical reaction device 40, 50 or 60. Then, the compound (A) and the compound (B) in the fluid α react 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 1c of the chemical reaction device 40, 50 or 60. Then, it moves to the inflow port of the cooling heat exchanger 69 through the pipe connected to the outflow port.

  In the production method of the present invention, since the Reynolds number and temperature can be changed, a microtubular channel such as the above-described chemical reaction device 40, 50 or 60 is formed as a heat transfer reaction vessel. It is preferable to carry out the reaction using a reaction apparatus in which a plurality of heat transfer reaction vessels are arranged in series.

  After obtaining urethane (meth) acrylate by the above method, the obtained reaction product 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. In this invention, it is preferable to cool by distribute | circulating to the cooling device which has a heat exchange function. As this cooler, a cooling heat transfer device in which a micro tubular channel is formed is preferable.

  In order to perform continuous cooling using this cooling heat transfer device, for example, 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.

  Specifically, a fluid β [urethane (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) 69 is used. ) Acrylate] is cooled while moving through the cooling heat exchanger 69 and reaches the outlet of the cooling heat exchanger 69. The fluid β is discharged from the cooling heat exchanger 69 through the pipe connected to the outlet, and is discharged to the receiving container 72 through the exhaust pressure valve 71.

  As the heat transfer device for cooling used in the present invention, the heat transfer reaction vessel in which a microtubular channel is formed can be preferably used as the heat transfer reaction vessel, and the 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. As such an apparatus, 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 reaction product or unreacted material may be discharged out of the reaction channel system. Generally, the higher the yield, the higher the viscosity of the reactants, so that the pressure loss increases and the flow rate decreases. For this reason, for example, the reaction from the early stage to the middle stage of the reaction, such as Reynolds number of 0.05 or more, more preferably, Reynolds number of 1 to 200, is carried out by the production method of the present invention, and subsequently, unreacted substances are included. The composition can be transferred to a batch reactor or storage tank, or a channel having a larger cross-sectional area, and the remaining unreacted materials can be reacted.

  In addition, 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.

  Moreover, you may add additives, such as a catalyst (initiator) and a polymerization inhibitor, to a compound (A) or a compound (B) in the range which does not obstruct | occlude a flow path as needed.

  As long as the compound (A) and the compound (B) used in the present invention are in a range that does not adversely affect the reaction, they may be supplied alone or in a mixed state in the flow path. 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. The catalyst (initiator) can be used, and examples thereof include metal catalysts such as dibutyltin diacetate and dibutyltin dilaurate.

  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, for example, methoquinone, hydroquinone and the like.

  Hereinafter, the present invention will be described in more detail with reference to specific examples.

<Chemical reaction device used in Examples and Comparative Examples>
In this example, 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. As the chemical reaction device, chemical reaction devices 40, 50, and 60 shown in FIG. 4 having different Reynolds numbers when the same flow rate was applied (when the flow rate was the same) were used.

  The chemical reaction device 40 is formed by alternately laminating 22 temperature control plates having 21 temperature control channels 6 formed by etching as well as 20 process plates having 21 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 198 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 60 is formed by alternately laminating five temperature control plates having five temperature control channels 6 formed by etching as well as four 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 cooling heat exchanger 69 is alternately laminated with 20 process plates having 21 reaction channels 4 formed by dry etching and 22 temperature plates having 21 temperature control channels 6 formed by etching. Has been. 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 198 mm.

(Reaction rate calculation method)
The reaction rate was determined by the following formula (1).
Reaction rate (%) = {(the theoretical value of NCO% in the total raw material) − (the measured value of NCO% in the reaction solution)} / (theoretical value of NCO% in the total raw material) × 100 (1)
NCO% was measured by the following method.
First, 1 g of the reacted sample was precisely weighed into a 300 ml conical stoppered flask and 15 ml of dehydrated ethyl acetate was added with a graduated cylinder to dissolve the sample. After complete dissolution, 10 ml of a 1 mol / L di-n-butylamine toluene solution was added with a whole pipette, mixed well, and allowed to stand at room temperature for 20 minutes or more. Bromophenol blue indicator was added and titrated with 0.5 mol / L hydrochloric acid aqueous solution, and the point where the color changed from purple to yellow was taken as the end point. At the same time, a blank test was also conducted. NCO% was calculated | required by following Formula (2).

NCO% = (B−T) × F × 0.5 × 42.02 × 100 / S × 1000 (Formula 2)
However,
B: Titration volume of hydrochloric acid required for the blank test (ml)
T: Titration volume of hydrochloric acid required for this test (ml)
F: hydrochloric acid titer S: amount of sample collected (g)

Example 1
In the manufacturing apparatus 80 shown in FIG. 4, ethylene glycol (hereinafter, referred to as “EG”) 61 (1.05 mol) and 2-methacryloyloxyethyl isocyanate (hereinafter, “ The reaction was carried out by mixing 63 (2.0 mol). In EG61, 50 ppm of dibutyltin diacetate as a catalyst and 200 ppm of hydroquinone as a polymerization inhibitor were mixed and dissolved in advance.

Using the plunger pumps 65 and 66, the EG61 in the first tank 62 and the MOI63 in the second tank 64 are mixed at a molar ratio of 1.05: 2.0, and the mixture of EG61 and MOI63 is Reynolds number. Is continuously flown to the mixer (mixing space) 67, the chemical reaction device 40, the heat exchanger 69 for cooling, and the exhaust pressure valve 71 so that the flow rate becomes 0.054 (flow rate: 1.6 × 10 ⁻³ m / sec). The discharged reaction mixture was received in a receiving container 72. In the mixer, EG and MOI were mixed. In the chemical reaction device 40, a temperature adjustment fluid (oil) of 120 ° C. was continuously flowed through the temperature adjustment flow path 6 of the temperature adjustment plate by the temperature adjustment device 68. In the cooling heat exchanger 69, hot water of 70 ° C. was continuously flowed by the temperature control device 70. The pressure inside the pipe was 1 MPa or more with the exhaust pressure valve 71.

  From the quantification result of the unreacted isocyanate group in the reaction mixture, urethane acrylate was produced at a reaction rate of 60% in a reaction time of 120 seconds. Moreover, no runaway reaction occurred. In the present invention, the reaction time refers to the time from when the mixed liquid of the compound (A) and the compound (B) is supplied from the end face of the chemical reaction device to being discharged from the end face of the cooling heat exchanger.

(Example 2)
In the manufacturing apparatus 80 shown in FIG. 4, EG61 (1.05 mol) and MOI63 (2.0 mol) were mixed and reacted using an apparatus in which ten chemical reaction devices 50 were connected in series. In EG61, 50 ppm of dibutyltin diacetate as a catalyst and 200 ppm of hydroquinone as a polymerization inhibitor were mixed and dissolved in advance.

Using the plunger pumps 65 and 66, the EG61 in the first tank 62 and the MOI63 in the second tank 64 are mixed at a molar ratio of 1.05: 2.0, and the mixture of EG61 and MOI63 is Reynolds number. Was continuously flown through the mixer 67, the chemical reaction device 50, the cooling heat exchanger 69, and the exhaust pressure valve 71 so that the flow rate was 1.19 (flow rate: 3.5 × 10 ⁻² m / sec). The reaction mixture was received in a receiving vessel 72. In the mixer, EG and MOI were mixed. In the chemical reaction device 50, a temperature adjustment fluid (oil) of 160 ° C. was continuously supplied to the temperature adjustment flow path 6 of the temperature adjustment plate by the temperature adjustment device 68. In the cooling heat exchanger 69, hot water of 70 ° C. was continuously flowed by the temperature control device 70. The pressure inside the pipe was 1 MPa or more with the exhaust pressure valve 71.

(Example 3)
In the production apparatus 80 shown in FIG. 4, EG61 (1.05 mol) and MOI63 (2.0 mol) were mixed and reacted using an apparatus in which 20 chemical reaction devices 60 were connected in series. In EG61, 50 ppm of dibutyltin diacetate as a catalyst and 200 ppm of hydroquinone as a polymerization inhibitor were mixed and dissolved in advance.

Using the plunger pumps 65 and 66, the EG61 in the first tank 62 and the MOI63 in the second tank 64 are mixed at a molar ratio of 1.05: 2.0, and the mixture of EG61 and MOI63 is Reynolds number. Was continuously supplied to the mixer 67, the chemical reaction device 60, the cooling heat exchanger 69, and the exhaust pressure valve 71 so as to be 9.5 (flow rate: 2.8 × 10 ⁻¹ m / sec). The discharged reaction mixture was received in the receiving container 72. In the mixer, EG and MOI were mixed. In the chemical reaction device 60, a temperature adjustment fluid (oil) of 180 ° C. was continuously supplied to the temperature adjustment flow path 6 of the temperature adjustment plate by the temperature adjustment device 68. In the cooling heat exchanger 69, hot water of 70 ° C. was continuously flowed by the temperature control device 70. The pressure inside the pipe was 1 MPa or more with the exhaust pressure valve 71. The time (reaction time) from when the mixed solution of EG and MOI was supplied from the end face of the chemical reaction device 80 until it was discharged from the end face of the cooling heat exchanger was 20 seconds.

  From the quantification result of the unreacted isocyanate group in the reaction mixture, urethane acrylate was produced at a reaction rate of 98% in a reaction time of 20 seconds. Moreover, no runaway reaction occurred.

Example 4
Except that the mixture of EG61 and MOI63 has a Reynolds number of 48 (flow rate: 1.41 m / sec), and 50 chemical reaction devices 60 are connected in series in the manufacturing apparatus 80 shown in FIG. A reaction mixture was obtained in the same manner as in Example 3. The time (reaction time) from when the mixed solution of EG and MOI was supplied from the end face of the chemical reaction device 60 to when it was discharged from the end face of the cooling heat exchanger was 4 seconds. From the quantification result of the unreacted isocyanate group in the reaction mixture, urethane acrylate was produced at a reaction rate of 70% in a reaction time of 4 seconds. Moreover, no runaway reaction occurred.

(Example 5)
In the production apparatus 80 shown in FIG. 4, using an apparatus in which ten chemical reaction devices 50 are connected in series, 2-perfluorohexylethanol (hereinafter referred to as “PFHE”) 61 (1.1 mol) and MOI64 (1 (0.0 mol) was mixed to carry out the reaction. In PFHE 61, 50 ppm of dibutyltin diacetate as a catalyst and 200 ppm of hydroquinone as a polymerization inhibitor were mixed and dissolved in advance.

  Using the plunger pumps 65 and 66, the PFHE 61 in the first tank 62 and the MOI 63 in the second tank 64 are mixed at a molar ratio of 1.1: 1.0 with a mixture ratio of PFHE 61 and MOI 63, the Reynolds number. Was continuously supplied to the mixer 67, the chemical reaction device 50, the cooling heat exchanger 69, and the exhaust pressure valve 71 so as to be 5.3 (flow rate: 0.104 m / sec). The discharged reaction mixture was received in the receiving container 72. In the mixer, PFHE and MOI were mixed. In the chemical reaction device 50, a temperature adjustment fluid (oil) of 140 ° C. was continuously supplied to the temperature adjustment flow path 6 of the temperature adjustment plate by the temperature adjustment device 68. In the cooling heat exchanger 69, hot water of 70 ° C. was continuously flowed by the temperature control device 70. The pressure inside the pipe was 1 MPa or more with the exhaust pressure valve 71. The time (reaction time) from when the mixed liquid of PFHE and MOI was supplied from the end face of the chemical reaction device 80 until it was discharged from the end face of the cooling heat exchanger was 29 seconds.

  From the quantification result of the unreacted isocyanate group in the reaction mixture, urethane acrylate was produced at a reaction rate of 100% in a reaction time of 29 seconds. Moreover, no runaway reaction occurred.

(Example 6)
In the production apparatus 80 shown in FIG. 4, the compound 61 (1.1 mol) of the specific example (A-8) and the MOI 63 (1.0 mol) are mixed using an apparatus in which ten chemical reaction devices 50 are connected in series. And reacted. In (A-8) 61, 50 ppm of dibutyltin diacetate as a catalyst, 200 ppm of hydroquinone as a polymerization inhibitor, and 1.0% by mass of methyl isobutyl ketone (hereinafter referred to as “MIBK”) as a solvent are mixed and dissolved in advance. did.

  Using the plunger pumps 65 and 66, the (A-8) 61 in the first tank 62 and the MOI 63 in the second tank 64 are mixed at a molar ratio of 1.1: 1.0 (A-8). The mixed liquid of 61 and MOI 63 is continuously supplied to the mixer 67, the chemical reaction device 50, the cooling heat exchanger 69, and the exhaust pressure valve 71 so that the Reynolds number becomes 1.5 (flow rate: 0.106 m / sec). Washed away. The discharged reaction mixture was received in the receiving container 72. In the mixer, (A-8) and MOI were mixed. In the chemical reaction device 50, a temperature adjustment fluid (oil) at 80 ° C. was continuously supplied to the temperature adjustment flow path 6 of the temperature adjustment plate by the temperature adjustment device 68. In the cooling heat exchanger 69, hot water of 70 ° C. was continuously flowed by the temperature control device 70. The pressure inside the pipe was 1 MPa or more with the exhaust pressure valve 71. The time (reaction time) from when the mixed liquid of (A-8) and MOI was supplied from the end face of the chemical reaction device 80 until it was discharged from the end face of the cooling heat exchanger was 28 seconds.

  From the quantification result of the unreacted isocyanate group in the reaction mixture, urethane acrylate was produced at a reaction rate of 85% in a reaction time of 28 seconds. Moreover, no runaway reaction occurred.

(Example 7)
In Example 6, the reaction was performed in the same manner as in Example 6 except that a temperature adjusting fluid (oil) at 140 ° C. was passed through the temperature adjusting device 68. From the quantification result of the unreacted isocyanate group in the reaction mixture, urethane acrylate was produced at a rate of 100% reaction rate. Moreover, no runaway reaction occurred.

(Comparative Example 1)
The reaction was conducted in the same manner as in Example 1 except that the flow rate of the mixed liquid of EG61 and MOI63 was 0.02 (flow rate: 6.3 × 10 ⁻⁴ m / sec) in Reynolds number. A mixture was obtained. The time (reaction time) from when the mixed solution of EG and MOI was supplied from the end face of the chemical reaction device 40 to when it was discharged from the end face of the cooling heat exchanger was 300 seconds. Although no runaway reaction occurred, the reaction rate was only 30% even at a reaction time of 300 seconds, and urethane acrylate could not be produced efficiently.

  Table 1 shows the temperature-controlled fluid temperature, the flow rate, the Reynolds number, the reaction time, and the reaction rate of the resulting urethane acrylate obtained by heating the chemical reaction devices of Examples 1 to 7 and Comparative Example 1. As is apparent from the results of Comparative Example 1, it can be seen that when the Reynolds number is small, the reaction rate is lowered despite the long reaction time, and urethane acrylate cannot be produced efficiently. Further, as is clear from the examples, the larger the Reynolds number, the faster the reaction rate, and the more efficient urethane acrylate can be produced.

(Comparative Example 2)
A four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, nitrogen inlet, and air inlet was charged with 294 g of compound (A-8), 0.14 g of hydroquinone, 0.018 g of dibutyltin diacetate, and 54 g of MIBK. The inside was heated to 80 ° C. After raising the temperature to 80 ° C., 70 g of MOI and 30 g of MIBK mixed and dissolved in advance were added dropwise over 2 hours, and the reaction was continued at 80 ° C. after completion of the addition. NCO% was measured every hour by the above method, and when the NCO% did not change, the reaction was terminated to obtain a comparative urethane acrylate.

(Comparative Example 3)
A four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, nitrogen inlet, and air inlet was charged with EG 33 g, MOI 155 g, and hydroquinone 0.04 g, and the temperature inside the flask was raised to 60 ° C. did. After raising the temperature to 60 ° C., the heating was stopped and 0.04 g of dibutyltin diacetate was charged. Immediately after dibutyltin diacetate is charged, heat is generated and control becomes impossible. The temperature in the flask rises to 240 ° C in about 2 minutes, eventually rises to 320 ° C and the flask gels, generating a large amount of gas from the flask. did.

  Table 2 below shows the reaction conditions and reaction results of Comparative Examples 2 and 3 together with the reaction conditions and reaction results of Examples 2 and 6.

  From the reaction conditions and reaction results shown in Table 2, it was found that in Example 2, the reaction was completed in a very short time without the occurrence of a runaway reaction. This is because the compound (A) and the compound (B) are supplied at a specific flow rate into a microchannel that satisfies a specific condition, and a reaction temperature that cannot normally be taken due to the risk of a runaway reaction in a batch type reaction mode such as a reaction kettle. It is the result achieved by making it react in a microchannel at (160 degreeC).

  In Comparative Example 1, ethylene glycol and 2-methacryloyloxyethyl isocyanate are supplied into a specific micro flow path at a speed at which the Reynolds number is less than 0.05. In a batch type reaction mode such as a reaction kettle, there is a risk of runaway reaction. The results of the reaction in a microchannel at a reaction temperature (120 ° C.) that cannot be usually taken are shown. When the Reynolds number is less than 0.05, even if the reaction is carried out at a very high reaction temperature, the viscosity of the reactant increases with the progress of the reaction, and the mixing property due to molecular diffusion decreases significantly. It was found that the reaction did not proceed in a short time.

  In the comparative example 2, the result of the batch system normally performed with a reaction kettle was shown. For the purpose of sufficiently controlling the temperature in the system while suppressing the runaway reaction, a solution reaction in the solvent methyl isobutyl ketone was performed, and 2-methacryloyloxyethyl isocyanate was continuously added dropwise, and the reaction was performed at a low temperature of 80 ° C. Therefore, it took 5 hours to complete the reaction.

  In Comparative Example 3, in order to shorten the reaction time, ethylene glycol and 2-methacryloyloxyethyl isocyanate were charged all at once, and the result of performing the reaction in a batch system was shown. As soon as the catalyst was added, a rapid exotherm was generated, causing gelation with intense gas generation, resulting in a so-called runaway reaction.

  By comparing the results of Comparative Examples 2 and 3 above with the results of Examples 1 to 7 which are the production method of the present invention, the production method of the present invention is a safe and efficient production of urethane (meth) acrylate. It turned out to be a method.

α... Fluid containing compound (A) and compound (B) β... Fluid containing reaction product of compound (A) and compound (B) Fluid conditioning 1 ... Chemical reaction device 1b ... End surface of chemical reaction device 1c ... End surface of chemical reaction device 1d ... Side side of device for chemical reaction 1e ... Side of device for chemical reaction 2 ... 1st plate (process plate)
2a ... the first plate surface 2b ... the first plate end surface 2c ... the first plate end surface 2d ... the first plate side surface 2e ... the first plate side surface 3 ... 2nd plate (temperature control plate)
3a ··· surface of the second plate 3b ··· end surface of the second plate 3c ··· end surface of the second plate 3d ··· side surface of the second plate 3e ··· side surface of the second plate 4... Cross-sectional groove-shaped channel 6... Cross-sectional groove-shaped temperature control channel 6 a... Cross-sectional groove-shaped main channel 6 b. Supply side flow path 6c ··· Discharge side flow path having a groove shape in cross section p ₀ · · · Predetermined interval w ₀ ··· width d ₀ ··· depth L ··· Flow path length 30 ... Connector 31 ... Joint part 32 ... Joint part 40 ... Chemical reaction device 50 ... Chemical reaction device 60 ...・ Chemical reaction device 80 ... Manufacturing equipment 61 ... Compound (A)
62... First tank 63... Compound (B)
64 ... Second tank 65 ... Plunger pump 66 ... Plunger pump 67 ... Mixer 68 ... Temperature controller 69 ... Heat exchanger for cooling 70 ... Temperature controller 71 ... Exhaust pressure valve 72 ... Receptacle container 80 ... Model of resin production equipment used in Examples and Comparative Examples Schematic configuration diagram

Claims (5)

Mixing of a compound (A) having a hydroxyl group and a compound (B) having an isocyanate group and a (meth) acryloyl group in the microtubular channel of a heat transfer reaction vessel having a microtubular channel formed therein It is a continuous production method of urethane (meth) acrylate in which a liquid is continuously and liquid-circulated and a hydroxyl group in the compound (A) and an isocyanate group in the compound (B) are reacted.
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 80 to 250 ° C., and reacted so that the Reynolds number of the reaction solution flowing in the microtubular channel is in the range of 0.05 to 300. A method for producing urethane (meth) acrylate, comprising continuously cooling a reaction product discharged from a thermal reaction vessel.   The method for producing urethane (meth) acrylate according to claim 1, wherein the reaction is carried out using a reaction apparatus in which a plurality of heat conductive reaction vessels each having a microtubular channel formed therein are arranged in series.   The urethane according to claim 1, wherein the heat transfer reaction vessel having a microtubular channel formed therein has a structure in which a plurality of heat transfer plate-like structures having a plurality of grooves formed on the surface are laminated. A method for producing (meth) acrylate. The mixed liquid of the said compound (A) and a compound (B) is distribute | circulated to a microtubular channel with the flow rate of 0.9 * 10 < ^-4 > -4.2m / sec. Of producing urethane (meth) acrylate.   The method for producing a urethane (meth) acrylate according to any one of claims 1 to 4, wherein the compound (A) is a compound having a fluorinated alkyl group (including those having an etheric oxygen atom).

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