Method for producing polymerization reactive mixture

Abstract

A mixing head 3 for mixing a first preparatory liquid formulation containing a norbornene-based monomer with a second preparatory liquid formulation containing a metathesis polymerization catalyst comprises a case 4, a cap 7 for sealing the case 4, and a mixing rotor 6 which is accommodated rotatably in the case 4, a plurality of projecting parts 622 formed on the peripheral surface of the mixing rotor 6 include first projecting parts 622a in each of which the width along the direction of the axis of the mixing rotor 6 is larger than the width thereof along the direction of the periphery of the mixing rotor 6 and second projecting parts 622b in each of which the width along the direction of the axis of the mixing rotor 6 is smaller than the width thereof along the direction of the periphery of the mixing rotor 6, and first projecting part rows 623a in each of which the first projecting parts 622a are arranged at regular intervals along the direction of the axis of the mixing rotor 6 and second projecting part rows 623b in each of which the second projecting parts 622b are arranged at regular intervals along the direction of the axis of the mixing rotor 6 are arranged alternately at regular intervals in the direction of the periphery of the mixing rotor 6.

Description

[Technical field]

[0001] The present invention relates to a method for producing a polymerization reactive liquid mixture used in reaction injection molding and the like. [Background technology]

[0002] A reaction injection molding method is known in which a monomer and a catalyst are subjected to bulk ring-opening polymerization to produce a resin molded product. In such a reaction injection molding method, when a Ru catalyst is used as the catalyst, the polymerization reaction starts immediately when the monomer and the catalyst are mixed. Therefore, in reaction injection molding using a Ru catalyst, a monomer liquid and a catalyst liquid as a premix are mixed just before the reaction to produce a polymerization reactive mixture liquid.

[0003] Conventionally, a mixer having a function of mixing two or more kinds of chemical liquids and discharging the mixed liquid has been used to mix a monomer liquid and a catalyst liquid. For example, a rotary mixer described in Patent Document 1 has a drive rotor and two driven rotors housed in a mixing space in a housing, and the rotation of the drive rotor rotates the two driven rotors that mesh with it in the opposite direction, and two kinds of chemical liquids supplied from the upper part of the housing are mixed while being pumped downward by the drive rotor and the driven rotor, and are discharged as a mixed liquid from a discharge port at the lower part of the housing. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2019-150786 A Summary of the Invention [Problem to be solved by the invention]

[0005] In reaction injection molding using Ru catalyst, the flow rate ratio of the monomer liquid to the catalyst liquid is a flow rate ratio in which the amount of the monomer liquid is overwhelmingly greater than that of the catalyst liquid. However, the above-mentioned rotary mixer does not support mixing at a flow rate ratio in which the amount of one chemical liquid is overwhelmingly greater than the other. Therefore, when the monomer liquid and the Ru catalyst liquid are mixed in the above-mentioned rotary mixer, the Ru catalyst liquid may flow back due to the large amount of monomer liquid, and the polymerization reaction may not occur properly. Furthermore, in reaction injection molding using Ru catalyst, the preliminary mixed liquid often contains a filler, but the above-mentioned rotary mixer cannot mix the mixed liquid containing the filler because the clearance between the rotor and the inner peripheral surface of the housing is almost zero.

[0006] The problem to be solved by the present invention is to provide a method for producing a polymerization-reactive mixture liquid, which is capable of uniformly mixing pre-mixture liquids having a wide range of flow rate ratios. [Means for solving the problem]

[0007] [1] A method for producing a polymerization-reactive mixture liquid according to the present invention includes the steps of: supplying a first pre-mixed liquid containing a norbornene-based monomer and a second pre-mixed liquid containing a metathesis polymerization catalyst to a mixing head of a rotary mixer; and mixing the first pre-mixed liquid and the second pre-mixed liquid by the mixing head. The mixing head includes a case having a cylindrical mixing chamber having one end closed and the other end open, and a discharge port provided at the closed end of the mixing chamber and from which the polymerization-reactive mixture liquid is discharged; a cap attached to the other open end of the mixing chamber to seal the inside of the mixing chamber, and having a first chemical liquid supply port for supplying the first pre-mixed liquid to the mixing chamber and a second chemical liquid supply port for supplying the second pre-mixed liquid to the mixing chamber; and a cylindrical rod extending along the axial direction of the mixing chamber and arranged in the mixing head so as to be rotatable around the central axis of the mixing chamber. the rotor body; a connecting portion provided at one end of the rotor body and connected to a driving source of the rotary mixer through a connecting hole provided in the cap; a plurality of convex portions provided on a circumferential surface of the rotor body and mixing the first pre-mixed liquid and the second pre-mixed liquid by rotation of the rotor body; and a bearing member attached to the closed end side of the mixing chamber and rotatably supporting the other end of the rotor body, wherein the plurality of convex portions include a first convex portion whose width along the axial direction of the rotor body is wider than its width along the circumferential direction, and a second convex portion whose width along the axial direction of the rotor body is narrower than its width along the circumferential direction, and a first convex portion row in which the plurality of first convex portions are arranged at predetermined intervals along the axial direction of the rotor body and a second convex portion row in which the plurality of second convex portions are arranged at predetermined intervals along the axial direction of the rotor body are alternately arranged at predetermined intervals in the circumferential direction of the rotor body.

[0008] [2] In the above invention, the first row of convex portions may be arranged at a position where the positions of the first convex portions are shifted in the axial direction relative to other first rows of convex portions arranged on either side of the adjacent second rows of convex portions.

[0009] [3] In the above invention, the second row of convex portions may be arranged at a position where the position of the second convex portion is shifted in the axial direction relative to another second row of convex portions arranged on either side of the adjacent first row of convex portions.

[0010] [4] In the above invention, the mixing head may be unitized so as to be detachable from the main body of the rotary mixer.

[0011] [5] In the above invention, the first row of protrusions and the second row of protrusions may be alternately arranged at positions that divide the peripheral surface of the rotor body into an even number of sections (6 to 18) along the circumferential direction.

[0012] [6] In the above invention, the internal volume of the mixing head defined by the inner circumferential surface of the mixing chamber, the inner surface of the cap, and the outer circumferential surface of the mixing rotor may be 1 to 20 mL.

[0013] [7] In the above invention, the distance between the inner circumferential surface of the mixing chamber and the circumferential surface of the mixing rotor on which the convex portions are provided may be 1 to 7 mm, and the distance between the inner circumferential surface of the mixing chamber and the first convex portions and the second convex portions may be 0.1 to 1 mm.

[0014] [8] In the above invention, a flow rate ratio of the first pre-mixed liquid to the second pre-mixed liquid may be 100:100 to 100:0.2.

[0015] [9] In the above invention, the flow rate ratio may be 100:3.5 to 100:0.4.

[0016]

[10] In the above invention, the first pre-mixed liquid may further contain a filler.

[0017]

[11] In the above-mentioned invention, the metathesis polymerization catalyst in the second pre-mixture may be a ruthenium carbene complex.

[0018]

[12] In the above invention, the case may include a discharge nozzle having the discharge port, and the discharge nozzle may be provided with a mounting portion to which an attachment for filling or applying the polymerization reactive liquid mixture to an object to be molded is attached.

[0019]

[13] In the above invention, the mixing head may further include a mixing head cooler that cools the first pre-mixed liquid and the second pre-mixed liquid supplied to the mixing chamber.

[0020]

[14] In the above invention, the rotary mixer may further include a first injector connected to the first chemical supply port via a first piping and supplying the first pre-mixed liquid to the mixing head, a second injector connected to the second chemical supply port via a second piping and supplying the second pre-mixed liquid to the mixing head, and a first piping cooler provided on the first piping and cooling the first pre-mixed liquid passing through the first piping.

[0021]

[15] In the above invention, the rotary mixer may further include a second pipe cooler provided in the second pipe for cooling the second pre-blended liquid passing through the second pipe.

[0022]

[16] The polymer according to the present invention comprises a step of obtaining a polymerization-reactive liquid mixture by the production method according to the above invention, and a step of polymerizing the polymerization-reactive liquid mixture. Effect of the Invention

[0023] As the mixing rotor rotates, the first and second convex portions push the first and second premixed liquids, causing them to flow inside the case. At that time, the gaps between the first convex portions, the gaps between the second convex portions, and the gaps between the first and second convex portions become flow paths for the first and second premixed liquids, and the first and second premixed liquids are repeatedly split and merged through these flow paths. This allows the premixed liquids with a wide range of flow ratios to be mixed uniformly. [Brief description of the drawings]

[0024] [Figure 1] FIG. 1 is a schematic diagram showing the configuration of a rotary mixer according to the present embodiment. [Diagram 2] FIG. 2 is an external perspective view of the mixing head shown in FIG. [Diagram 3] FIG. 3 is an exploded perspective view showing the configuration of the mixing head shown in FIG. [Figure 4] FIG. 4 is a cross-sectional view of the mixhead shown in FIG. [Diagram 5] FIG. 5 is a side view of the mixing rotor shown in FIG. [Figure 6] FIG. 6 is a flow chart showing a procedure for producing a polymerization reactive mixture liquid using the rotary mixer shown in FIG. [Figure 7] FIG. 7 is an explanatory diagram showing the flow of the first pre-mixed liquid and the like caused by the mixing rotor shown in FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. This embodiment relates to a rotary mixer that mixes a first premixed liquid with a second premixed liquid to produce a polymerization-reactive mixture, and supplies the produced polymerization-reactive mixture to electrical components, electronic components, and trace components as a sealing material, a heat dissipation material, or the like. As shown in FIG. 1, the rotary mixer 1 of this embodiment includes a mixer body 2 and a mixing head 3 attached to the mixer body 2. The mixer body 2 supplies the first premixed liquid containing a norbornene-based monomer and the second premixed liquid containing a metathesis polymerization catalyst to the mixing head 3. The mixing head 3 mixes the supplied first premixed liquid with the second premixed liquid to produce a polymerization-reactive mixture, and supplies the polymerization-reactive mixture to a molding object such as an electrical component.

[0026] First, the mixing head 3 will be described. Figures 2, 3, and 4 show an external perspective view, an exploded perspective view, and a cross-sectional view of the mixing head 3. The mixing head 3 includes a substantially cylindrical case 4, a bearing member 5 attached inside the case 4, a mixing rotor 6 housed inside the case 4, and a cap 7 that seals the case 4. The case 4, the bearing member 5, the mixing rotor 6, and the cap 7 are made of synthetic resin, metal, ceramic, or the like, and are unitized as the mixing head 3 constituting the rotary mixer 1 so as to be detachable from the mixer main body 2.

[0027] The case 4 has a hollow cylindrical shape, and a cylindrical mixing chamber 41 that houses the bearing member 5 and the mixing rotor 6 is provided coaxially therein. The mixing chamber 41 is closed at one end (lower side) and open at the other end (upper side). A cylindrical discharge nozzle 42 with a reduced diameter is provided coaxially at the bottom of the case 4. A discharge passage 43 that communicates with the mixing chamber 41 is formed coaxially inside the discharge nozzle 42. The lower end of the discharge passage 43 opens at the lower end face of the discharge nozzle 42, and serves as a discharge port 44 from which the polymerization reactive mixture is discharged. The tip of the discharge nozzle 42 is provided with an attachment 42a to which an attachment such as a syringe needle or a brush can be attached in order to fill or apply the polymerization reactive mixture to a molding object such as an electric component. By using the attachment attached to this attachment 42a, the polymerization reactive mixture can be supplied to a small part of an electric component or an electronic component.

[0028] A generally disk-shaped flange portion 45 having a diameter larger than the outer diameter of the case 4 is provided on the upper portion of the case 4. An open recess 46 is provided on the inner edge of the flange portion 45, which communicates with the mixing chamber 41 and has an inner diameter larger than the inner diameter of the mixing chamber 41. The flange portion 45 serves as a fixing portion for a cap nut, for example, when the mixing head 3 is attached to the mixer body 2 using a cap nut or the like.

[0029] The bearing member 5 includes an annular portion 51 having a substantially annular shape with a diameter slightly smaller than the inner diameter of the mixing chamber 41 of the case 4, a bearing portion 53 disposed at the central axial position of the annular portion 51 and provided with a conical bearing recess 52, and three spokes 54 connecting the annular portion 51 and the bearing portion 53. Three openings 55 defined by the annular portion 51, the bearing portion 53, and the three spokes 54 serve as passages for sending the polymerization reactive mixture from the mixing chamber 41 to the discharge passage 43.

[0030] The mixing rotor 6 is housed in the mixing chamber 41 so as to be rotatable around the central axis of the mixing chamber 41, and is equipped with a cylindrical rotor body 61 extending along the axial direction of the mixing chamber 41, and a mixing member 62 fitted onto the outer periphery of the rotor body 61. A conically protruding support shaft 611 is provided at the axial center position of the lower end surface of the rotor body 61. In addition, a key groove 612 used for connecting with the motor 21 of the mixer body 2 is provided on the upper end surface of the rotor body 61.

[0031] The mixing member 62 has a hollow cylindrical shape, and a cylindrical rotor insertion part 621 is provided coaxially inside. The rotor body 61 is inserted into the rotor insertion part 621. The mixing member 62 has a plurality of protrusions 622 on its outer circumferential surface, which mix the first pre-mixed liquid and the second pre-mixed liquid by the rotation of the mixing rotor 6.

[0032] The protrusions 622 include a first protrusion 622a having a width in the axial direction of the rotor body 61 that is wider than the width in the circumferential direction, and a second protrusion 622b having a width in the axial direction of the rotor body 61 that is narrower than the width in the circumferential direction. As shown in FIG. 5, which is a side view of the mixing rotor 6, the first protrusions 622a form a first protrusion row 623a arranged at a predetermined interval along the axial direction of the rotor body 61, and the second protrusions 622b form a second protrusion row 623b arranged at a predetermined interval along the axial direction of the rotor body 61. The first protrusion row 623a and the second protrusion row 623b are alternately arranged at a predetermined interval in the circumferential direction of the rotor body 61. More specifically, for example, the first protrusion row 623a and the second protrusion row 623b are arranged alternately at positions obtained by dividing the peripheral surface of the rotor body 61 into an even number of sections (6 to 18), more specifically, 12 sections, along the circumferential direction.

[0033] Also, the first convex row 623a is disposed at a position where the first convex portion 622a is shifted in the axial direction from the other first convex row 623a disposed with the adjacent second convex row 623b in between. Similarly, the second convex row 623b is disposed at a position where the second convex portion 622b is shifted in the axial direction from the other second convex row 623b disposed with the adjacent first convex row 623a in between.

[0034] The cap 7 has a disk shape with an outer diameter substantially equal to the inner diameter of the opening recess 46 provided on the inner edge of the flange portion 45 of the case 4, and the thickness dimension of the cap 7 is greater than the depth dimension of the opening recess 46. A connecting hole 71 is provided at the central axial position of the cap 7, through which a connecting shaft (not shown) is inserted to connect the motor 21 of the mixer body 2 and the key groove 612 of the rotor body 61. An annular groove 72 that is recessed radially outward is provided on the inner peripheral wall of the connecting hole 71, and an O-ring 73 that seals the inside of the mixing chamber 41 in close contact with the connecting shaft is fitted into the annular groove 72. In addition, the cap 7 is provided with a first chemical supply port 74 that supplies the first pre-blended liquid to the mixing chamber 41 and a second chemical supply port 75 that supplies the second pre-blended liquid to the mixing chamber 41 on both sides of the connecting hole 71.

[0035] The mixing head 3 is assembled as follows. The bearing member 5 is inserted into the mixing chamber 41 of the case 4 from the opening at the top end of the case 4, and is placed at the bottom end of the mixing chamber 41 with the bearing recess 52 of the bearing member 5 facing upward. Next, the mixing rotor 6 is inserted into the mixing chamber 41 of the case 4 from the bottom end side, and the support shaft 611 provided at the bottom end of the mixing rotor 6 is rotatably supported by the bearing recess 52 of the bearing member 5. Finally, the cap 7 is press-fitted into the opening recess 46 at the top end of the case 4. This seals the mixing chamber 41 with the mixing rotor 6 rotatably housed in the case 4.

[0036] In the mixing head 3 of this embodiment, in order to mix the first preliminary blend liquid even when the first preliminary blend liquid contains a filler, the distance CL1 between the inner peripheral surface of the mixing chamber 41 and the first convex portion 622a and the second convex portion 622b is preferably 0.1 to 1 mm, more preferably 0.2 to 0.8 mm. The distance CL1 can be, for example, 0.5 mm. The distance CL2 between the inner peripheral surface of the mixing chamber 41 and the peripheral surface on which the convex portion 622 of the mixing rotor 6 is provided (the peripheral surface of the mixing member 62) is preferably 1 to 7 mm, more preferably 1.5 to 7 mm, and even more preferably 2 to 5 mm. The distance CL2 can be, for example, 3.5 mm.

[0037] The mixing head 3 of this embodiment is used to supply the produced polymerization-reactive mixture to electric or electronic components as a sealing material, a heat dissipation material, or the like, but the internal volume is made relatively small so that the supply can be completed before the produced polymerization-reactive mixture solidifies. Specifically, the internal volume of the mixing head 3 is determined by the inner peripheral surface of the mixing chamber 41, the inner surface of the cap 7, and the outer peripheral surface of the mixing rotor 6, and is preferably 1 to 20 mL, more preferably 1 to 10 mL, even more preferably 2 to 5 mL, and particularly preferably 2.5 to 4.5 mL. The internal volume of the mixing head 3 can be, for example, 3.5 mL. Furthermore, in order to accommodate the mixing of the first pre-mixed liquid containing a norbornene monomer and the second pre-mixed liquid containing a metathesis polymerization catalyst, the flow rate ratio (mass ratio) of the first pre-mixed liquid to the second pre-mixed liquid is preferably 100:100 to 100:0.2, more preferably 100:100 to 100:0.3, even more preferably 100:100 to 100:0.4, particularly preferably 100:100 to 100:0.5, and can also be 100:100 to 100:1.1. When, for example, a Ru catalyst is used as the metathesis polymerization catalyst, the flow rate ratio (mass ratio) is typically preferably 100:3.5 to 100:0.4, more preferably 100:3.5 to 100:0.5.

[0038] As shown in Fig. 1, the mixing head 3 is attached to the mixer body 2 by fitting a cap nut (not shown) having a through hole through which the case 4 can be inserted and a pressing portion that abuts against the flange portion 45, into the block 24 of the mixer body 2. The block 24 is in contact with the cap 7 of the mixing head 3 when the mixing head 3 is attached to the mixer body 2. The mixer body 2 also includes a motor 21 that is a drive source for the mixing head 3. The motor 21 is connected to the mixing rotor 6 of the mixing head 3 via a through hole (not shown) formed in the block 24 by using a connecting shaft (not shown), and rotates the mixing rotor 6.

[0039] The mixer body 2 includes a first injector 22 that supplies a first premixed liquid containing a norbornene-based monomer to the mixing chamber 41 through a first chemical supply port 74 of the mixing head 3, and a second injector 23 that supplies a second premixed liquid containing a metathesis polymerization catalyst to the mixing chamber 41 through a second chemical supply port 75. One end of a first pipe 221 through which the first premixed liquid passes is connected to the first injector 22. A through hole through which the first pipe 221 can be inserted is formed in the block 24, and the other end of the first pipe 221 is connected to the first chemical supply port 74 via the block 24. In addition, one end of a second pipe 231 through which the second premixed liquid passes is connected to the second injector 23. Block 24 is formed with a through hole through which second pipe 231 can be inserted, and the other end of second pipe 231 is connected to second liquid supply port 75 via block 24. First injector 22 and second injector 23 are configured with supply pumps equipped with a metering function. Note that, for the supply pump of first injector 22, a gear pump is used when the first pre-mixed liquid does not contain a filler, and a snake pump is used when the first pre-mixed liquid contains a filler.

[0040] The rotary mixer 1 in this embodiment is preferably further provided with a first pipe cooler (not shown) that is provided in the first pipe 221 and cools the first pre-blended liquid passing through the first pipe 221. The first pipe cooler is, but is not limited to, a double-pipe type cooler and has a jacket that is concentrically attached to the outside of the first pipe 221. The jacket is, but is not limited to, provided in the first pipe 221 in a section between the pump outlet of the first injector and the block 24. The first pipe cooler can cool the first pre-blended liquid passing through the first pipe 221 by circulating a refrigerant inside the jacket. The jacket is, but is not limited to, for example, a rubber tube.

[0041] The rotary mixer 1 in this embodiment is preferably further provided with a second pipe cooler (not shown) that is provided in the second pipe 231 and cools the second pre-blended liquid passing through the second pipe 231. The second pipe cooler is a double-pipe type cooler like the first pipe cooler, but is not particularly limited, and is provided with a jacket that is concentrically attached to the outside of the second pipe 231. The jacket is provided in the section between the pump outlet of the second injector and the block 24 in the second pipe 231, but is not particularly limited. The second pipe cooler can cool the second pre-blended liquid passing through the second pipe 231 by circulating a refrigerant inside the jacket. In the following, the first pipe cooler and the second pipe cooler will be collectively referred to as the "pipe cooler" as appropriate.

[0042] According to this embodiment, since the rotary mixer 1 is provided with a piping cooler, it is possible to suppress the temperature rise of the first and second pre-mixed liquids due to the influence of the outside air until the first and second pre-mixed liquids are supplied to the mixing chamber 41. That is, according to this embodiment, the first pre-mixed liquid and the second pre-mixed liquid can be supplied to the mixing chamber 41 while being kept at a low temperature, and mixed. Therefore, according to this embodiment, the temperature of the polymerization-reactive mixed liquid produced by mixing the first pre-mixed liquid and the second pre-mixed liquid can be kept low compared to a case in which the rotary mixer is not provided with a piping cooler, and therefore the time from when the polymerization-reactive mixed liquid is discharged until when it hardens (pot life) can be made longer.

[0043] In addition, the rotary mixer 1 in this embodiment is preferably provided with a mixing head cooler (not shown) that cools the first and second pre-blended liquids supplied to the mixing chamber 41 of the mixing head 3. The mixing head cooler is, but is not limited to, an air-cooled plate cooler, and is provided so that the cooling plate of the cooler is in contact with the block 24. The mixing head cooler can cool the first pre-blended liquid passing through the first pipe 221 inserted into the block 24 by dissipating heat received from the block 24 through the cooling plate and the heat dissipation fins attached to the cooling plate. That is, the mixing head cooler can cool the first pre-blended liquid immediately before the first pre-blended liquid is supplied from the first chemical supply port 74 into the mixing chamber 41. Similarly, the mixing head cooler can cool the second pre-blended liquid passing through the second pipe 231 inserted into the block 24. That is, the mixing head cooler can cool the second pre-blended liquid immediately before the second pre-blended liquid is supplied from the second chemical supply port 75 into the mixing chamber 41 .

[0044] According to this embodiment, since the rotary mixer 1 is provided with a mixing head cooler, even if the temperatures of the first and second pre-mixed liquids rise due to the influence of outside air, the first and second pre-mixed liquids can be cooled just before they are supplied to the mixing chamber 41. This makes it possible to supply the first and second pre-mixed liquids to the mixing chamber 41 while maintaining their temperatures low, and mix them. Therefore, according to this embodiment, the temperature of the polymerization-reactive mixture produced by mixing the first and second pre-mixed liquids can be maintained low compared to a case in which the rotary mixer is not provided with a mixing head cooler, and therefore the pot life of the polymerization-reactive mixture can be extended.

[0045] As described above, the rotary mixer 1 in this embodiment is preferably provided with a piping cooler installed in the first pipe 221 and the second pipe 231 and a mixing head cooler installed in the block 24, either alone or in appropriate combination, as a cooling mechanism for the first and second premixed liquids. The cooling of the mixed liquid by these piping coolers and mixing head cooler is carried out by controlling the temperature (T 1in ) and the temperature of the blended liquid at the discharge port 44 (T out ) difference (ΔT1=T 1in -T out ), and the temperature of the second premix at the outlet of the feed pump of the second injector 23 (T 2in ) and the temperature of the blended liquid at the discharge port 44 (T out ) difference (ΔT2=T 2in -T out ) are preferably carried out so that ΔT1 and ΔT2 are each within the above range. By carrying out cooling so that ΔT1 and ΔT2 are each within the above range, the pot life of the polymerization-reactive mixture liquid can be extended by 30 to 60 minutes compared to a case in which the polymerization-reactive mixture liquid is produced at room temperature without cooling. This can improve the formation stability of the polymerization-reactive mixture liquid.

[0046] Although a method of lengthening the pot life of the polymerization-reactive mixture liquid may be to incorporate a polymerization retarder into each of the first and second pre-mixed liquids, according to this embodiment, even if neither the first nor the second pre-mixed liquids contain a polymerization retarder, the pot life of the polymerization-reactive mixture liquid can be lengthened by cooling the first and second pre-mixed liquids. That is, according to this embodiment, it is possible to lengthen the pot life of the polymerization-reactive mixture liquid while suppressing changes in the physical properties of the cured product caused by incorporating a polymerization retarder.

[0047] Next, the first preliminary blend liquid containing a norbornene-based monomer used in this embodiment will be described. The norbornene-based monomer is a cyclic olefin monomer having a norbornene ring structure in the molecule, and is not particularly limited. Among them, it is preferable to use a polycyclic norbornene-based monomer having two or more rings, since a molded product having excellent heat resistance can be obtained.

[0048] Examples of norbornene-based monomers include two-ring monomers such as norbornene and norbornadiene; three-ring monomers such as dicyclopentadiene (cyclopentadiene dimer) and dihydrodicyclopentadiene; four-ring monomers such as tetracyclododecene; five-ring monomers such as cyclopentadiene trimer; and seven-ring monomers such as cyclopentadiene tetramer. These norbornene-based monomers may have a substituent such as an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, an alkenyl group having 2 to 8 carbon atoms, such as a vinyl group, an alkylidene group having 2 to 8 carbon atoms, such as an ethylidene group, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a tolyl group, or a naphthyl group. These norbornene-based monomers may also have a polar group, such as an ester bond [-C(=O)O-]-containing group, an ether bond (-O-)-containing group, a cyano group, or a halogen atom.

[0049] Specific examples of norbornene-based monomers include norbornene, dicyclopentadiene, tetracyclododecene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidenenorbornene, 5-cyclohexenylnorbornene, 1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a,5,6,7, Examples of such ethylenediamine compounds include 8,8a-octahydronaphthalene, 6-ethylidene-1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4-methano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 1,4,5,8-dimethano-1,4,4a,5,6,7,8,8a-hexahydronaphthalene, and ethylenebis(5-norbornene).

[0050] The norbornene-based monomers may be used alone or in combination of two or more kinds. Among the above norbornene-based monomers, dicyclic, tricyclic, tetracyclic or pentacyclic norbornene-based monomers are preferred because they are easily available, have excellent reactivity, and give molded articles with excellent heat resistance.

[0051] In addition, it is preferable that the polymer produced is a thermosetting type, and for this purpose, the norbornene monomer contains at least a crosslinkable monomer having two or more reactive double bonds, such as a symmetrical cyclopentadiene trimer. The content of the crosslinkable monomer in the total norbornene monomer is usually preferably 2 to 30% by weight.

[0052] As long as the object of the present invention is not impaired, monocyclic olefin monomers copolymerizable with the norbornene-based monomer, such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene, may be used as comonomers.

[0053] Next, the second preliminary blend liquid containing the metathesis polymerization catalyst used in this embodiment will be described. The metathesis polymerization catalyst is a complex formed by bonding a plurality of ions, atoms, polyatomic ions, and / or compounds with a transition metal atom as the central atom. As the transition metal atom, atoms of Groups 5, 6, and 8 (long-period periodic table, the same applies below) are used. The atoms of each group are not particularly limited, but an example of an atom of Group 5 is tantalum, an example of an atom of Group 6 is molybdenum or tungsten, and an example of an atom of Group 8 is ruthenium or osmium. Among these transition metal atoms, ruthenium and osmium of Group 8 are preferred. That is, as the metathesis polymerization catalyst used in the present invention, a complex having ruthenium or osmium as the central atom is preferred, and a complex having ruthenium as the central atom is more preferred. As the complex having ruthenium as the central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferred. Here, "carbene compound" is a general term for compounds having a methylene free radical, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (>C:). Ruthenium carbene complexes have excellent catalytic activity during bulk ring-opening polymerization, so the resulting polymer has little odor derived from unreacted monomers, and high-quality polymers can be obtained with good productivity. In addition, they are relatively stable against oxygen and moisture in the air and are not easily deactivated, so they can be used in the atmosphere.

[0054] Examples of the ruthenium carbene complex include those represented by the following general formula (1) or (2).

[0055] [ka]

[0056] In the above general formulas (1) and (2), R 1 and R 2are each independently a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom; these groups may have a substituent and may be bonded to each other to form a ring. 1 and R 2 Examples of groups bonded to each other to form a ring include optionally substituted indenylidene groups such as a phenylindenylidene group.

[0057] Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aryloxy group having 1 to 8 ... Examples of the organic groups include alkylthio groups, carbonyloxy groups, alkoxycarbonyl groups having 1 to 20 carbon atoms, alkylsulfonyl groups having 1 to 20 carbon atoms, alkylsulfinyl groups having 1 to 20 carbon atoms, alkylsulfonic acid groups having 1 to 20 carbon atoms, arylsulfonic acid groups having 6 to 20 carbon atoms, phosphonic acid groups, arylphosphonic acid groups having 6 to 20 carbon atoms, alkylammonium groups having 1 to 20 carbon atoms, and arylammonium groups having 6 to 20 carbon atoms. These organic groups having 1 to 20 carbon atoms, which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, may have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0058] X 1 and X 2 each independently represents an arbitrary anionic ligand. The anionic ligand is a ligand that has a negative charge when separated from the central metal atom, and examples of the anionic ligand include a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, and a carboxyl group.

[0059] L 1 and L 2 represents a heteroatom-containing carbene compound or a neutral electron donor compound other than a heteroatom-containing carbene compound. A heteroatom-containing carbene compound or a neutral electron donor compound other than a heteroatom-containing carbene compound generates a neutral electron when separated from a central metal. A heteroatom is a compound having a charge. From the viewpoint of improving catalytic activity, a heteroatom-containing carbene compound is preferred. The heteroatom means an atom of Groups 15 and 16 of the periodic table, and specific examples thereof include a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, an arsenic atom, and a selenium atom. Among these, from the viewpoint of obtaining a stable carbene compound, a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom are preferred, and a nitrogen atom is particularly preferred.

[0060] The heteroatom-containing carbene compound is preferably a compound represented by the following general formula (3) or (4), and from the viewpoint of improving catalytic activity, a compound represented by the following general formula (3) is particularly preferred.

[0061] [ka]

[0062] In the above general formulas (3) and (4), R 3 , R 4 , R 5 and R 6 each independently represents a hydrogen atom, a halogen atom, or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom are the same as those in the above general formulas (1) and (2).

[0063] Also, R 3 , R 4 , R 5 and R 6may be bonded to each other in any combination to form a ring.

[0064] In addition, since the effect of the present invention becomes more remarkable, R 5 and R 6 is preferably a hydrogen atom. 3 and R 4 is preferably an aryl group which may have a substituent, more preferably a phenyl group having an alkyl group having 1 to 10 carbon atoms as a substituent, and particularly preferably a mesityl group.

[0065] Examples of the neutral electron donor compound include oxygen atoms, water, carbonyls, ethers, nitriles, esters, phosphines, phosphinites, phosphites, sulfoxides, thioethers, amides, imines, aromatics, cyclic diolefins, olefins, isocyanides, and thiocyanates.

[0066] In the above general formulas (1) and (2), R 1 , R 2 , X 1 , X 2 , L 1 and L 2 may be used alone and / or linked to each other in any combination to form multidentate chelating ligands.

[0067] In addition, as the ruthenium carbene complex used in the present invention, from the viewpoint of improving the heat resistance and insulating property of the norbornene-based crosslinked polymer of the present invention in a well-balanced manner, among the compounds represented by the above general formula (1) or (2), the compound represented by the above general formula (1) is preferred, and among them, the compound represented by the following general formula (5) or general formula (6) is more preferred. It is presumed that by using such a compound as a metathesis polymerization catalyst, the polymerization reaction proceeds appropriately, the generation of bubbles is suppressed, and the heat resistance and insulating property of the norbornene-based crosslinked polymer of the present invention are improved in a well-balanced manner.

[0068] General formula (5) is shown below.

[0069] [ka]

[0070] In the above general formula (5), Z is an oxygen atom, a sulfur atom, a selenium atom, NR 12 , P.R. 12 or AsR 12 and R 12 is a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom; however, Z is preferably an oxygen atom because the effects of the present invention become more pronounced.

[0071] In addition, R 1 , R 2 , X 1 and L 1 are the same as those in the above general formulas (1) and (2), and may be used alone and / or may be bonded to each other in any combination to form a multidentate chelating ligand, but X 1 and L 1 does not form a multidentate chelating ligand, and R 1 and R 2 are preferably bonded to each other to form a ring, are more preferably an indenylidene group which may have a substituent, and are particularly preferably a phenylindenylidene group.

[0072] Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the general formulae (1) and (2) above.

[0073] In the above general formula (5), R 7 and R 8are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a heteroaryl group having 6 to 20 carbon atoms, and these groups may have a substituent or may be bonded to each other to form a ring. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and when a ring is formed, the ring may be any of an aromatic ring, an alicyclic ring, and a heterocyclic ring, but it is preferable to form an aromatic ring, more preferably an aromatic ring having 6 to 20 carbon atoms, and particularly preferably an aromatic ring having 6 to 10 carbon atoms.

[0074] In the above general formula (5), R 9 , R 10 and R 11 are each independently a hydrogen atom, a halogen atom, or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, and these groups may have a substituent or may be bonded to each other to form a ring. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom are the same as those in the above general formulas (1) and (2).

[0075] R 9 , R 10 and R 11 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0076] Specific examples of the compound represented by the general formula (5) and its production method include those described in International Publication No. 03 / 062253 (JP Patent Publication No. 2005-515260), etc. The catalyst deactivation temperature of the compound is usually 230° C. or lower.

[0077] General formula (6) is shown below.

[0078] [ka]

[0079] In the above general formula (6), m is 0 or 1. m is preferably 1, in which case Q is an oxygen atom, a nitrogen atom, a sulfur atom, a methylene group, an ethylene group or a carbonyl group, and is preferably a methylene group.

[0080] [ka]

[0081] is a single bond or a double bond, preferably a single bond.

[0082] R 1 , X 1 , X 2 and L 1 are the same as those in the above general formulas (1) and (2), and may be used alone and / or may be bonded to each other in any combination to form a multidentate chelating ligand, but X 1 , X 2 and L 1 does not form a multidentate chelating ligand, and R 1 is preferably a hydrogen atom.

[0083] R 13 ~R 21 are each independently a hydrogen atom, a halogen atom, or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, and these groups may have a substituent or may be bonded to each other to form a ring. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom are the same as those in the above general formulas (1) and (2).

[0084] R 13 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and R 14 ~R 17is preferably a hydrogen atom, R 18 ~R 21 is preferably a hydrogen atom or a halogen atom.

[0085] Specific examples of the compound represented by the general formula (6) and its production method include those described in International Publication No. 11 / 079799 (JP Patent Publication No. 2013-516392), etc. The catalyst deactivation temperature of the compound is usually 230° C. or lower.

[0086] The amount of the metathesis polymerization catalyst used is preferably 0.01 mmol or more, more preferably 0.1 to 50 mmol, and further preferably 0.1 to 20 mmol, per mol of the monomer component containing a norbornene-based monomer.

[0087] The second preliminary blend liquid can be prepared, for example, by dissolving or dispersing the metathesis polymerization catalyst in a small amount of a suitable solvent, such as aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and trimethylbenzene; ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone.

[0088] The first pre-mixed liquid and the second pre-mixed liquid may each contain other components in addition to the norbornene-based monomer and the metathesis polymerization catalyst described above. Examples of such other components include an activator, a polymerization retarder, a filler, a radical generator, a modifier, an antioxidant, a colorant, a light stabilizer, and a flame retardant.

[0089] The activator is a compound that acts as a cocatalyst for the metathesis polymerization catalyst and improves the polymerization activity of the metathesis polymerization catalyst.The activator is not particularly limited, but specific examples thereof include organic aluminum compounds such as alkyl aluminum halides such as ethyl aluminum dichloride and diethyl aluminum chloride, and alkoxy alkyl aluminum halides; organic tin compounds such as tetrabutyl tin; organic zinc compounds such as diethyl zinc; chlorosilane compounds such as dimethyl monochlorosilane, dimethyl dichlorosilane, diphenyl dichlorosilane, tetrachlorosilane, bicycloheptenyl methyl dichlorosilane, phenyl methyl dichlorosilane, dihexyl dichlorosilane, phenyl trichlorosilane, and methyl trichlorosilane; and the like.

[0090] The amount of the activator used is not particularly limited, but is preferably 0.1 mol or more, more preferably 1 mol or more, relative to 1 mol of the metathesis polymerization catalyst, and the upper limit of the amount used is preferably 100 mol or less, more preferably 20 mol or less. If the amount of the activator used is too small, the polymerization activity becomes too low, and the time required for the reaction becomes long, resulting in a decrease in production efficiency. Conversely, if the amount used is too large, the reaction becomes too vigorous, and it tends to be difficult to obtain the desired polymer.

[0091] The polymerization retarder is used to suppress the initiation of polymerization during the preparation of a compound by mixing a monomer component with a metathesis polymerization catalyst. Examples of such polymerization retarders include phosphines, phosphites, vinyl ether derivatives, ethers, esters, nitrile compounds, pyridine derivatives, alcohols, acetylenes, and α-olefins.

[0092] The amount of the polymerization retarder used is not particularly limited, but is preferably 15 parts by mass or more and 5,000 parts by mass or less, more preferably 15 to 1,800 parts by mass, more preferably 50 to 900 parts by mass, and even more preferably 150 to 500 parts by mass, relative to 100 parts by mass of the metathesis polymerization catalyst.

[0093] The filler is not particularly limited, but examples thereof include fibrous fillers having an aspect ratio of 5 to 100 and particulate fillers having an aspect ratio of 1 to 2. Furthermore, these fibrous fillers and particulate fillers can be used in combination.

[0094] Specific examples of fibrous fillers include glass fiber, carbon fiber, wollastonite, potassium titanate, zonolite, basic magnesium sulfate, aluminum borate, tetrapod-type zinc oxide, gypsum fiber, phosphate fiber, alumina fiber, acicular calcium carbonate, acicular boehmite, etc. Among these, wollastonite is preferred because it can increase rigidity with a small amount added and does not inhibit the bulk ring-opening polymerization reaction.

[0095] Specific examples of particulate fillers include calcium carbonate, calcium hydroxide, calcium silicate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, barium titanate, silica, alumina, carbon black, graphite, antimony oxide, red phosphorus, various metal powders, clay, various ferrites, hydrotalcite, and the like. Among these, silica, alumina, and aluminum hydroxide are preferred because they do not inhibit the bulk ring-opening polymerization reaction. In addition, hollow particles may be used as the filler. The hollow particles are not particularly limited, and may be hollow inorganic microspheres, hollow organic microspheres, or hollow organic-inorganic composite microspheres. Examples of hollow inorganic microspheres include hollow glass balloons and other glass hollow balloons, hollow silica balloons, hollow alumina balloons and other metal compound hollow balloons, and hollow ceramic balloons and other porcelain hollow balloons. Examples of hollow organic microspheres include hollow balloons made of resin, such as hollow acrylic balloons, hollow vinylidene chloride balloons, phenol balloons, and epoxy balloons.

[0096] In addition, the above-mentioned filler is preferably one whose surface has been hydrophobized. By using a hydrophobized filler, the aggregation and sedimentation of the filler in the blend can be prevented, and the filler can be uniformly dispersed in the resulting polymer. Examples of the treatment agent used for the hydrophobization treatment include silane coupling agents such as vinyltrimethoxysilane, titanate coupling agents, aluminate coupling agents, fatty acids such as stearic acid, oils and fats, surfactants, waxes, etc. The hydrophobization treatment of the filler can also be performed by simultaneously mixing the treatment agent with the filler when preparing the blend.

[0097] The amount of the filler is preferably 10 to 1000 parts by mass, and more preferably 100 to 500 parts by mass, based on 100 parts by mass of the monomer component containing the norbornene-based monomer. By setting the amount of the filler in the above range, the strength of the obtained polymer can be increased.

[0098] The radical generator includes known organic peroxides, diazo compounds, non-polar radical generators, etc. Among them, organic peroxides are preferred.

[0099] Examples of organic peroxides include hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; etc. Dialkyl peroxides are preferred because they cause less hindrance to the metathesis polymerization reaction. The amount of the radical generator is usually 0.5 to 2.0 parts by mass per 100 parts by mass of the monomer component including the norbornene-based monomer.

[0100] Other modifiers and the like are also known and can be used in desired amounts.

[0101] In this embodiment, such a first pre-mixed liquid and a second pre-mixed liquid are supplied from the mixer body 2 to the mixing head 3, and mixed in the mixing head 3 to form a polymerization-reactive mixed liquid, which is then supplied to an object to be molded, such as an electric part, and the polymerization-reactive mixed liquid is polymerized on the surface of the object to be molded to form a polymer, thereby forming a sealing film or a heat-dissipating film made of such a polymer on the surface of the object to be molded, such as an electric part. Note that at this time, heating may be performed as necessary to promote the polymerization reaction.

[0102] Alternatively, the polymerization-reactive mixture liquid mixed in the mixing head 3 can be supplied to a mold to produce a polymer having, for example, a film shape, a column shape, or any other desired three-dimensional shape. In this case, the polymerization-reactive mixture liquid is heated in the mold to cause a polymerization reaction, and a polymer having a shape corresponding to the mold is obtained.

[0103] The mold is not particularly limited, but it is preferable to use a mold having a split mold structure formed of a male mold and a female mold. The mold used does not necessarily need to be an expensive mold with high rigidity, and a mold made of resin or the like can be used. The material of the mold is not particularly limited, but examples thereof include steel, aluminum, zinc alloy, nickel, copper, chromium, etc., and the mold may be manufactured by any method such as casting, forging, spraying, electroforming, etc., or may be plated.

[0104] The temperature of the mold is preferably 10 to 150° C., more preferably 30 to 120° C., and further preferably 50 to 100° C. The mold clamping pressure is usually in the range of 0.01 to 10 MPa. The polymerization reaction time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes, after the completion of injection of the polymerization reactive mixture liquid.

[0105] After the polymerization reaction is completed, the mold is opened and the polymer is removed from the mold to obtain the polymer.

[0106] In the above-described embodiment, a norbornene-based monomer is used as the first pre-mixed liquid, and a metathesis polymerization catalyst is used as the second pre-mixed liquid. However, the above-described embodiment exemplifies a case in which the metathesis polymerization catalyst used does not require an activator (co-catalyst).

[0107] On the other hand, when a metathesis polymerization catalyst that requires an activator is used, the first pre-mixed liquid may contain a norbornene-based monomer and an activator, and the second pre-mixed liquid may contain a norbornene-based monomer and a metathesis polymerization catalyst.

[0108] Next, the operation of the above embodiment will be described. As shown in the flow chart of Fig. 6, the mixing head 3 is attached to the mixer body 2 (step S1). When the mixing head 3 is attached to the mixer body 2, the motor 21 of the mixer body 2 is connected to the mixing rotor 6 by a connecting shaft (not shown).

[0109] The mixer body 2 supplies the premixed liquid to the mixing head 3 (step S2). Specifically, the first injector 22 of the mixer body 2 supplies a predetermined amount of a first premixed liquid containing a norbornene-based monomer to the mixing chamber 41 through the first pipe 221 and the first chemical supply port 74 of the mixing head 3 by a supply pump having a metering function. The second injector 23 supplies a predetermined amount of a second premixed liquid containing a metathesis polymerization catalyst to the mixing chamber 41 through the second pipe 231 and the second chemical supply port 75. At this time, the first and second premixed liquids can be supplied to the mixing chamber 41 while being cooled by a pipe cooler and a mixing head cooler.

[0110] When the first pre-mixture does not contain a filler, the flow rate ratio (mass ratio) of the first pre-mixture to the second pre-mixture is, for example, 100:3.5. In this way, in reaction injection molding using a Ru catalyst, the flow rate ratio is such that the amount of the monomer liquid is overwhelmingly greater than that of the catalyst liquid.

[0111] The mixer main body 2 drives the motor 21 to rotate the mixing rotor 6, and mixes the first pre-mixed liquid and the second pre-mixed liquid in the mixing chamber 41 (step S3). As the mixing rotor 6 rotates, the first pre-mixed liquid and the second pre-mixed liquid are pushed by the first convex portion 622a and the second convex portion 622b, and a horizontal flow is generated in the mixing chamber 41. At that time, the first pre-mixed liquid and the second pre-mixed liquid repeatedly split and merge with the gap between the first convex portion 622a and the second convex portion 622b as a flow path, as shown by the two-dot chain line in FIG. In particular, in the mixing rotor 6 of this embodiment, the first convex row 623a consisting of the first convex portion 622a and the second convex row 623b consisting of the second convex portion 622b are alternately arranged in the circumferential direction, and the positions of the first convex portion 622a and the second convex portion 622b are shifted in the first convex row 623a and the second convex row 623b, so that the first pre-blended liquid and the second pre-blended liquid flow through a complicated flow path. As a result, the first pre-blended liquid and the second pre-blended liquid can be mixed uniformly even though the flow rate ratio of the first pre-blended liquid is overwhelmingly higher.

[0112] The polymerization-reactive mixture produced by mixing in the mixing chamber 41 of the case 4 moves downward along the gap between the first convex portion 622a and the second convex portion 622b, passes through the opening 55 of the bearing member 5 arranged at the lower end of the mixing chamber 41, passes through the discharge path 43, and is discharged from the discharge port 44 of the discharge nozzle 42 (step S4). The discharged polymerization-reactive mixture is supplied to an electric or electronic component arranged below the mixing head 3, and is used as a sealing material, a heat dissipation material, or the like. In addition, when an attachment such as a syringe needle or a brush is attached to the mounting portion 42a at the tip of the discharge nozzle 42, the polymerization-reactive mixture is supplied to the electric component or the like through the attachment. In the next step S5, the polymerization reaction of the polymerization-reactive mixture supplied to the electric or electronic component progresses, and the polymerization-reactive mixture solidifies.

[0113] In the above step S2, if the first pre-mixed liquid contains a filler, the flow rate ratio of the first pre-mixed liquid to the second pre-mixed liquid is, for example, 100:0.5. Then, in step S3, the first pre-mixed liquid containing the filler and the second pre-mixed liquid are mixed. However, in the mixing head 3 of the present embodiment, the distance CL1 between the inner circumferential surface of the mixing chamber 41 and the first convex portion 622a and the second convex portion 622b is preferably 0.1 to 1 mm, more preferably 0.2 to 0.8 mm, so that even the pre-mixed liquid containing the filler can be mixed uniformly.

[0114] As described above, according to this embodiment, the mixing head 3 used in the process of mixing the first pre-mixed liquid and the second pre-mixed liquid is provided with a mixing rotor 6 having a plurality of protrusions 622 provided on its peripheral surface, and the plurality of protrusions 622 are composed of first protrusions 622a whose width along the axial direction of the rotor body 61 is wider than the width along the circumferential direction, and second protrusions 622b whose width along the axial direction of the rotor body 61 is narrower than the width along the circumferential direction, and a first protrusion row 623a in which the plurality of first protrusions 622a are arranged at predetermined intervals along the axial direction of the rotor body 61, and a second protrusion row 623b in which the plurality of second protrusions 622b are arranged at predetermined intervals along the axial direction of the rotor body 61 are alternately arranged at predetermined intervals in the circumferential direction of the rotor body 61.

[0115] As a result, the first convex portion 622a and the second convex portion 622b push the first premixed liquid and the second premixed liquid by the rotation of the mixing rotor 6, so that a horizontal flow is generated in the mixing chamber 41. At that time, the first premixed liquid and the second premixed liquid repeatedly branch and merge through the gap between the first convex portion 622a and the second convex portion 622b as a flow path. In particular, since the first convex portion row 623a consisting of the first convex portion 622a and the second convex portion row 623b consisting of the second convex portion 622b are alternately arranged in the circumferential direction, the first premixed liquid and the second premixed liquid flow through a complicated flow path. As a result, even if the flow rate ratio of the first premixed liquid is overwhelmingly higher, the first premixed liquid and the second premixed liquid can be mixed uniformly.

[0116] According to this embodiment, the first convex row 623a is arranged at a position where the first convex 622a is shifted in the axial direction from the other first convex row 623a arranged with the adjacent second convex row 623b in between. Also, the second convex row 623b is arranged at a position where the second convex 622b is shifted in the axial direction from the other second convex row 623b arranged with the adjacent first convex row 623a in between. As a result, the first pre-blended liquid and the second pre-blended liquid flow through a more complicated flow path, so that the first pre-blended liquid and the second pre-blended liquid can be mixed uniformly even if the flow rate ratio of the first pre-blended liquid is overwhelmingly higher.

[0117] According to the present embodiment, the mixing head 3 is unitized so as to be detachable from the mixer body 2 of the rotary mixer 1. Therefore, when the polymerization-reactive mixture adhering to the inside of the mixing head 3 solidifies, the mixing head 3 can be replaced with a new one.

[0118] According to this embodiment, the first convex row 623a and the second convex row 623b are alternately arranged at positions obtained by dividing the circumferential surface of the rotor body 61 into an even number of sections (6 to 18) along the circumferential direction. Therefore, the arrangement of the convex portions of the mixing rotor 6 can be optimized depending on the types of the first pre-mixed liquid and the second pre-mixed liquid, etc.

[0119] According to this embodiment, the distance between the inner circumferential surface of the mixing chamber 41 and the circumferential surface on which the convex portion 622 of the mixing rotor 6 is provided is preferably 1 to 7 mm, more preferably 1.5 to 7 mm, and even more preferably 2 to 5 mm, and the distance between the inner circumferential surface of the mixing chamber 41 and the first convex portion 622a and the second convex portion 622b is preferably 0.1 to 1 mm, and more preferably 0.2 to 0.8 mm, so that the pre-mixed liquid containing the filler can be appropriately mixed.

[0120] According to this embodiment, the discharge nozzle 42 of the case 4 is provided with the mounting portion 42a to which an attachment for filling or applying the polymerization-reactive liquid mixture to the molding object is attached, so that the polymerization-reactive liquid mixture can be filled or applied to a very small or large area of ​​the molding object.

[0121] According to this embodiment, the first and second preliminary blended liquids can be supplied to the mixing chamber 41 while being cooled by the piping cooler and the mixing head cooler so that the temperature difference (ΔT1) between the blended liquids at the supply pump outlet and the discharge port 44 of the first injector 22 and the temperature difference (ΔT2) between the blended liquids at the supply pump outlet and the discharge port 44 of the second injector 23 are each 5 to 10° C. This allows the produced polymerization-reactive blended liquid to be discharged from the discharge port while maintaining its temperature low, thereby making it possible to extend the pot life of the blended liquid compared to the case where cooling is not performed.

[0122] In the above embodiment, the mixing head 3 is installed substantially vertically so that the first chemical supply port 74 and the second chemical supply port 75 are arranged at the top and the discharge port 44 is arranged at the bottom, and the first and second pre-mixed liquids are supplied from the first and second chemical supply ports 74 and 75 at the top, and the mixed polymerization-reactive mixed liquid is discharged from the discharge port at the bottom. However, the present invention is not limited to such an arrangement. For example, the mixing head 3 may be installed substantially vertically so that the first chemical supply port 74 and the second chemical supply port 75 are arranged at the bottom and the discharge port 44 is arranged at the top, and the first and second pre-mixed liquids are supplied from the first and second chemical supply ports 74 and 75 at the bottom, and the mixed polymerization-reactive mixed liquid is discharged from the discharge port 44 at the top. The mixing head 3 may be arranged so that its axial direction is horizontal, and the supply of the first pre-mixture liquid and the second pre-mixture liquid and the discharge of the polymerization-reactive mixture liquid may be performed horizontally, or the mixing head 3 may be arranged so as to be inclined at a predetermined angle. EXAMPLES

[0123] As the first preliminary mixture, a mixture containing dicyclopentadiene as a norbornene monomer was prepared. In addition, 0.6 parts by mass of a ruthenium catalyst (VC843, molecular weight 843, manufactured by Strem Chemicals) represented by the following formula (7) as a metathesis polymerization catalyst and 15 parts by mass of 2,6-di-t-butyl-p-cresol (BHT, anti-aging agent) were dissolved in 82 parts by mass of cyclopentanone, and then 2.2 parts by mass of 3,4-dimethylpyridine and 0.1 parts by mass of phenyltrichlorosilane were mixed to obtain the second preliminary mixture. 87 parts by mass of alumina was mixed as a filler into 13 parts by mass of the first preliminary mixture, and this was obtained as the third preliminary mixture.

[0124] [ka]

[0125] Example 1 Then, the first pre-mixture and the second pre-mixture prepared and adjusted as described above were used in a rotary mixer 1 shown in Figs. 1 to 5 to mix the first pre-mixture and the second pre-mixture with a mixing head 3 to obtain a polymerization-reactive mixture. At this time, the temperature of the first pre-mixture at the outlet of the first injector 22 was measured, and the temperature of the second pre-mixture at the outlet of the second injector 23 was measured. At this time, the flow rate ratio of the first pre-mixture and the second pre-mixture was 100:3.5 in terms of the flow rate ratio (mass ratio) of "first pre-mixture:second pre-mixture", the discharge amount was about 2 g, and the rotation speed of the mixer was 250 rpm. In this embodiment, the mixing rotor 6 was a rotor body 61 with the first convex row 623a and the second convex row 623b arranged alternately at positions where the peripheral surface of the rotor body 61 was divided into 12 sections along the peripheral direction. The capacity of the mixing head 3 was 3.5 mL, the distance CL1 between the inner peripheral surface of the mixing chamber 41 and the first convex portion 622a and the second convex portion 622b was 0.5 mm, and the distance CL2 between the inner peripheral surface of the mixing chamber 41 and the peripheral surface (peripheral surface of the mixing member 62) on which the convex portion 622 of the mixing rotor 6 was provided was 3.5 mm. The color of the obtained polymerization-reactive mixture was visually confirmed. The obtained polymerization-reactive mixture was discharged into a SUS mold and heated in an oven at 150° C. for 1 hour to obtain a cured product. When the polymerization-reactive mixture was discharged, about 2 g was discharged once, and a total of 10 discharges were performed. The discharge amount (g) of each discharge was measured, and the average value, standard deviation, and CV (coefficient of variation) (%) of the 10 discharge amounts (g) were calculated. The amount of unreacted components of the cured product was measured as a weight loss rate using a TG-DTA (differential thermal thermogravimetry) device. The measurement conditions were a temperature rise at a rate of 20°C / min, and calculations were performed in the range of 50°C to 200°C. The glass transition temperature of the cured product was measured using a DSC (differential scanning calorimeter) in accordance with JIS K7121. The measurement conditions were a temperature rise at a rate of 10°C / min. When the mixed state and discharge state were confirmed by the above method, the obtained polymerization-reactive mixture was a good one in which the first preliminary mixture and the second preliminary mixture were uniformly mixed, and the polymer obtained using such a polymerization-reactive mixture was also uniform overall (evaluation of mixed discharge in Table 1: ◯ (fair)).Furthermore, the dispersion in the amount of the polymerizable reactive liquid mixture discharged was small, and discharge could be performed with high repeatability.

[0126] Example 2 The third preliminary mixture and the second preliminary mixture were poured into the mixer at a ratio of 100:0.4. The rotation speed of the mixing rotor was set to 800 rpm. Obtaining and measuring the cured product were carried out in the same manner as in Example 1.

[0127] Example 3 A rotary mixer 1 equipped with a first pipe cooler, a second pipe cooler, and a mixing head cooler was used, the first pre-mixed liquid was supplied while being cooled by the first pipe cooler and the mixing head cooler, the second pre-mixed liquid was supplied while being cooled by the second pipe cooler and the mixing head cooler, and the amount of discharge was about 10 g. Except for this, a polymerization-reactive mixture was produced and a cured product was obtained in the same manner as in Example 1. Each evaluation was performed in the same manner as in Example 1. The temperature of the polymerization-reactive mixture immediately after discharge was measured, and the difference (ΔT1) between the temperature of the first pre-mixed liquid at the outlet of the first injector 22 and the temperature difference (ΔT2) between the temperature of the second pre-mixed liquid at the outlet of the second injector 23 were calculated. ΔT1 was 9.5°C and ΔT2 was 7.5°C. The pot life of the polymerization-reactive mixed liquid obtained by mixing the first pre-mixed liquid and the second pre-mixed liquid was measured by checking the time it took for the viscosity of the polymerization-reactive mixed liquid to increase by 1,000 Pa s from the viscosity immediately after discharge. The pot life was 54 minutes longer than that of Example 1.

[0128] Comparative Example 1 A rotary mixer described in JP 2019-150786 A was used instead of the rotary mixer 1 shown in Figures 1 to 5. When obtaining and measuring a cured product were performed in the same manner as in Example 2, the driving rotor was damaged, mixing was not possible, and a cured product of the polymerization reactive mixture was not obtained (evaluation of mixing and discharging in Table 1: × (not possible)).

[0129] [Table 1] [Explanation of symbols]

[0130] 1. Rotary mixer 2. Mixer body 21...Motor (drive source) 22…First injector 221…First pipe 23…Second injector 231…Second pipe 24…Block 3. Mixing head 4. Case 41…Mixing room 42…Discharge nozzle 42a…Mounting part 43...Discharge path 45…Flange section 5...Bearing material 52...Bearing recess 55…Opening 6…Mixing rotor 61...Rotor body 611…Support shaft 612...Key groove (connecting part) 62...Mixing member 622a…First protrusion 622b…Second protrusion 623a…First row of protrusions 623b…Second row of protrusions

Claims

1. A method for producing a polymerization-reactive mixture, comprising: a step of supplying a first pre-mixture containing a norbornene-based monomer and a second pre-mixture containing a metathesis polymerization catalyst to a mixing head of a rotary mixer; and a step of mixing the first pre-mixture and the second pre-mixture by the mixing head, The mixing head comprises: a case including a cylindrical mixing chamber having one end side closed and the other end side open, and a discharge port provided at the closed end side of the mixing chamber and through which the polymerization reactive liquid mixture is discharged; a cap attached to the other open end of the mixing chamber to seal the inside of the mixing chamber, the cap including a first chemical supply port for supplying the first pre-mixed liquid to the mixing chamber and a second chemical supply port for supplying the second pre-mixed liquid to the mixing chamber; a mixing rotor including: a cylindrical rotor body that is accommodated in the mixing chamber so as to be rotatable about a central axis of the mixing chamber and extends along an axial direction of the mixing chamber; a connection portion that is provided at one end of the rotor body and that is connected to a drive source of the rotary mixer through a connection hole provided in the cap; and a plurality of protrusions that are provided on a circumferential surface of the rotor body and that mix the first pre-mixed liquid and the second pre-mixed liquid by rotation of the rotor body; a bearing member attached to the closed end side of the mixing chamber and rotatably supporting the other end of the rotor body, The plurality of protrusions are a first protruding portion having a width along an axial direction of the rotor body that is wider than a width along a circumferential direction, and a second protruding portion having a width along the axial direction of the rotor body that is narrower than a width along the circumferential direction, A method for producing a polymerization reactive mixture, in which a first convex row in which a plurality of the first convex portions are arranged at a predetermined interval along the axial direction of the rotor body and a second convex row in which a plurality of the second convex portions are arranged at a predetermined interval along the axial direction of the rotor body are alternately arranged at predetermined intervals in a circumferential direction of the rotor body.

2. A method for producing the polymerization reactive liquid mixture according to claim 1, comprising the steps of: The first convex row is disposed at a position shifted in the axial direction with respect to another first convex row disposed on either side of the adjacent second convex row.

3. A method for producing the polymerization reactive mixture liquid according to claim 1 or 2, comprising the steps of: The second convex row is disposed at a position shifted in the axial direction with respect to another second convex row disposed on either side of the adjacent first convex row.

4. A method for producing the polymerization reactive mixture liquid according to any one of claims 1 to 3, comprising the steps of: The method for producing a polymerization-reactive liquid mixture, wherein the mixing head is unitized so as to be freely attached to and detached from the main body of the rotary mixer.

5. A method for producing the polymerization reactive liquid mixture according to any one of claims 1 to 4, comprising the steps of: The first row of protrusions and the second row of protrusions are alternately arranged at positions obtained by dividing the peripheral surface of the rotor body into an even number of sections (6 to 18) along a circumferential direction.

6. A method for producing the polymerization reactive mixture liquid according to any one of claims 1 to 5, comprising the steps of: A method for producing a polymerization-reactive mixture liquid, wherein the internal volume of the mixing head defined by the inner circumferential surface of the mixing chamber, the inner surface of the cap, and the outer circumferential surface of the mixing rotor is 1 to 20 mL.

7. A method for producing the polymerization reactive liquid mixture according to any one of claims 1 to 6, comprising the steps of: a distance between an inner circumferential surface of the mixing chamber and a circumferential surface of the mixing rotor on which the convex portions are provided is 1 to 7 mm, and a distance between the inner circumferential surface of the mixing chamber and the first convex portion and the second convex portion is 0.1 to 1 mm.

8. A method for producing the polymerization reactive liquid mixture according to any one of claims 1 to 7, comprising the steps of: A method for producing a polymerization reactive mixture, wherein a flow rate ratio of the first pre-mixture and the second pre-mixture is 100:100 to 100:0.

2.

9. A method for producing the polymerization reactive liquid mixture according to claim 8, comprising the steps of: The flow rate ratio is 100:3.5 to 100:0.

4.

10. A method for producing the polymerization reactive liquid mixture according to any one of claims 1 to 9, comprising the steps of: The method for producing a polymerization reactive liquid mixture, wherein the first pre-mixture further contains a filler.

11. A method for producing the polymerization reactive liquid mixture according to any one of claims 1 to 10, comprising the steps of: The method for producing a polymerization reactive mixture, wherein the metathesis polymerization catalyst of the second pre-mixture is a ruthenium carbene complex.

12. A method for producing the polymerization reactive liquid mixture according to any one of claims 1 to 11, comprising the steps of: the case includes a discharge nozzle having the discharge port, The method for producing a polymerization-reactive liquid mixture, wherein the discharge nozzle is provided with a mounting portion to which an attachment for filling or applying the polymerization-reactive liquid mixture to an object to be molded is attached.

13. A method for producing the polymerization reactive liquid mixture according to any one of claims 1 to 12, comprising the steps of: The mixing head further includes a mixing head cooler that cools the first pre-mixed liquid and the second pre-mixed liquid supplied to the mixing chamber.

14. A method for producing the polymerization reactive liquid mixture according to any one of claims 1 to 13, comprising the steps of: The rotary mixer comprises: a first injector connected to the first chemical supply port via a first pipe and configured to supply the first preliminary blend to the mixing head; a second injector connected to the second chemical supply port via a second pipe and configured to supply the second preliminary blend to the mixing head; a first pipe cooler provided in the first pipe and configured to cool the first pre-mixed liquid passing through the first pipe.

15. A method for producing the polymerization reactive liquid mixture according to claim 14, comprising the steps of: The rotary mixer further includes a second pipe cooler that is provided in the second pipe and cools the second pre-mixed liquid passing through the second pipe.

16. A method for producing a polymer, comprising the steps of obtaining a polymerization-reactive liquid mixture by the production method according to any one of claims 1 to 15, and polymerizing the polymerization-reactive liquid mixture.

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