JP2006225613A - Manufacturing method of blocked terminal-type polyamide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide such a manufacturing method of a blocked terminal-type polyamide resin as is capable of forming in a short time a polymerizate with a narrow molecular-weight distribution and uniformity. <P>SOLUTION: The manufacturing method of the blocked terminal-type polyamide resin comprises introducing and mixing a first solution containing (A) a diamine compound and a second solution containing (B) a dicarboxylic acid chloride compound by ways of the first hollow passage and the second hollow passage respectively into the first hollow mixer having such a minute space with a cross sectional area of 10<SP>2</SP>-10<SP>7</SP>μm<SP>2</SP>as a region of the reaction between the above diamine compound (A) and the above dicarboxylic acid chloride compound (B) and thus obtaining a third solution containing (C) a polyamide compound, and preferably comprises introducing and mixing the above third solution obtained and a fourth solution containing (D) a dicarboxylic acid anhydride compound by ways of the third hollow passage and the fourth hollow passage respectively into the second hollow mixer having such a minute space with a cross sectional area of 10<SP>2</SP>-10<SP>7</SP>μm<SP>2</SP>as a region of the reaction between the above polyamide compound (C) and the above dicarboxylic acid anhydride compound (D). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a terminal-capped polyamide resin.

In the conventional method for producing an end-capped polyamide resin by polycondensation reaction, the production was carried out through two steps of synthesis of the polyamide resin and end-capping, but the first stage resin synthesis reaction ( In the formation of a polymer structure), the dicarboxylic acid chloride compound is added to the solution containing the diamine compound as a powder and reacted, or the solution in which the dicarboxylic acid chloride compound is dissolved is slowly dropped and reacted. The two compounds described above were mixed in a uniform state, resulting in variations in the reaction molar ratio, which could have a significant effect on the three-dimensional structure of the resulting polymer (see, for example, Non-Patent Document 1).
In the second-stage sealing reaction, it is difficult to efficiently mix the solution containing the high-viscosity polymer obtained in the first-stage synthesis and the solution containing the low-viscosity organic compound. It is difficult to obtain a uniform end-capped polymer structure. Further, since these reactions are reactions accompanied by a rapid exotherm, hot spots are generated in the reaction solution, and it is difficult to obtain a uniform polymer structure (see, for example, Non-Patent Document 2), and the resulting resin. The molecular weight distribution of was also wide.

Imai Itsuo and Yokota Rikio, "Latest Polyimides-Fundamentals and Applications", NTS Corporation, January 2002 Material / Process Committee Microreactor Working Group, Microreactor WG Research Report “Research on Microreactor Technology Oriented to Chemical Synthesis”, Chemical Technology Strategy Promotion Organization, June 2000

  An object of the present invention is to provide a method for producing a terminal-capped polyamide resin having a narrow molecular weight distribution and capable of producing a uniform polymerization product in a short time.

In the present invention, a first solution containing a diamine compound (A) and a second solution containing a dicarboxylic acid chloride compound (B) are respectively added to the diamine compound ( The reaction mixture of A) and the dicarboxylic acid chloride compound (B) is introduced into and mixed with a first hollow mixer having a fine space with a cross-sectional area of 10 ² to 10 ⁷ μm ² and contains a polyamide compound (C). It is a manufacturing method of the terminal block type polyamide resin characterized by obtaining 3 solutions, More preferably, the obtained 3rd solution and the 4th solution containing dicarboxylic anhydride compound (D) are each, A fine space having a cross-sectional area of 10 ² to 10 ⁷ μm ² , which is a reaction region between the polyamide compound (C) and the dicarboxylic anhydride compound (D), is formed from the third hollow channel portion and the fourth hollow channel portion. 2nd in having Introduced into the mixing machine, a method for producing a terminal-sealed type polyamide resin, characterized by mixing.

The first solution preferably contains a base because the molecular weight can be further increased.
In the method for producing an end-capped polyamide resin of the present invention, the reaction molar ratio of the dicarboxylic acid chloride compound (B) to the diamine compound (A) in the reaction region in the first hollow mixer is the same as that of the first solution. It is adjusted by the concentration of the second solution and / or the linear velocity immediately before mixing the first solution and the second solution, or the reaction molar ratio of the dicarboxylic anhydride compound (D) to the polyamide compound (C) is By adjusting the concentration of the third solution and the fourth solution and / or the linear velocity immediately before the mixing of the third solution and the fourth solution, a more uniform reaction can be achieved.

The reaction molar ratio (B / A) of the dicarboxylic acid chloride compound (B) to the diamine compound (A) in the reaction region in the first hollow mixer is preferably in the range of 0.5 to 1.0, and the second The reaction molar ratio (D / C) of the dicarboxylic acid anhydride compound (D) to the polyamide compound (C) in the reaction region in the hollow mixer is preferably in the range of 0.1 to 5.0. The linear velocities immediately before the mixing of the first solution, the second solution, the third solution, and the fourth solution in the four hollow flow path portions are preferably 10 ⁻⁴ to 10 ² m / second, respectively. More preferably, the linear velocity of the solution and the linear velocity of the fourth solution have a linear velocity ratio (third solution / fourth solution) of 1/1 to 1/10.

Moreover, it is preferable to carry out by controlling the reaction temperature in the reaction zone in said 1st and / or said 2nd hollow mixer from 20 degreeC to 30 degreeC.
The molecular weight distribution (Mw / Mn) of the end-capped polyamide resin obtained by the production method is preferably 3.0 or less.

  According to the present invention, a uniform polymerization product of polyimide can be generated in a short time, and an end-capped polyamide resin having a narrow molecular weight distribution as compared with the conventional method can be obtained.

In the present invention, a first solution containing a diamine compound (A) and a second solution containing a dicarboxylic acid chloride compound (B) are respectively added to the diamine compound ( The polyamide compound is introduced into a first hollow mixer having a fine space having a cross-sectional area of 10 ² to 10 ⁷ μm ² , which is a reaction region between A) and the dicarboxylic acid chloride compound (B), and mixed at high speed. A method for producing an end-capped polyamide resin comprising a first step of obtaining a third solution containing (C), more preferably a third solution containing the polyamide compound (C) and a dicarboxylic acid The fourth solution containing the anhydride compound (D) is a reaction region of the polyamide compound (C) and the dicarboxylic anhydride compound (D) from the third hollow channel and the fourth hollow channel, respectively. cross section It is characterized by having a second step of introducing into a second hollow mixer having a fine space with a product of 10 ² to 10 ⁷ μm ² and mixing at high speed uniformly.

In the method for producing a terminal-capped polyamide resin of the present invention, the reaction molar ratio (B / A) of the dicarboxylic acid chloride compound (B) to the diamine compound (A) in the reaction region in the first hollow mixer is adjusted. It is preferable to carry out by changing the concentrations of the first solution and the second solution as appropriate and / or appropriately changing the linear velocity immediately before the mixing of the first solution and the second solution.
Furthermore, the adjustment of the reaction molar ratio (D / C) of the dicarboxylic anhydride compound (D) to the polyamide compound (C) may be performed by appropriately changing the concentrations of the third solution and the fourth solution and / or It is preferable to carry out by appropriately changing the linear velocity immediately before the mixing of the third solution and the fourth solution.

  By adjusting reaction molar ratio (B / A) and (D / C) by such a method, it can react uniformly, and it is preferable. According to the production method of the present invention, it is possible to uniformly mix reaction materials at a high speed in a multistage reaction. Moreover, since the reaction is performed in a fine space, the ratio of the surface area to the volume of the reaction region is increased, and the temperature rise of the reaction solution due to reaction heat can be suppressed. Therefore, it is possible to produce a uniform end-capped polyamide resin in a short time without causing hot spots.

The reaction apparatus used in the production process of the present invention and the hollow mixer constituting the reaction apparatus will be described with reference to the drawings.
FIG. 1 is a diagram schematically showing an entire reaction apparatus according to an embodiment of the present invention. The configuration shown in the figure can be applied to a so-called microreactor, for example.
As a manufacturing process, in the first process, the first solution and the second solution are respectively supplied to the first hollow tube 01 (first hollow flow path) and the second hollow tube 02 (second The first solution and the first hollow mixer 03 are continuously supplied to the first hollow mixer 03 via the hollow flow path portion), and the first solution and the first solution are mixed in the fine space 15 provided as a flow cell type reaction region in the first hollow mixer 03. When the second solution is mixed, a polycondensation reaction occurs and a polyamide compound can be generated.

  Further, in the second step, the third solution flowing out from the first hollow mixer 03 is passed through the third hollow tube 04 (third hollow flow path portion), while the fourth solution is fed by the liquid feeding device 11 to the first solution. Fine space provided as a flow cell type reaction region in the second hollow mixer 06 continuously supplied to the second hollow mixer 06 via the four hollow tubes 05 (fourth hollow flow path). In 19, the third solution and the fourth solution are mixed to cause an end-capping reaction, thereby producing an end-capped polyamide compound.

In the present invention, in order to improve the mixing efficiency of the reaction materials in the fine spaces 15 and 19 in the hollow mixers 03 and 06 used in the first step and the second step, the cross-sectional area of each fine space is 10 ² to. 10 ⁷ μm ² is preferable.
Here, the fine space, which is the reaction region in the hollow mixer, refers to the supply flow of each reaction material, and the traveling direction of each supply flow is adjusted so that each supply flow forms an appropriate angle with each other at the junction. However, the region upstream of the confluence where the liquid is fed toward the confluence (hereinafter sometimes referred to as “region before confluence”) and the supply streams collide with each other at an appropriate angle and linear velocity to start mixing. Including a region of a merging point (hereinafter sometimes referred to as a “merging region”) and a region downstream of a merging point where mixing and reaction proceed (hereinafter also referred to as a “post-merging region”). It is a space for performing the reaction process.
Further, in the present invention, “a cross-sectional area of a fine space” or “a cross-sectional area of a hollow flow path portion” means a cross-sectional area perpendicular to the axial direction of the flow path (advancing direction of supply flow).

FIG. 2 is a cross-sectional view showing the fine structure of the first hollow mixer 03 constituting the first process portion in the reaction apparatus.
The first hollow mixer 03 includes a first fine space 15, a first inlet connection portion 12 that connects the first fine space 15 and the first hollow tube 01, and the first fine space 15 and the second hollow tube 02. And the first inlet connection part 13 that connects the first minute space 15 and the first outlet connection part 14 that connects the third hollow tube 04 can be used.
In the case of such a configuration, the first solution and the second solution are passed through the first hollow tube 01 and the second hollow tube 02 by the liquid feeding devices 09 and 10 configured by a syringe pump, a plunger pump, or the like. The first inlet connection portions 12 and 13 are continuously supplied to the first fine space 15 provided in the first hollow mixer 03, respectively. The supplied first solution and second solution react in the fine space to generate a polyamide compound, which can be discharged from the first outlet connection portion 14.

Here, the first hollow mixer 03 illustrated in FIG. 2 has a T-shaped flow path, and each supply flow of the first solution and the second solution flowing in from the first inlet connection portions 13 and 14 is as follows. , They collide relative to each other at an angle of substantially 180 ° at the confluence of the first fine space 15 and are mixed to produce a reaction, and the third solution containing the reaction product is separated from each other in the region before the confluence. The liquid is fed in a direction that forms an angle of 90 ° with respect to the traveling direction of the supply flow, and is discharged to the downstream side through the first outlet connection portion 14. It may be a shape.
From the viewpoint of improving the mixing efficiency, the collision angle of the respective feed streams traveling in the pre-merging region is preferably in the range of 60 ° to 300 °, particularly in the range of 120 ° to 180 °. The traveling direction of the mixed flow after (especially immediately after the merging point) is within a range of 30 ° to 150 °, particularly 60 ° to 120 °, with respect to the traveling direction of the respective feed streams in the region before the merging (especially immediately before the merging point). It is preferable to be within the range.
In addition, as a mixing area | region in a 1st hollow mixer, the cross-sectional area of the area | region before the confluence | merging of the micro space 15 to which a 1st solution and a 2nd solution are each supplied is 1.96 * 10 < ⁵ > micrometer < ² > (inner diameter 500 micrometers), for example. The structure which was made is mentioned.

In order to improve productivity, in the first hollow mixer 03, it is preferable to connect a plurality of mixing regions including the fine spaces in parallel.
Examples of the method for controlling the reaction temperature include a method in which a temperature control unit is provided in the vicinity of the mixing space, and a method in which the hollow mixer is immersed in a temperature-controlled water bath.

FIG. 3 is a cross-sectional view showing the fine structure of the second hollow mixer 06 constituting the second step portion in the reaction apparatus.
As the second hollow mixer 06, the second fine space 19, the second inlet connection part 16 connecting the second fine space 19 and the third hollow tube 04, the second fine space 19 and the fourth hollow tube 05 are connected. And the second inlet connection part 17 connecting the second minute space 19 and the fifth hollow tube 07 can be used.

  In the case of such a configuration, the third solution and the fourth solution are respectively passed through the third hollow tube 04 and the fourth hollow tube 05 by the liquid feeding devices 09 to 11 such as a syringe pump and a plunger pump. The two inlet connection portions 16 and 17 are continuously supplied to the second fine space 19 provided in the second hollow mixer 06. The supplied third solution and fourth solution react in the fine space to generate a terminal-capped polyamide compound, which can be discharged from the second outlet connection portion 18.

Here, the second hollow mixer 06 illustrated in FIG. 3 has a T-shaped channel as in the case of the first hollow mixer. Other shapes may be used.
From the viewpoint of improving the mixing efficiency, the collision angle of each supply flow traveling in the region before merging and the traveling direction of the mixed flow after merging are the same angular range as in the case of the first hollow mixer 03. It is preferable to adjust to.

  In the second hollow mixer, the third solution contains a polymer, and the viscosity and flow rate are greatly different from those of a solution containing a monomer or the like, making mixing difficult. In order to efficiently mix the third solution containing such a polymer and the fourth solution containing a compound having a low viscosity unlike the polymer, the fourth hollow tube 05 and / or the second hollow tube for supplying the fourth solution are used. The inner diameter of the pre-merging region for supplying the fourth solution in the fine space (cross section of the flow path for supplying the fourth solution) is set in the third hollow tube 04 for supplying the third solution and / or in the second fine space. It is more preferable because the mixing efficiency can be improved by making it narrower than the inner diameter (cross section of the flow path for supplying the third solution) of the region before joining the third solution and increasing the linear velocity.

As the mixing region in the second hollow mixer, for example, the cross-sectional area of the region before joining the fine space 15 in the first hollow mixer is set to the above-mentioned size, and the fine space 19 in the second hollow mixer is The cross-sectional area of the region before merging for supplying the third solution is 3.14 × 10 ⁶ μm ² (inner diameter 2000 μm), and the cross-sectional area of the region before merging for supplying the fourth solution in the fine space 19 is 1 .96 × 10 ⁵ or 4.91 × 10 ⁴ μm ² (inner diameter 500 or 250 μm) or, as shown in FIG. 3, as described above as the fourth hollow tube for supplying the fourth solution with those having a cross-sectional area 1.96 × 10 ⁵ or 4.91 × 10 ⁴ μm ² (inner diameter 500 or 250 [mu] m), by inserting the fourth hollow tube to a second hollow mixer, the tip opening It can be cited an arrangement with the structure to match the position of the confluence of the 3 solution.

In order to improve productivity, in the second hollow mixer 06, it is preferable to provide a plurality of mixing regions composed of the fine spaces in parallel.
Examples of the method for controlling the reaction temperature include a method in which a temperature controller is provided near the mixing space and a method in which the hollow mixer is immersed in a temperature-controlled water bath.

In the first and second hollow mixers described above, the fine space preferably has a cross-sectional area of 10 ² to 10 ⁷ μm ² , and the inner diameter of the fine spaces 15 and 19 is preferably 1 to 2000 μm, and is preferably 25 to 1500 μm. Is more preferable, and it is still more preferable that it is 50-1300 micrometers.

  Examples of the diamine compound (A) used in the present invention include m-phenylenediamine, p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, bis (4-aminophenyl) ether, and 1,4-cyclohexanediamine. O-toluidinediamine, p-toluidinediamine, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl and 4 , 4'-diamino-2,2'-bis (trifluoromethyl) biphenyl and the like. These may be used alone or in combination of two or more.

  Examples of the dicarboxylic acid chloride compound (B) used in the present invention include phthalic acid chloride, isophthalic acid chloride, terephthalic acid chloride, 2-methylisophthalic acid chloride, 3-methylphthalic acid chloride, 2-methylterephthalic acid chloride, 2, 4,5,6-tetramethylisophthalic acid chloride, 3,4,5,6-tetramethylphthalic acid chloride, 2-fluoroisophthalic acid chloride, 3-fluorophthalic acid chloride, 2-fluoroterephthalic acid chloride, 2,4 , 5,6-tetrafluoroisophthalic acid chloride, 3,4,5,6-tetrafluorophthalic acid chloride, 4,4'-oxybisbenzoic acid chloride, 3,3'-oxybisbenzoic acid chloride, 3,4'- Oxybisbenzoic acid chloride, 2,4′-oxybisbenzoic acid chloride, 3,4 ′ Oxybis benzoic acid chloride, 2,3'-oxybis benzoic acid chloride, 4,4'-oxy-bis-octafluoro acid chloride and 3,3'-oxy-bis-octafluoro acid chloride, and the like. These may be used alone or in combination of two or more.

  Examples of the dicarboxylic acid anhydride compound (D) used in the present invention include phthalic acid anhydride, maleic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, cis-1 , 2-cyclohexyldicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, and the like. These may be used alone or in combination of two or more.

  The first solution preferably contains a base because the molecular weight can be further increased. Examples of the base used in the present invention include pyridine, N, N-dimethylaminopyridine, 2,4,6-trimethylpyridine, 2-trimethylsilylpyridine, triethylamine and the like. These may be used alone or in combination of two or more.

  As a method for producing the end-capped polyamide resin of the present invention, first, a diamine compound (A), a dicarboxylic acid chloride compound (B), and a dicarboxylic acid anhydride compound (C), if necessary, a base, N , N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. are dissolved in an organic solvent to prepare a first solution, a second solution, and a third solution, respectively. These solutions are sequentially sent to the reaction apparatus by a syringe pump or a plunger pump, introduced into a first or second hollow mixer having a fine space, and reacted in a specific temperature region, thereby end-capping. A solution of the stationary polyamide compound is obtained. The reaction temperature is preferably 20 to 30 ° C. and more preferably 23 to 27 ° C. in order to form a polymer structure. The reaction temperature may be the same or different in the first hollow mixer and the second hollow mixer.

In the method for producing a polyamide resin of the present invention, the reaction molar ratio of the dicarboxylic acid chloride compound (B) to the diamine compound (A) is the concentration of the first solution and the second solution, or the first in the first hollow mixer. It is preferable to adjust the linear velocity immediately before mixing the solution and the second solution (immediately before the confluence), more preferably to adjust by the linear velocity, the concentration of the first solution and the second solution, and the linear velocity. More preferably, the speed is adjusted.
The reaction molar ratio of the dicarboxylic acid anhydride compound (D) to the polyamide compound (C) is the concentration of the third solution and the fourth solution, or the mixing of the third solution and the fourth solution in the second hollow mixer. It is preferable to adjust the linear velocity immediately before (immediately before the merging point) by changing appropriately, more preferably to adjust by the linear velocity, and further to adjust the concentrations of the third solution and the fourth solution and the linear velocity. preferable.
The linear velocity immediately before the mixing of each of the first solution, the second solution, the third solution, and the fourth solution (immediately before the confluence) is the cross-sectional area (inner diameter of the hollow tube) of the hollow flow path for each solution and / or It can be adjusted by appropriately changing the cross-sectional area of the flow path in the region before joining in the fine space.

The reaction molar ratio (B / A) of the dicarboxylic acid chloride compound (B) to the diamine compound (A) is preferably 0.5 to 1.0, and the dicarboxylic acid anhydride compound to the polyamide compound (C). The reaction molar ratio (D / C) of (D) is preferably 0.1 to 0.5.
Moreover, the addition amount in the case of adding a base is preferably 0.0 to 3.0 in terms of a molar ratio (base / A) to the diamine compound (A).

The linear velocity immediately before mixing of the feed streams of the diamine compound (A) and the dicarboxylic acid chloride compound (B) in the reaction zone is 10 ⁻⁴ to 10 ² m in order to exhibit sufficient mixing ability and control the molecular weight. / ³ is preferable, and 10 ^{−3 to} 10 m / second is more preferable. If the upper limit is exceeded, the time for staying in the fine space that is the reaction region is too short and the reaction does not proceed sufficiently, so the molecular weight may not increase, and if it is less than the lower limit, the fluid collision becomes weak and mixing occurs. May not be sufficiently performed, and the molecular weight distribution may become wide.
In addition, the linear velocity immediately before mixing of the feed streams of the polyamide compound (C) and the dicarboxylic anhydride compound (D) in the reaction region is 10 ⁻⁴ to in order to exhibit sufficient mixing ability and control the molecular weight. 10 ² m / sec is preferable, and 10 ^{−3 to} 10 m / sec is more preferable.
The total reaction time is preferably 1 to 60 seconds when calculated from the linear velocity.

  Here, the linear velocity immediately before mixing of each solution (immediately before merging) may be measured directly at the position immediately before merging, or the linear velocity of the solution in the hollow channel portion, the cross-sectional area of the hollow channel portion, and the fine space It may be calculated from other measured values such as the cross-sectional area of the region before joining. In addition, when the cross-sectional area of the hollow flow path portion is the same as the cross-sectional area of the region before confluence of the fine space, or when the hollow tube constituting the hollow flow passage portion is inserted to the depth of the confluence of the fine space, The linear velocity of the solution in the passage can be specified as it is as the linear velocity immediately before mixing (immediately before joining) of the solution.

  In particular, it is preferable to provide a linear velocity ratio in order to improve the mixing efficiency of the third solution and the fourth solution. As the linear velocity ratio of the third solution and the fourth solution (third solution / fourth solution), for example, a linear velocity ratio of 10/1 to 1/10 is preferable, and 2/1 to 1/10. The linear velocity ratio is more preferable, and in particular, from the viewpoint of increasing the linear velocity of the solution having a smaller viscosity, the linear velocity ratio is preferably 1/1 to 1/10.

In the method using the first hollow mixer and the second hollow mixer as described above, the diamine compound (A), the dicarboxylic acid chloride compound (B), the polyamide compound (C), and the dicarboxylic acid anhydride compound (D). And the reaction molar ratio between the diamine compound (A) and the dicarboxylic acid chloride compound (B) and the reaction molar ratio between the polyamide compound (C) and the dicarboxylic anhydride compound (D). By adjusting the above, the end-capped polyamide compound can be produced by controlling the molecular weight, and the end-capped polyamide resin obtained therefrom also has a narrow molecular weight distribution.
Specifically, according to the production method of the present invention, the molecular weight distribution (Mw / Mn) is 3.0 or less, more preferably the molecular weight distribution (Mw / Mn) is in the range of 1.0 to 3.0. Such an end-capped polyamide resin having a narrow molecular weight distribution can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by this.

  Including the reaction time in Examples and Comparative Examples, and the results of the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the respective resins calculated using gel permeation chromatography, These results are summarized in Table 1.

Example 1
(1) Procedure 1.6059 g (about 8.0 mmol) of bis (4-aminophenyl) ether, 1.5461 g (about 7.6 mmol) of isophthalic acid chloride, 0.2655 g of 5-norbornene-2,3-dicarboxylic acid anhydride (About 1.6 mmol) were dissolved in 20.0 ml of dried N-methyl-2-pyrrolidone, 20.0 ml of γ-butyrolactone and 8.0 ml of N-methyl-2-pyrrolidone, respectively, to prepare each reaction solution.
The first solution (bis (4-aminophenyl) ether solution) and the second solution (isophthalic acid chloride solution) are sucked into a gas tight syringe manufactured by Hamilton, and the first hollow mixing is performed using a PHD 2000 Programmable Syringe Pump manufactured by Harvard. Supplied to the machine. Subsequently, the third solution (reaction solution of the first solution and the second solution) discharged from the first hollow mixer is sent to the second hollow mixer, and the fourth solution (5-norbornene-2 , 3-dicarboxylic acid anhydride solution) is sucked into a Hamilton gastight syringe and supplied to the second hollow mixer using a Harvard PHD 2000 Programmable Syringe Pump, and end-sealed from the outlet of the second hollow mixer. A reaction liquid containing a stationary polyamide resin was obtained.
Each gas tight syringe was connected to the first and second hollow mixers with a Tefzel tube 50 cm (inner diameter 800 μmφ, outer diameter 1/16 inch; Tefzel is a resin tube trade name obtained from DuPont). . A Tefzel tube 50 cm (inner diameter 800 μmφ, outer diameter 1/16 inch) was attached to the outlet of the second hollow mixer.
(2) Reaction conditions Regarding the linear velocity of the solution in the hollow mixer, the linear velocity immediately before the mixing of the first solution and the second solution supplied to the first hollow mixer is 4.24 × 10 ⁻¹ m / The linear velocity immediately before mixing the third solution supplied to the second hollow mixer is set to 8.49 × 10 ⁻¹ m / second, and the fourth solution supplied to the second hollow mixer is set. The linear velocity immediately before mixing was set to 8.49 × 10 ⁻² m / sec, and the mixture was fed to each hollow mixer to perform mixing and reaction.
In addition, about the cross-sectional area of the fine space in a 1st and 2nd hollow mixer, the cross-sectional area of the area before joining for supplying a 1st, 2nd, 3rd, and 4th solution is all 1.96x. 10 ⁵ μm ² .
In the first and second hollow mixers, the inner diameter of the region before joining for supplying the first, second, third and fourth solutions is 500 μm.
All reactions were performed at room temperature. The reaction temperature was measured using a wide range temperature data logger TR-81 manufactured by T & D Corporation.
The reaction time calculated from the linear velocity was 2.9 seconds, and the linear velocity ratio between the third solution and the fourth solution was 10/1.
(3) Results The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polyamide resin were abbreviated as “GPC permeation chromatography” (hereinafter abbreviated as GPC). ) Using polystyrene conversion to be 2.97 × 10 ⁴ and 2.61 respectively.

(Example 2)
(1) Procedure In Example 1, the amounts of bis (4-aminophenyl) ether, isophthalic acid chloride, and 5-norbornene-2,3-dicarboxylic acid anhydride were 1.6027 g (about 8.0 mmol) and 1. A terminal-capped polyamide resin was synthesized in the same manner as in Example 1 except that 5449 g (about 7.6 mmol) and 0.7893 g (about 4.8 mmol) were changed.
(2) Reaction conditions The same as in Example 1.
(3) Results When the weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the end-capped polyamide resin obtained were determined using GPC in the same manner as in Example 1, 2.96 × 10 ⁴ and 2.42.

(Example 3)
(1) Procedure In Example 1, the amounts of bis (4-aminophenyl) ether, isophthalic acid chloride, and 5-norbornene-2,3-dicarboxylic acid anhydride were 1.6079 g (about 8.0 mmol) and 1. Except that the reaction conditions were changed as follows, the end-capped polyamide resin was changed to 5467 g (about 7.6 mmol) and 0.2671 g (about 1.6 mmol). Synthesized.
(2) Reaction conditions Regarding the linear velocity of the solution in the hollow mixer, the linear velocity immediately before the mixing of the first solution and the second solution supplied to the first hollow mixer is 4.24 × 10 ⁻¹ m / The linear velocity immediately before mixing of the third solution supplied to the second hollow mixer is set to 5.31 × 10 ⁻² m / second and the fourth solution supplied to the second hollow mixer is set to The linear velocity immediately before mixing was set to 8.49 × 10 ⁻² m / sec, and the mixture was fed to each hollow mixer to perform mixing and reaction.
In addition, about the cross-sectional area of the fine space in a 1st and 2nd hollow mixer, the cross-sectional area of the area | region before the merging for supplying a 1st and 2nd solution is 1.96 * 10 < ⁵ > micrometer ² both. The cross-sectional area of the region before joining for supplying the third solution is 3.14 × 10 ⁶ μm ² , and the cross-sectional area of the region before joining for supplying the fourth solution is 1.96 × 10 ^5. μm ² .
In the first and second hollow mixers, the inner diameter of the region before joining for supplying the first and second solutions is 500 μm, and the inner diameter of the region before joining for supplying the third solution is The inner diameter of the region before joining for supplying the fourth solution is 2000 μm.
All reactions were performed at room temperature. The reaction temperature was measured using a wide range temperature data logger TR-81 manufactured by T & D Corporation.
The reaction time calculated from the linear velocity was 2.9 seconds, and the linear velocity ratio between the third solution and the fourth solution was 5/8.
(3) Results When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polyamide resin were determined using GPC in the same manner as in Example 1, 2.89 × 10 ⁴ and 2.42.

Example 4
(1) Procedure In Example 3, the amounts of bis (4-aminophenyl) ether, isophthalic acid chloride, and 5-norbornene-2,3-dicarboxylic acid anhydride were 1.6063 g (about 8.0 mmol) and 1. A terminal-capped polyamide resin was synthesized in the same manner as in Example 3 except that the amount was changed to 5489 g (about 7.6 mmol) and 0.7910 g (about 4.8 mmol).
(2) Reaction conditions The same as in Example 1.
(3) Results When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polyamide resin were determined using GPC in the same manner as in Example 1, 2.84 × 10 ⁴ and 2.37.

(Example 5)
(1) Procedure In Example 1, the amounts of bis (4-aminophenyl) ether, isophthalic acid chloride, and 5-norbornene-2,3-dicarboxylic acid anhydride were 1.6083 g (about 8.0 mmol), 1 .5464 g (about 7.6 mmol), 0.2675 g (about 1.6 mmol), and except that the reaction conditions were changed as described below, all in the same manner as in Example 1 except that the end-capped polyamide resin was used. Was synthesized.
(2) Reaction conditions Regarding the linear velocity of the solution in the hollow mixer, the linear velocity immediately before the mixing of the first solution and the second solution supplied to the first hollow mixer is 4.24 × 10 ⁻¹ m / The linear velocity immediately before mixing of the third solution supplied to the second hollow mixer is set to 5.31 × 10 ⁻² m / second and the fourth solution supplied to the second hollow mixer is set to The linear velocity immediately before mixing was set to 3.40 × 10 ⁻¹ m / sec, and the mixture was fed to each hollow mixer for mixing and reaction.
In addition, about the cross-sectional area of the fine space in a 1st and 2nd hollow mixer, the cross-sectional area of the area | region before the merging for supplying a 1st and 2nd solution is 1.96 * 10 < ⁵ > micrometer ² both. The cross-sectional area of the region before joining for supplying the third solution is 3.14 × 10 ⁶ μm ² , and the cross-sectional area of the region before joining for supplying the fourth solution is 4.91 × 10 ^4. μm ² .
In the first and second hollow mixers, the inner diameter of the region before joining for supplying the first and second solutions is 500 μm, and the inner diameter of the region before joining for supplying the third solution is The inner diameter of the region before joining for supplying the fourth solution is 250 μm.
All reactions were performed at room temperature. The reaction temperature was measured using a wide range temperature data logger TR-81 manufactured by T & D Corporation.
The reaction time calculated from the linear velocity was 2.9 seconds, and the linear velocity ratio between the third solution and the fourth solution was 5/32.
(3) Results When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polyamide resin were determined using GPC in the same manner as in Example 1, they were 2.97 ×. 10 ⁴ and 2.35.

(Example 6)
(1) Procedure In Example 5, the amounts of bis (4-aminophenyl) ether, isophthalic acid chloride, and 5-norbornene-2,3-dicarboxylic acid anhydride were 1.6059 g (about 8.0 mmol), 1 An end-capped polyamide resin was synthesized in the same manner as in Example 5 except that it was changed to 0.5496 g (about 7.6 mmol) and 0.7914 g (about 4.8 mmol).
(2) Reaction conditions The same as in Example 1.
(3) Results When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polyamide resin were determined using GPC in the same manner as in Synthesis Example 1, they were each 2.88 ×. 10 ⁴ and 2.31.

(Comparative Example 1)
In a glass three-necked flask, 0.8042 g (about 4.0 mmol) of bis (4-aminophenyl) ether was added and dissolved in 10.0 ml of dried N-methyl-2-pyrrolidone. Thereafter, a solution of 0.7759 g (about 3.8 mmol) of isophthalic acid chloride in 10.0 ml of γ-butyrolactone was added at 25 ° C. under a nitrogen atmosphere, and stirring was continued for 90 minutes. Next, a solution prepared by dissolving 0.0676 g (about 0.4 mmol) of 5-norbornene-2,3-dicarboxylic anhydride in 1.0 ml of N-methyl-2-pyrrolidone was added, and stirring was further continued for 90 minutes. All reactions were performed at room temperature. The reaction temperature was measured using a wide range temperature data logger TR-81 manufactured by T & D Corporation. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polyamide resin were determined using GPC in the same manner as in Example 1, 3.24 × 10 ⁴ and 2.77.

(Comparative Example 2)
In Comparative Example 1, the amounts of bis (4-aminophenyl) ether, isophthalic acid chloride, and 5-norbornene-2,3-dicarboxylic acid anhydride were 0.8046 g (about 4.0 mmol) and 0.7766 g (about 3), respectively. 0.8 mmol) and 0.1993 g (about 1.2 mmol), except that the end-capped polyamide resin was synthesized in the same manner as in Comparative Example 1. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polyamide resin were determined using GPC in the same manner as in Example 1, 3.14 × 10 ⁴ and 2.64.

* 1: In the numerical values of the cross-sectional area, linear velocity and Mw, “E + x” means 10 ^x (10 to the power of x) times, and “E−x” means 10 ^x (10 xth power).
* 2: The flow rate is the amount of solution used for the reaction.
* 3: In the example group, the reaction time means that the bis (4-aminophenyl) ether solution and the isophthalic acid chloride solution are injected into the first hollow mixer and then connected to the downstream side of the second hollow mixer. It means the time required for the reaction product to flow out from the hollow tube 07 (see FIG. 1).
* 4: Reaction temperature is room temperature (24.0 ° C) ± change in reaction temperature (° C)

  From the results of Examples and Comparative Examples summarized in Table 1, it is clear that the end-capped polyamide resin synthesized by the production method of the present invention is efficiently synthesized in a short time compared to the conventional product, In addition, since the reaction temperature can be precisely controlled within a specific temperature range, a uniform end-capped polyamide resin is produced, and the molecular weight distribution is narrower than conventional polymerization methods. I understand that.

  Since the end-capped polyamide resin obtained by the production method of the present invention is a uniform polymerization product having a narrow molecular weight distribution, it is suitable for use in photosensitive resins and high-performance resins that require such characteristics. is there.

It is a figure which simplifies and shows the whole reactor of one Embodiment of this invention. It is sectional drawing which shows the 1st hollow mixer 03 which has the microstructure which comprises a reaction apparatus. It is sectional drawing which shows the 2nd hollow mixer 06 which has the microstructure which comprises a reaction apparatus.

Explanation of symbols

01 1st hollow tube 02 2nd hollow tube 03 1st hollow mixer 04 3rd hollow tube 05 4th hollow tube 06 2nd hollow mixer 07 5th hollow tube 08 Recovery container 09-11 Liquid feeding device 12, 13 1st 1 inlet connection part 14 1st outlet connection part 15 1st micro space 16, 17 2nd inlet connection part 18 2nd outlet connection part 19 2nd micro space

Claims (14)

The first solution containing the diamine compound (A) and the second solution containing the dicarboxylic acid chloride compound (B) are respectively sent from the first hollow channel portion and the second hollow channel portion to the diamine compound (A) and the above-mentioned The third solution containing the polyamide compound (C) is introduced into a first hollow mixer having a fine space having a cross-sectional area of 10 ² to 10 ⁷ μm ² , which is a reaction region with the dicarboxylic acid chloride compound (B), and mixed. A process for producing a terminal-capped polyamide resin, comprising a first step of obtaining   The method for producing a terminal-capped polyamide resin according to claim 1, wherein the first solution contains a base. A third solution containing the polyamide compound (C) and a fourth solution containing the dicarboxylic acid anhydride compound (D) are respectively added to the polyamide compound (C) from a third hollow channel portion and a fourth hollow channel portion. Or a second step of mixing and introducing into a second hollow mixer having a fine space having a cross-sectional area of 10 ² to 10 ⁷ μm ² , which is a reaction region between the carboxylic acid anhydride compound (D) and the dicarboxylic acid anhydride compound (D). 2. A method for producing the end-capped polyamide resin according to 2.   The method for producing a terminal-capped polyamide resin according to any one of claims 1 to 3, wherein the first and / or the second hollow mixer has a plurality of the fine spaces.   The reaction molar ratio of the dicarboxylic acid chloride compound (B) to the diamine compound (A) in the reaction zone in the first hollow mixer is the concentration of the first solution and the second solution and / or the first solution and the second solution. The method for producing a terminal-capped polyamide resin according to any one of claims 1 to 4, which is adjusted by a linear velocity immediately before mixing.   The reaction molar ratio of the dicarboxylic anhydride compound (D) to the polyamide compound (C) in the reaction zone in the second hollow mixer is the concentration of the third solution and the fourth solution and / or the third solution and the fourth solution. The method for producing a terminal-capped polyamide resin according to any one of claims 3 to 5, which is adjusted by a linear velocity immediately before mixing of the solution.   The end-capping type according to any one of claims 1 to 6, wherein a reaction molar ratio (B / A) of the dicarboxylic acid chloride compound (B) to the diamine compound (A) is 0.5 to 1.0. A method for producing a polyamide resin.   The end-capping according to any one of claims 3 to 7, wherein a reaction molar ratio of the dicarboxylic acid anhydride compound (D) to the polyamide compound (C) is (D / C) 0.1 to 0.5. Of manufacturing a type polyamide resin. The method for producing a terminal-capped polyamide resin according to any one of claims 5 to 8, wherein linear velocities immediately before mixing the first solution and the second solution are 10 ^-4 to 10 ² m / sec. The method for producing a terminal-capped polyamide resin according to any one of claims 6 to 9, wherein linear velocities immediately before mixing the third solution and the fourth solution are 10 ^-4 to 10 ² m / sec, respectively.   11. The linear velocity of the third solution and the linear velocity of the fourth solution have a linear velocity ratio (third solution / fourth solution) of 1/1 to 1/10. A method for producing the end-capped polyamide resin described in 1.   The method for producing a terminal-capped polyamide resin according to claim 11, wherein the linear velocity ratio is adjusted by a cross-sectional area of the hollow channel and / or the fine space.   The method for producing an end-capped polyamide resin according to any one of claims 1 to 12, wherein a reaction temperature in a reaction region in the first and / or the second hollow mixer is controlled from 20 ° C to 30 ° C. .   The method for producing a terminal-capped polyamide resin according to any one of claims 1 to 13, wherein a molecular weight distribution (Mw / Mn) of the terminal-capped polyamide resin obtained by the production method is 3.0 or less.

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