JP3915304B2 - Continuous polycondensation equipment - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a horizontal continuous condensation polymerization apparatus, and more particularly to a horizontal continuous condensation polymerization apparatus capable of increasing the polymerization reaction rate of a condensation polymerization type polymer.
[0002]
[Prior art]
As a continuous polymerization apparatus for producing a polycondensation type high viscosity polymer such as polyester or polycarbonate, for example, Japanese Patent Publication No. 53-1228 and Japanese Patent Application Laid-Open No. 10-259242 are known. The former continuous polymerization equipment scoops up the liquid to be treated while rotating a stirrer with a scraper attached to a ring-shaped disk, and drops it onto a porous disk or wire mesh disk to form a thin film, thereby promoting evaporation of volatiles. It is made to let you. Further, the latter continuous polymerization apparatus is a stirrer in which the liquid to be treated is treated with a stirrer comprising a hollow disc provided with a scraper plate on the outer peripheral portion in a low-viscosity region, and then a scraper plate is provided radially in a region of medium viscosity. Is processed.
[0003]
However, each polymerization apparatus simply drops the liquid to be treated on the perforated disk or wire mesh disk in the direction of gravity, so that it increases the volatile surface area, which is an important factor in increasing the reaction rate. Then there was a limit. Therefore, it cannot be said that a sufficient effect has been obtained for the problem of further increasing the polymerization reaction rate.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a horizontal continuous polycondensation apparatus capable of increasing the polymerization reaction speed by increasing the volatile surface area and further improving the productivity.
[0005]
[Means for Solving the Problems]
The horizontal continuous condensation polymerization apparatus of the present invention that achieves the above object is provided with a raw material supply port at one end in the longitudinal direction of a horizontally long container, a polymer outlet at the other end, and a volatiles discharge port at the top, and an opening at the center of rotation. A plurality of stirring disk groups each having a state in which a plurality of wire mesh disks or perforated disks arranged coaxially at a small interval are arranged as a unit, and arranged in groups in the longitudinal direction of the container, The disc interval w is increased as the stirring disc group is located farther from the raw material supply port.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
1A and 1B show an embodiment of a horizontal continuous condensation polymerization apparatus of the present invention.
In FIG. 1, the container 1 of the main body is configured as a cylindrical body having a horizontally long side view and an oval cross-sectional shape. At one end of the container 1 in the longitudinal direction, a raw material supply port 2 is provided on the bottom surface, and a polymer outlet 3 for a polymerization reaction product is provided on the bottom surface of the other end. Further, a volatile matter discharge port 4 is provided on the upper side of the container 1 on the side close to the raw material supply port 2.
[0007]
A large number of stirring disk groups 5 are arranged in the container 1 so as to be separated at a predetermined interval along the longitudinal direction thereof. As shown in the enlarged view of FIG. 2, each of these stirring disk groups 5 is configured such that a plurality (two in the figure) of wire mesh disks or perforated disks 5A (unit disks) are coaxially arranged with a small interval w. Has been. Moreover, the disk interval w in each stirring disk group 5 is set so as to increase as the stirring disk group 5 is located farther from the raw material supply port 2 toward the polymer outlet 3 side.
[0008]
In FIG. 2, the unit disk constituting the stirring disk group 5 is a wire mesh disk 5A formed in a donut shape having a circular opening 5q at the center of rotation, and the donut-shaped annular surface has a large number of small holes 5p. To form an E mesh. As the unit disk, a large number of small holes 5p may be formed in a donut-shaped annular surface.
[0009]
A large number of stirring disk groups 5 arranged in the longitudinal direction have no rotation shaft at the center of rotation, and a plurality of connecting rods 6 are arranged at equal intervals in the circumferential direction on the outer periphery of the donut, and they are skewered. They are penetrated and connected and fixed together. Support plates 7 and 8 are fixed to both ends of a plurality of connecting rods 6 to which a large number of agitation disk groups 5 are connected and fixed, and rotating shafts 9 and 10 are connected to the center of rotation of the support plates 7 and 8 and their rotation The shafts 9 and 10 are pivotally supported on the bearing portions 11 and 12 of the container 1, respectively. A driving device (not shown) is connected to one of the rotating shafts 9 and 10 so that a large number of stirring disk groups 5 are integrally rotated.
[0010]
In this way, the large number of stirring disk groups 5 provided in the horizontally long container 1 form a narrow gap 13 with respect to both side surfaces and the bottom surface of the container 1, and a large space between the top surface of the container 1. The part 14 is formed.
The polycondensation reaction is carried out by the horizontal continuous polycondensation apparatus as follows.
[0011]
When the reaction intermediate polymerization liquid is supplied as a raw material liquid from the raw material supply port 2 to the container 1 while rotating the multi-row stirring disk group 5 integrally, the raw material liquid is stirred by the stirring disk group 5 and unit disks in each group. A thin film is formed with a small hole 5p on the annular surface of 5A and an opening 5q in the center, the polymerization reaction proceeds while generating volatile components from the thin film, and gradually moves toward the polymer outlet 3 side while increasing the viscosity.
[0012]
In the continuous condensation polymerization apparatus of the present invention, the disk interval w in each stirring disk group 5 is narrow in the stirring disk group 5 in the region close to the raw material supply port 2, and the stirring disk group 5 located at a position far from the raw material supply port 2. It is set large. On the other hand, a reaction liquid having a low viscosity, in which the polymerization reaction has not progressed, tends to form a thin film having a large volatile surface area when the disk interval w is narrow. Since a wider film tends to form a larger volatile surface area, the condensation polymerization reaction apparatus of the present invention in which the disk interval w of the stirring disk group 5 is set as described above expands the volatile surface area of the reaction solution as much as possible. And increase the polymerization reaction rate.
[0013]
The above-described effect is achieved by satisfying the following formula (1) according to the distance X in which each stirring disk group 5 is separated from the raw material supply port 2 for the disk interval w (mm) in each stirring disk group 5. More preferably, it can be further improved by setting so as to satisfy the following expression (1) '. In each of the formulas (1) and (1), the distance X is a percentage (%) with respect to the distance L between the raw material supply port 2 and the polymer outlet 3.
[0014]
2.64 × (0.196 × X ² + 4.48 × X + 17) ^0.46 × 0.8 + 7
≧ w ≧ 2.64 × (0.196 × X ² + 4.48 × X + 17) ^0.46 × 0.8 −7 (1)
2.64 × (0.196 × X ² + 4.48 × X + 17) ^0.46 × 0.8 + 5
≧ w ≧ 2.64 × (0.196 × X ² + 4.48 × X + 17) ^0.46 × 0.8 −5 ▲ 1 ▼ '
[0015]
When the disk interval w is narrower than the range of the above formula (1), the volatile surface area of the thin film formed in the small hole 5p or the opening 5q of the wire mesh disk or the porous disk 5A becomes small, and more than the range of the formula (1). If it is wide, the reaction solution cannot be held between the disks and a thin film cannot be formed.
[0016]
The number of unit disks 5A constituting the stirring disk group 5 needs to be two or more in order to form a thin film having a large volatile surface area. However, if the number of sheets is too large, the volatile surface area is rather reduced. Therefore, the range of 2 to 4 sheets is preferable.
[0017]
Further, it is important that the unit disk 5A constituting the stirring disk group 5 is a wire mesh disk or a porous disk. More preferably, the hole diameter d (mm) of the small holes 5p provided on the annular surface of the wire mesh disk or the porous disk and the porosity R (%) based on the large number of small holes 5p are represented by the following formulas (2) and (3), respectively. It is preferable to satisfy the formula (2) at the same time, and more preferably satisfy the formulas (2) and (3) below.
[0018]
^{2.64 × (0.196 × X 2 +} 4.48 × X + 17) 0.46 +9
≧ d ≧ 2.64 × (0.196 × X ² + 4.48 × X + 17) ^0.46 −9 (2)
55 ≦ R ≦ 95 ▲ 3 ▼
2.64 × (0.196 × X ² + 4.48 × X + 17) ^0.46 +5
≧ d ≧ 2.64 × (0.196 × X ² + 4.48 × X + 17) ^0.46 −5 ▲ 2 ▼ '
65 ≦ R ≦ 85 ▲ 3 ▼ '
[0019]
Here, the hole diameter d is a diameter of a small hole provided in a wire mesh disk or a porous disk. If the shape of the small hole is a non-circular shape such as a triangle or a square, as illustrated in FIG. The circumscribed circle diameter (mm) is regarded as the diameter of the small hole. Moreover, since the porosity R is a porosity based on a small hole, it is the porosity of the annular surface except the opening 5q provided in the rotation center part. That is, it is the ratio (%) of the total area of the small hole area to the total disk area of the portion excluding the opening 5q.
[0020]
If the diameter d of the small holes is smaller than the range of the formula (2), in order to obtain the porosity R represented by the formula (3), it is necessary to drill a large number of small holes in the wire mesh disk or the porous disk. Production costs are very high. On the other hand, when the diameter d of the small holes is larger than the range of the formula (2), the reaction solution thin film formed in the small holes is likely to be cut, which is disadvantageous for increasing the volatile surface area. Further, if the porosity R is smaller than the range of the formula (3), the area efficiency for forming the thin film is deteriorated, and if it is larger than the range of the formula (3), the strength of the wire mesh disk or the porous disk is lowered. Durability decreases.
[0021]
In the continuous condensation polymerization apparatus of the present invention, the opening 5q is provided at the center of rotation of the wire mesh disk or perforated disk 5A, and no rotation shaft is provided. If there is a rotation shaft at the center of rotation, a large amount of the reaction solution is likely to accumulate on this rotation shaft, and the reaction solution is filled between the stirring disk groups 5 and 5 to significantly reduce the volatile surface area. Further, when the viscosity of the reaction liquid changes due to changes in operating conditions such as the degree of vacuum and temperature, it takes a long time for the liquid surface of the reaction liquid to become stable when there is a rotating shaft. Since the retention amount of the reaction liquid is a factor directly related to the reaction time, it is extremely important in the continuous condensation polymerization apparatus to maintain the retention amount constant. Therefore, since the rotation axis does not exist in the rotation center portion, the volatile surface area of the reaction solution can be expanded and the polymerization reaction rate can be further increased.
[0022]
As described above, the effect obtained by providing the opening at the center of rotation of the stirring disk group is that the diameter Dq of the opening of the wire mesh disk or the porous disk (and hence the stirring disk group) is set to the diameter D of the stirring disk group. It can be further improved by adjusting the content to 20 to 50%, preferably 30 to 40%.
[0023]
Moreover, according to the horizontal continuous condensation polymerization apparatus described above, since the relatively wide space portion 14 is provided in the upper part of the container 1, the volatile matter evaporating from the thin film can be easily transferred to the volatile matter outlet 10 via the space portion 14. Can be moved. Therefore, the flow of the volatile matter does not destroy the thin film formed in the small holes 5p and the openings 5q of the stirring disk group 5, and the volatile surface area can be increased, which can be advantageous for increasing the polymerization reaction rate.
[0024]
In general, the volatile matter discharge port 4 is provided on the polymer outlet 3 side in order to reduce the pressure loss of the volatile matter flow. However, if the volatile matter outlet 4 is provided on the polymer outlet 3 side, the polymer is discharged from the volatile matter outlet 4 together with the volatile matter. Therefore, when the distillate is circulated and reused, it cannot be used as it is. There was a problem. However, if the space 14 is provided above the stirring disk group 5 as described above, it is not necessary to consider the pressure loss of the flow of volatile matter, so the volatile matter discharge port 4 may be provided on the raw material supply port 2 side. It becomes possible, and the above-mentioned problems can be solved at once.
[0025]
In order to promote the function and effect of the upper space portion 14, the vertical distance of the space portion 14 is set to 8 to 35%, preferably 13 to 30%, more preferably 17 to the diameter D of the stirring disk group 5. It is good to be in the range of ˜26%.
[0026]
The continuous polycondensation apparatus of the present invention is preferably applied to polycondensation reaction of polycondensation type high-viscosity polymers such as polyester, polyamide and polycarbonate, and is particularly suitable for polycondensation of polyester. The polyester here means, for example, a repeating structural unit obtained by continuously performing an esterification reaction and a polycondensation reaction from terephthalic acid and ethylene glycol or terephthalic acid and ethylene glycol and other third components. 75% or more of polyester is ethylene terephthalate.
[0027]
For example, a part of the terephthalic acid component may be phthalic acid, isophthalic acid, adipic acid, sebacic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, p-β-hydroxyethoxybenzoic acid, p-hydroxybenzoic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′diphenyletherdicarboxylic acid, 4,4′diphenyldicarboxylic acid, 1,2′-diphenoxyethane, A bifunctional carboxylic acid such as p, p'-dicarboxylic acid or 2,6-naphthalenedicarboxylic acid or an ester-forming derivative thereof is substituted, or a part of the glycol component is trimethylene glycol, hexamethylene glycol -Rule, triethylene glycol, polyethylene glycol, propylene glycol, neopentyl Ricol, tetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-bis-β-hydroxyethoxybenzene, bisphenol A, trimesic acid, mono Aliphatic, alicyclic and aromatic dioxy compounds such as methoxypolyethylene glycol and naphthoic acid or ester-forming derivatives thereof may be used.
[0028]
Further, the polyester may contain additives such as pigments such as titanium oxide and carbon black, ultraviolet absorbers, fluorescent brighteners, or insoluble nucleating agents such as kaolin.
[0029]
【The invention's effect】
As described above, according to the present invention, a group of stirring disks having a unit of a state in which a plurality of wire mesh disks or perforated disks are coaxially arranged at a small interval is divided into a large number of groups at intervals in the longitudinal direction of a horizontally long container. The stirrer disk group located in the stirrer disk group is set to be larger as the stirrer disk group located farther away from the raw material supply port, and an opening is provided at the center of rotation of the stirrer disk group. Since the structure is not provided, the volatile surface area of the reaction solution can be increased as much as possible, and the polymerization reaction rate can be further increased.
[Brief description of the drawings]
FIG. 1 shows a horizontal continuous condensation polymerization apparatus according to an embodiment of the present invention, in which (A) is a longitudinal sectional view thereof, and (B) is a sectional view taken along line XY of (A).
2 is an enlarged longitudinal sectional view showing a main part of the apparatus shown in FIG.
FIG. 3 is an explanatory view of a method for measuring a small hole diameter of a wire mesh disk used in the present invention.
[Explanation of symbols]
1 Container 2 Raw material supply port 3 Polymer outlet 4 Volatile outlet 5 Stirring disk group 5A Wire mesh disk or perforated disk (unit disk)
5p Small hole 5q Opening 6 Connecting rod 9, 10 Rotating shaft

Claims (4)

A raw material supply port is provided at one end in the longitudinal direction of a horizontally long container, a polymer outlet is provided at the other end, and a volatile matter discharge port is provided at the top. A plurality of stirring disk groups each having a unit arranged in a row are arranged in the longitudinal direction of the container at intervals, and the disk spacing w in each stirring disk group is positioned at a distance far from the raw material supply port. Horizontal continuous condensation polymerization equipment that is larger than the disk group. The disk interval w (mm) in each stirring disk group is defined by the ratio X (%) of the distance from the raw material supply port of the stirring disk group to the distance L between the raw material supply port and the polymer outlet. The horizontal continuous polycondensation apparatus according to claim 1, which has a size satisfying the following formula (1).
2.64 × (0.196 × X ² + 4.48 × X + 17) ^0.46 × 0.8 + 7
≧ w ≧ 2.64 × (0.196 × X ² + 4.48 × X + 17) ^0.46 × 0.8 −7 (1) The hole diameter d (mm) and the porosity R (%) of a large number of small holes formed in the wire mesh disk or perforated disk in the stirring disk group are the distances from the raw material supply port of the stirring disk group, respectively. The horizontal continuous shrinkage according to claim 1 or 2, wherein the horizontal continuous shrinkage has a size satisfying the following formulas (2) and (3) defined by the ratio X (%) to the distance L between the raw material supply port and the polymer take-out port. Polymerization equipment.
^{2.64 × (0.196 × X 2 +} 4.48 × X + 17) 0.46 +9
≧ d ≧ 2.64 × (0.196 × X ² + 4.48 × X + 17) ^0.46 −9 (2)
55 ≦ R ≦ 95 ▲ 3 ▼ The horizontal continuous condensation polymerization apparatus according to claim 1, 2, or 3, wherein the diameter of the opening at the center of rotation is 20 to 50% of the diameter of the stirring disk group.

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