JPH10114829A - Cooling and heating apparatus and production of polymer compound solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cooling and heating apparatus which decreases energy loss, is small-sized, and dispenses with a complicatied control mechanism by combining a cooling apparatus using a screw mixer equipped with a spiral rotatable transport mechanism with a heating apparatus using a static mixer equipped with partition elements. SOLUTION: A substance mixed in a stirring tank 1 is led through an inlet port 2 into a tubular cooling container 3. In the container 3, a rotatable spiral transport mechanism 4 for stirring and transporting the substance is installed and the rotation speed of the mechanism 4 is controlled with a speed adjusting machine 6 by the power of a drive motor 5. A cooling mechanism 7 in the form of a jacket is installed around the container 3. A cooling medium comes in through an inlet port 8 and is discharged through an outlet port 9. The cooled substance is introduced through an inlet port 11 into a tubular heating container 12. The flow of the substance is divided in two, and elements 13 are installed for rotating the direction of flow of the substance divided. A heating medium comes in through an inlet port 15 and is discharged through an outlet port 16.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cooling / heating apparatus and a method for producing a polymer compound solution.

[0002]

2. Description of the Related Art Polymer compounds are used in various fields. Polymer materials, such as plastic films,
It is manufactured from a liquid in which the polymer compound is melted by heating or a solution in which the polymer compound is dissolved in a solvent. In the method using a solution, the solvent is evaporated after the formation of the polymer material. The solvent used for the polymer compound solution is a liquid that can dissolve the polymer compound to a required concentration. The solvent used is required to have an appropriate boiling point for safety and evaporation. In particular, in recent years, there has been a strong demand for solvents with respect to human bodies and the environment. For this reason, even if an attempt is made to select a solvent that satisfies these requirements from a liquid that can dissolve the polymer compound, a situation has arisen in which no suitable solvent is found.

For example, for cellulose triacetate, methylene chloride has been conventionally used as a solvent. However, the use of methylene chloride has been significantly restricted due to problems with the human body and the global environment. Acetone, a general-purpose organic solvent, has a moderate boiling point (boiling point: 56 ° C.), and is suitable for the human body and the global environment.
Less problematic than other organic solvents. However, although cellulose triacetate swells with acetone, it cannot be dissolved in acetone by a usual method.

[0004] M. G. FIG. Cowie et al., Mak
romol, Chem. 143, 105 (197
1 year) is a cellulose acetate having a substitution degree of 2.80 (60.1% of acetylation degree) to a substitution degree of 2.90 (61.3% of acetylation degree) in acetone from -80 ° C to -70 ° C. It is reported that after cooling, heating was performed to obtain a dilute solution in which 0.5 to 5% by weight of cellulose acetate was dissolved in acetone. Hereinafter, a method of obtaining a solution by cooling the mixture of the polymer compound and the solvent and then heating the mixture is referred to as a “cooling dissolution method”. The dissolution of cellulose acetate in acetone is also described in a paper by Kenji Ueide et al., "Dry spinning of cellulose triacetate from acetone solution", Journal of Textile Machinery Society, 34, 57-61 (1981). is there. This paper, as its title, applied the cooling melting method to the technical field of spinning method. In the paper, the cooling dissolution method is studied while paying attention to the mechanical properties, dyeability and cross-sectional shape of the obtained fiber. In the method described in this paper, 10 to 25
A solution of cellulose acetate having a concentration of% by weight is obtained.

[0005]

When the cooling dissolution method is used, the polymer compound can be dissolved in the solvent even if the polymer compound and the solvent are insoluble at ordinary temperature. In the cooling dissolution method, a solution is prepared by cooling and heating a swollen mixture. In order to put the cooling and melting method into practical use, a cooling and heating device is required. The present inventor has proposed a cooling device, a heating device or a stirring device (for example, the devices described in JP-A-53-8668, JP-A-1-291748 and JP-A-7-133500). ) Was examined, but no apparatus suitable for the cooling dissolution method was found. In the cooling dissolution method, in addition to the energy required for cooling and heating the swollen mixture, a large amount of energy is required for transporting and stirring the swollen mixture. That is,
The swollen mixture hardly hardens upon cooling (it becomes a very viscous state even without hardening). In the conventionally known devices, the energy loss is too large, which has been a serious problem for putting the cooling melting method to practical use. In addition, devices that require large amounts of energy require huge and complicated equipment with powerful power sources. Another object of the present invention is to provide a cooling / heating device that can be preferably used for the cooling / dissolving method. It is a further object of the present invention to provide a method for producing a polymer compound solution which improves the cooling dissolution method, requires less energy for cooling, heating, transporting and stirring the swollen mixture, and can be carried out with a simple apparatus. .

[0006]

The object of the present invention has been attained by a cooling / heating device of the following (1) and a manufacturing method of the following (2). (1) a cylindrical cooling container, a cooling container inlet provided in the container, a rotatable spiral transfer mechanism provided in the container, and a cooling mechanism provided around the container. A cooling device including a cooling container outlet provided in the container; and a cylindrical heating container, a heating container inlet provided in the container, and a plurality of heating containers provided in the container. A dividing element for dividing the flow of the substance into a plurality of parts and rotating the flow direction of the divided substance in the container, a heating mechanism provided around the container, and a heating mechanism provided in the container. A cooling / heating device comprising a heating device including a heating container outlet, wherein the cooling container outlet and the heating container inlet are connected. The partition element divides the flow of the substance in the heating vessel into two, and rotates the flow clockwise in the vessel in a clockwise direction, and controls the flow of the substance in the heating vessel. It is divided into two and consists of a counterclockwise element that rotates the flow counterclockwise in the heating vessel, and the clockwise element and the counterclockwise element are alternately arranged in the vessel by being shifted by about 90 degrees. preferable. The shapes of the cylindrical cooling container and the spiral transfer mechanism of the cooling mechanism are designed so that the heat value defined by the following equations (1) and (2) is as low as possible. preferable.

[0007]

(Equation 3)

Where E _v is the viscous heat generation (unit: W) between the screw groove and the cylinder; μ is the viscosity (Pa · S) of the substance in the container; and N is the screw rotation speed ( S ^-1 ); D _b is the cylinder (barrel) inner diameter (m); W is the width (m) of the screw groove (flow path); L is the length of the screw (m); is an average lead angle of the screw; H is a depth of the screw groove (m); θ _b is an average lead angle of the screw flight tip; Q is an liquid feed rate (kg / s); and _Qd is the traction flow (kg / s).

[0009]

(Equation 4)

Where E _f is the viscous heating value (unit: W) between the screw groove and the cylinder; μ _f is the viscosity of the substance at the tip of the flight (Pa · S); N is the screw rotation A number (S ^-1 ); D _b is the cylinder inner diameter (m)
E is the flight tip width (m); δ _f is the flight tip to cylinder clearance (m); and L is the screw length (m).

(2) mixing the polymer compound and a solvent and swelling the polymer compound with the solvent; cooling the swollen mixture to -100 to -10 ° C; and cooling the swollen mixture to 0 to 120 ° C. A method of producing a polymer compound solution comprising the steps of: dissolving a polymer compound in a solvent by heating the mixture in the solvent, wherein in the heating step, the swelling mixture is introduced into a cylindrical container; In the flow of the swollen mixture is divided into a plurality, the direction of the flow of the divided mixture is rotated in the container, while repeating this division and rotation,
A method for producing a polymer compound solution, comprising heating a swelled mixture from around the container. In the heating step, the swollen mixture is preferably heated at a rate of 1 ° C./min or more.

[0012]

The cooling / heating device of the present invention comprises a cooling device using a screw-type mixer having a helically rotatable conveying mechanism, and a static mixing device in which mixing is performed by a plurality of partition elements in a container. It consists of a combination with a heating device using a vessel. This device is characterized by a very low energy loss, a small size and no need for complicated control mechanisms. In a screw-type cooling device, when a fluid substance to be cooled is sent in the axial direction of a cylindrical container with the rotation of a spiral (screw), heat is transferred to the outside of the container provided with a cooling mechanism, and the material is cooled. Is cooled. When the temperature is lowered by cooling, the viscosity of the substance increases, but because of the drag flow caused by the rotation of the screw, there is almost no pressure loss and a constant amount of the fluid substance can be stably conveyed. The material extruded from the screw cooling device is heated in a static heating device. Energy for transporting and stirring the substance in the stationary heating device is supplied from a screw-type cooling device (more precisely, rotational energy of the screw). When a drive device is attached to both the cooling device and the heating device, a plurality of power control mechanisms are required, and the size of the entire device is increased. In the cooling / heating device of the present invention, since only the cooling device is required for the drive device, the entire device is small and does not require a complicated control mechanism. The energy for transporting and stirring the substance in the static mixer causes a considerable loss due to the contact between the container and the fluid substance. However, in the apparatus of the present invention, since the material is heated from the outside of the cylindrical container, the viscosity of the substance in contact with the container is reduced and the fluidity is increased, so that the loss of energy required for transportation and stirring is small.

As for the combination of the screw type mixer and the stationary type mixer, JP-A-53-8668 discloses a thermoplastic resin foaming extruder. This device is
It is a combination of a melt extruder using a screw mixer and a cooler using a type of static mixer (Static ^MixerTM ). That is, a screw mixer is applied for heating, and a static mixer is applied for cooling. When a static mixer is applied to cool a substance, the viscosity of the substance in contact with the container increases due to the cooling, and the fluidity of the substance decreases. Therefore, the loss of energy required for transportation and stirring becomes very large. The method for producing a polymer compound solution of the present invention is characterized on the heating treatment side. Heating treatment using a static mixer (specifically, a specific partition element in a container) is particularly effective for producing a polymer compound by a cooling dissolution method. That is, according to the method of the present invention, the energy required for cooling, heating, transporting and stirring the swollen mixture is small, and the polymer compound solution can be produced by a simple apparatus.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION

[Cooling / heating device] The cooling / heating device of the present invention is a combination of two types of different mixers. Mixers are divided into powered mixers that require mechanical moving parts and stationary mixers that do not require mechanical moving parts. The screw mixer used as a cooling device in the present invention is a typical power type mixer, and the mixer using a partition element used as a heating device in the present invention is a typical static mixer. . Screw type mixers are classified into single-shaft type and multi-shaft type (Werner type, welding type). A multi-shaft type can be used, but a single-shaft type is preferable. Single-screw screw mixers are further classified into many types depending on the attached devices and functions. Attached devices and functions include a barrier to promote melting, a screw that disturbs the flow (eg, mixing pin screw), and a compression function that increases the pressure inside the container by adjusting the shape of the screw and the outlet of the container. There is. These devices and functions may be provided in the cooling section of the cooling / heating device of the present invention. However, when used in the production of a polymer compound solution by a cooling dissolution method, it is preferable to use a screw type mixer having a simple structure without these devices and functions.

The screw mixer having the simplest structure is
A cylindrical container, an inlet provided in the container for introducing a fluid substance or a plurality of components for preparing the same into the container, a container for transporting the inside of the cylindrical container while stirring the substance It comprises a rotatable helical transport mechanism provided therein and an outlet provided in a container for discharging material. When this is used as the cooling unit of the cooling / heating device of the present invention, a cooling mechanism for cooling the substance in the container may be provided around the container. Note that, in addition to the cooling mechanism outside the container, the substance in the container may be cooled from the axis of the spiral. A screw mixer is generally used for mixing a plurality of substances. In the apparatus of the present invention, the excellent substance mixing function of the screw mixer is used for uniform and rapid cooling of the substance.

In the static mixer, the flow of a substance in a container is divided into a plurality of parts, and the divided substances are mixed by rotating the direction of the flow of the substance in the container. In particular,
By a plurality of partition elements provided in the container,
Divide and rotate the flow of material in the container. Depending on the type of partitioning element, static mixers are divided into those that simply divide and rotate the flow in the vessel and those that provide a plurality of curved passage tubes in the vessel. Both static mixers are commercially available. Examples of the former commercially available products include Static Mixer ^TM (Kenix), Square Mixer ^TM (Sakura Seisakusho Co., Ltd.), Shimazaki Pipe Mixer ^TM (Koritsu Kogyo Co., Ltd.) and High Mixer ^TM (Toray Co., Ltd.) ) Is included. Examples of the latter commercially available products include Ross ISG Mixer ^™ (Charles Ross),
Includes Static Mixing Element ^TM (Sulzer) and Honeycomb Mixer (Tatsumi Kogyo). In the present invention, a static mixer is used as a heating device, and in order to heat from the outside of the container, the former without a passage pipe,
It is preferable in terms of heat efficiency. The simplest type of static mixer has a cylindrical container, an inlet provided in the container for introducing the substance into the container, and a flow of the substance in the container divided into a plurality of parts. It comprises a plurality of partition elements provided in the container for rotating the flow direction in the container and an outlet provided in the container for discharging the substance. When this is used as a heating unit of the cooling / heating device of the present invention, a heating mechanism for heating a substance in the container may be attached around the container. Static mixers are also commonly used for mixing multiple substances. In the apparatus of the present invention, the excellent substance mixing function of the static mixer is used for uniform and rapid heating of the substance.

The partition element divides the flow of the substance in the container into a plurality. It is sufficient to split the flow into two, which is preferable because the structure of the partition element is simplified. The partition element has a threaded structure to rotate the flow of the substance in the container. When splitting a stream into two, the stream is generally rotated about 180 degrees. The partition elements are preferably arranged such that clockwise elements and counterclockwise elements are alternately arranged. When the flow is divided into two, the clockwise element and the counterclockwise element are generally arranged with a shift of about 90 degrees. A plurality of partition elements are provided in the container. If n elements are provided to divide the flow of material into two, the flow is split into 2 n powers. For example, ten elements cause 2 ¹⁰ (= approximately 1000) splits and rotations of the flow. The static mixer has a simple structure such as a partition element, and is characterized in that mixing is performed repeatedly by repeating division and rotation. The number of partition elements is preferably 4 to 200, and more preferably 8 to 100, in the container.

The cooling / heating device of the present invention is a device in which the cooling unit and the heating unit as described above are connected, specifically, the outlet of the cooling unit and the inlet of the heating unit. The outlet of the cooling unit and the inlet of the heating unit may be directly connected or may be connected by a pipe. However, the energy driven by the screw of the cooling unit needs to be transmitted to the heating unit by the flow of the substance. The cooling / heating device of the present invention is used for cooling and heating various fluid substances. Fluid material means liquid, gas or powder. It is particularly effective for cooling and heating a swelled mixture for preparing a liquid, especially a polymer compound solution.

FIG. 1 is a schematic sectional view of a preferred embodiment of the cooling / heating device of the present invention. The apparatus shown in FIG. 1 includes a stirring tank (1), a cooling unit (2 to 10), and a heating unit (11 to 11).
17). The substance mixed in the stirring tank (1)
It is introduced from the inlet (2) into a cylindrical cooling vessel (3). Inside the container (3), a rotatable spiral transfer mechanism (4) for transferring the inside of the cylindrical container while stirring the substance is provided. The transport mechanism (4) is rotated by the power of the drive motor (5) outside the container while adjusting the rotation speed by the speed adjuster (6). On the outside of the container (3), a cooling mechanism (7) is mounted in a jacket shape.
A cooling medium flows inside the cooling mechanism (7). The cooling medium enters the cooling mechanism (7) from the refrigerant inlet (8) and is discharged from the refrigerant outlet (9). The material thus cooled is discharged from the outlet (10). It is desirable that the cooling container (3) be substantially sealed in order to avoid water contamination due to condensation during cooling.

The cooled substance is supplied to the outlet (10) of the cooling section.
From the inlet (11) directly connected to the heating vessel (1)
2) is introduced. Inside the container (12), a plurality of partition elements (13) for dividing the flow of the substance in the container into two and rotating the flow direction of the divided substance in the container are provided. . A heating mechanism (14) is mounted on the outside of the container (12) in a jacket shape. A heating medium flows inside the heating mechanism (14). The heating medium enters the heating mechanism (14) from the heating medium inlet (15), and is discharged from the heating medium outlet (16). The substance thus heated is discharged from the outlet (17). FIG. 2 is a schematic diagram showing a combination of partition elements. As shown in FIG. 2, it is preferable to use the clockwise element (21) and the counterclockwise element (22) in combination. The arrows in FIG. 2 indicate the flow of the substance. When the clockwise and counterclockwise elements are combined, the directions of rotation are alternated and the balance of the rotational force is maintained.

The cooling device shown in FIG. 1 is an application of a screw mixer provided with a spiral rotatable transport mechanism. Screw mixers are commonly used for stirring materials at high temperatures. In a conventional screw mixer, the heat generated by stirring is neglected, or the heat generated by stirring is actively used for maintaining a high temperature in many cases. Therefore, in the conventional screw type mixer,
The shape of the screw and container was designed so that heat was generated by stirring. An example in which a screw mixer is used for stirring a substance at a relatively low temperature is disclosed in JP-A-7-133500. In the invention described in the publication, a screw-type mixer is used for stirring a high-viscosity material (specifically, soap) at a relatively low temperature. Therefore, a compression processing unit is provided in the first half of the mixer, and the compression processing unit To cool the high viscosity material. The screw-type mixer described in the publication is designed so that the volume between the screw and the container is gradually reduced, and that portion corresponds to a compression processing section. The compressed high viscosity material is
It is sent to the latter half of the usual screw-type mixer, where the pressure drops, the bulk density increases and the temperature further decreases.

The screw mixer disclosed in JP-A-7-133500 can also be applied to the cooling device of the present invention. However, in the present invention, the screw mixer is positively used for cooling the substance. The invention described in the above publication is an invention which is effective for maintaining a relatively low temperature state (preventing a rise in temperature), and in which the shape of a screw or a container which suppresses the heat generation due to stirring is described. No design is disclosed. According to the study of the present inventor, the calorific value due to stirring is calculated by the following equations (1) and (2).
The viscous heat value (E _v ) between the screw groove and the container (cylinder) and the viscous heat value (E _v ) between the screw flight tip and the container (cylinder), respectively, defined as
_f ) becomes a problem.

[0023]

(Equation 5)

In the equation (1), E _v is the viscous heat generation (unit: W) between the screw groove and the cylinder;
Is the viscosity (Pa · S) of the substance in the container; N is the screw rotation speed (S ^-1 ); _Db is the cylinder (barrel) inner diameter (m); W is the screw groove (flow path). L is the length (m) of the screw; θ
Is an average lead angle of the screw; H is a depth of the screw groove (m); θ _b is an average lead angle of the screw flight tip; Q is an liquid feed rate (kg / s);
_Qd is the traction flow rate (kg / s).

[0025]

(Equation 6)

In the equation (2), E _f is the viscous heat generation (unit: W) between the screw groove and the cylinder;
_f is the viscosity (Pa · S) of the substance at the tip of the flight;
N is the screw rotation speed (S ^-1 ); D _b is the cylinder inner diameter (m); e is the flight tip width (m); δ _f is the gap between the flight tip and the cylinder (m). Yes; and L is the length (m) of the screw.

Therefore, in the design of the screw mixer, the calorific value (E) defined by the above equations (1) and (2)
_The screw rotation speed (N), cylinder inner diameter (D _b ), screw groove width (W), screw length (L), average screw advance so that _v and E _f ) are as small as possible. Angle (θ), screw groove depth (H),
Average advancing angle (θ _b ) at the tip of the screw flight, liquid feed flow (Q), traction flow (Q _d ), flight tip width (e), and clearance between the flight tip and cylinder (δ
_f ) can be adjusted. FIG. 4 is a view showing a screw shape suitable for cooling designed based on the definitions of the above equations (1) and (2). In FIG. 4, W, e, and L are dimensions having the same definitions as in equations (1) and (2). Equations (1) and (2) and the parameters of each equation are described in Principles of Plastics Processing (1991), pages 446 to 451 (especially, pages 450 to 451) and Engineering Principles of Plasticating Extrusion ( Engineering Principles
232-2 of Plasticating Extrusion) (1970)
An explanation is given on page 45 (especially page 234). The viscosities of the formulas (1) and (2) were measured for the substance (liquid) used, and the empirical formula of the following formula (3) was obtained.

[0028]

(Equation 7)

In the formula (3), μ is the viscosity (unit: Pa · S) of the substance in the container; T is the absolute temperature (° K) at the time of measurement; N is the screw rotation speed (S ^−1). _Db is the cylinder inner diameter (m); and H is the screw groove depth (m). Further, an experiment was conducted by changing the screw shape under the conditions of Example 2 described later, and from the experimental results and the above equations (1) to (3), the total (E) of the viscous heat generation was calculated by the following equation (4). I got

[0030]

(Equation 8)

In the formula (4), E _v is the viscous heat generation (unit: W) between the screw groove and the cylinder;
_f is the viscous heating value (unit: W) between the screw groove and the cylinder; _Db is the cylinder inner diameter (m);
N is the screw rotation speed (S ^-1 ); H is the depth (m) of the screw groove; W is the width (m) of the screw groove (flow path); s); Q _d
Is the traction flow rate (kg / s); θ is the average lead angle of the screw; θ _b is the average lead angle at the tip of the screw flight; H is the depth of the screw groove (m);
δ _f is the clearance (m) between the flight tip and the cylinder; e is the flight tip width (m); and A and B are parameters depending on the measurement conditions.

According to the definition of equation (4), the calorific value (E _v ) decreases as the depth (H) of the screw groove (flow path) increases. This also corresponds to the results obtained experimentally. FIG. 5 is a graph plotting the results of the relationship between the screw calorific value / dope calorific value change and the screw rotation speed and screw groove depth obtained experimentally. In FIG. 5, points indicated by triangles have a groove depth of 7.0 mm, points indicated by squares have a groove depth of 5.5 mm, and points indicated by diamonds have a groove depth of 3.
0 mm, the points indicated by white circles indicate the results using a groove depth of 1.5 to 4.5 mm, and the points indicated by black circles indicate the results using a screw with a groove depth of 1.5 mm. The points indicated by white circles are described in
13 shows an experimental result of a device provided with a compression mechanism (three-fold compression) similar to the device disclosed in JP-A-133500. Therefore, the groove depth of the screw changes from 1.5 mm to 4.5 mm. ing. The results shown in FIG.
This indicates that the deeper the screw groove (flow path), the smaller the amount of generated heat.

According to the definition of equation (4), the calorific value (E _v ) decreases as the cylinder inner diameter (D _b ) increases. Groove depth (H) is 3.0 mm, liquid flow rate Q is 60
kg / h, the temperature of the substance before cooling was 30 ° C., the temperature of the substance after cooling was −50 ° C., and the temperature of the refrigerant was −55 ° C., the result of calculation using equation (4) ( Theoretical values are shown in FIG. FIG. 6 is a graph showing the relationship between the change in calorific value of the screw / the calorific value of the dope and the inner diameter of the cylinder. As shown in FIG. 6, it is preferable to design the cooling screw so that the inner diameter of the cylinder is large in order to reduce the amount of heat generated.

[Polymer Compound and Solvent] As the polymer compound and the solvent, at a certain temperature in the range of 0 to 55 ° C. (temperature at which the solution is to be used), the polymer compound and the solvent are swollen by the solvent. A combination of a molecular compound and a solvent is used. If the polymer compound does not swell with the solvent, it is almost impossible to dissolve even by using a cooling dissolution method. Even when the polymer compound is dissolved in the solvent at the above-mentioned temperature, a uniform solution can be obtained more quickly by using the cooling dissolution method of the present invention than by the conventional method of stirring at normal temperature or high temperature. Examples of the polymer compound include polyamides, polyolefins (eg, norbornene), polystyrenes, polycarbonates, polysulfones, polyacrylic acids, polymethacrylic acids, polyether ether ketones, polyvinyl alcohols,
Polyvinyl acetates and cellulose derivatives (eg, lower fatty acid esters of cellulose) are used. Particularly preferred are lower fatty acid esters of cellulose.

The lower fatty acid ester of cellulose, which is a preferred polymer compound, will be further described. The lower fatty acid means a fatty acid having 6 or less carbon atoms. The number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Cellulose acetate is more preferable, and cellulose triacetate (acetylation degree: 5
8.0 to 62.5%) is particularly preferred. A mixed fatty acid ester of cellulose such as cellulose acetate propionate or cellulose acetate butyrate may be used.

As the solvent, an organic solvent is preferable to an inorganic solvent. Examples of the organic solvent include ketones (eg, acetone, methyl ethyl ketone, cyclohexanone), esters (eg, methyl formate, methyl acetate, ethyl acetate, amyl acetate, butyl acetate), ethers (eg, dioxane,
Dioxolan, THF, diethyl ether, methyl-t
-Butyl ether), hydrocarbons (eg, benzene, toluene, xylene, hexane) and alcohols (eg, methanol, ethanol). As the solvent, an organic solvent is preferable to an inorganic solvent. Examples of organic solvents include:
Ketones (eg, acetone, methyl ethyl ketone, cyclohexanone), esters (eg, methyl formate, methyl acetate, ethyl acetate, amyl acetate, butyl acetate), ethers (eg, dioxane, dioxolan, THF, diethyl ether, methyl-t) -Butyl ether), hydrocarbons (eg, benzene, toluene, xylene, hexane) and alcohols (eg, methanol, ethanol). As described above, a liquid that swells the polymer compound is used as the solvent. Therefore, the type of the specific solvent is determined according to the type of the polymer compound used. For example, when the polymer compound is cellulose triacetate, polycarbonates or polystyrenes, acetone or methyl acetate is used as a preferred solvent. In the case of a norbornene-based polymer, benzene, toluene, xylene, hexane, acetone and methyl ethyl ketone are used as preferred solvents. In the case of polymethyl methacrylate, acetone, methyl ethyl ketone, methyl acetate,
Butyl acetate and methanol are used as preferred solvents. Two or more solvents may be used in combination.

A methyl acetate solvent containing at least 50% by weight of methyl acetate is particularly preferably used. The proportion of methyl acetate in the solvent is preferably at least 60% by weight,
More preferably, it is 0% by weight or more. Only methyl acetate (100% by weight) can be used as the solvent. Also, by using other solvents in combination with methyl acetate,
Properties of the solution to be produced (for example, the viscosity may be adjusted. The above-mentioned organic solvent can be used in combination with methyl acetate. Particularly preferred are hydrocarbons and alcohols. Two or more kinds of solvents may be used in combination with methyl acetate. The boiling point of the solvent is preferably from 20 to 300 ° C., more preferably from 30 to 200 ° C., even more preferably from 40 to 100 ° C., and most preferably from 50 to 80 ° C.

[Swelling Step] In the swelling step, the polymer compound and a solvent are mixed, and the polymer compound is swelled by the solvent. The temperature of the swelling step is preferably from -10 to 55C. It is usually performed at room temperature. The ratio between the polymer compound and the solvent is determined according to the concentration of the finally obtained solution. However, when replenishing the solvent in the cooling step described later, the amount of the solvent is reduced by the replenishment amount. Generally, the amount of the polymer compound in the swelling step is preferably 5 to 30% by weight of the solution to be prepared, more preferably 8 to 20% by weight,
Most preferably, it is 10 to 15% by weight. The swelling mixture of the solvent and the polymer compound is preferably stirred until the polymer compound swells sufficiently. The stirring time is 1
0 to 150 minutes, preferably 20 to 120 minutes.
More preferably, it is minutes. In the swelling step, components other than the solvent and the polymer compound, for example, a plasticizer, a deterioration inhibitor and an ultraviolet absorber may be added.

[Cooling Step] In the cooling step, the swollen mixture is cooled to -100 to -10 ° C. The cooling temperature is
Preferably, the temperature is such that the swelling mixture solidifies. The cooling rate is preferably 1 ° C / min or more, more preferably 2 ° C / min or more, still more preferably 4 ° C / min or more, and most preferably 8 ° C / min or more. . The cooling rate is preferably as high as possible,
C / sec is the theoretical upper limit, 1000 C / sec is the technical upper limit, and 100 C / sec is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature. In order to rapidly cool the swelling mixture, it is preferable that the swelling mixture is transported in a cylindrical container while stirring, and the swelling mixture is cooled from around the container. The device described above is preferably used for that. Also, -105 to -15 ° C
The cooled solvent can be added to the swollen mixture to allow for more rapid cooling. The temperature of the solvent to be replenished is -10
It is preferably from 0 to -25 ° C, and from -95 to -3.
More preferably, the temperature is 5 ° C, from -85 to -55 ° C.
Is most preferred.

[Heating Step] In the heating step, the cooled swelled mixture is cooled to 0 to 120 ° C., preferably 0 to 55 ° C.
Warm to ° C. The final temperature of the heating step is usually room temperature. The heating rate is preferably 1 ° C./min or more,
It is more preferably at least 2 ° C / min, more preferably at least 4 ° C / min, most preferably at least 8 ° C / min. The heating rate is preferably as fast as possible.
0000 ° C / sec is the theoretical upper limit, 1000 ° C sec is the technical upper limit, and 100 ° C / sec is the practical upper limit. The heating rate is a value obtained by dividing the difference between the temperature at which heating is started and the final heating temperature by the time from when heating is started to when the final heating temperature is reached. is there.

In order to rapidly heat the swelling mixture, the swelling mixture is introduced into a cylindrical container, the flow of the swelling mixture is divided into a plurality of parts in the container, and the flow direction of the divided mixture is adjusted in the container. It is preferable that the swollen mixture is heated from around the container while repeating this division and rotation. The device described above is preferably used for that.
When the dissolution is insufficient, the cooling step and the heating step may be repeatedly performed. Whether or not the dissolution is sufficient can be determined only by visually observing the appearance of the solution.

[Treatment after Production of Solution] The produced solution can be subjected to processes such as concentration adjustment (concentration or dilution), filtration, temperature adjustment, and addition of components, as necessary. The component to be added is determined according to the use of the polymer compound solution. Typical additives are plasticizers, degradation inhibitors (eg, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers), dyes and UV absorbers. Solutions must be stored within a stable temperature range. For example, in a solution prepared by cooling dissolution method of cellulose triacetate using acetone as a solvent, in a practical storage temperature range,
There are two phase separation regions in the high temperature region and the low temperature region. In order to store this solution stably, it is necessary to maintain the temperature in the middle homogeneous phase region. The obtained polymer compound solution is used for various uses.

[Production of Polymer Film] Production of a polymer film by a solvent casting method, which is a typical use of a polymer compound solution, will be described. The polymer compound solution is cast on a support and the solvent is evaporated to form a film. The solution before casting has a solid content of 18-35%
It is preferable to adjust the concentration so that The surface of the support is preferably finished in a mirror surface state. A drum or a band is used as the support. For casting and drying methods in the solvent casting method,
U.S. Pat. Nos. 2,336,310, 2,369,603, 2,
492078, 2492977, 249297
No. 8, No. 2607704, No. 2739069, No. 2
No. 739070, British Patent Nos. 640731, 7368
No. 92, JP-B Nos. 45-4554 and 49-5
No. 614, JP-A-60-176834 and JP-A-60-20
No. 3430 and No. 62-115035. In the case of a solution of cellulose acetate, the solution is preferably cast on a support having a surface temperature of 10 ° C. or lower. After casting, it is preferable to dry by blowing on the air for 2 seconds or more. The obtained film can be peeled off from the support and dried with high-temperature air having a temperature gradually changed from 100 to 160 ° C. to evaporate the residual solvent. The above method is described in JP-B-5-17844. According to this method, the time from casting to stripping can be reduced.

FIG. 3 is a flowchart showing a combination of each step and apparatus of the manufacturing method of the present invention. In the swelling step, the polymer compound (P) and the solvent (S1) are added to the stirring tank (31). The polymer compound and the solvent are mixed in the stirring tank, and the polymer compound is swollen by the solvent. The swollen swollen mixture is sent from the liquid sending pump (32) to the cooling device (33). As the liquid sending pump (2), a snake pump suitable for sending a viscous liquid is used.

The cooling device (33) is provided with a rotatable helical transfer mechanism (33-) provided in the container for transferring the inside of the cylindrical container while stirring the swollen mixture.
1) and a cooling mechanism (33-2) provided around the container for cooling the swollen mixture in the container.
By rotating the spiral transport mechanism (33-1),
The swelled mixture is sent while being sheared, mixed and cooled without stagnation (for example, the swelled mixture stagnating on the wall of the container is also scraped off). The cooling mechanism shown in FIG.
3-2) is mounted around the container in a jacket shape. A cooling tank (5) is provided inside the cooling mechanism (33-2).
The refrigerant (54) sent from 1) is flowing. As the refrigerant, for example, a mixture of methanol and water is used. The refrigerant used for cooling returns to the refrigerant tank (51). The refrigerant is cooled by the refrigerator (52). The heat generated by this cooling is processed in the cooling tower (53). The cooling device (33) shown in FIG. 3 has a mechanism for refilling the solvent further cooled to −105 to −15 ° C. into the container. The replenishing solvent (S2) is stored in the cooling stock tank (4
It is cooled to a required temperature in 9) and sent to the container of the cooling device (33) by the liquid sending pump (50). By adding the replenisher solvent thus cooled, the swollen mixture can be cooled very quickly. In the above cooling device, the swollen mixture is cooled quickly and uniformly. The cooled swollen mixture is sent to a heating device (34).

A heating device (34) is provided in the container for dividing the flow of the substance in the cylindrical container and the container into two, and rotating the flow of the divided substance in the container. And a heating mechanism (34-2) provided around the container for heating the swollen mixture in the container. As the swollen mixture passes through the partition element in the container, the swollen mixture is uniformly heated. The heating mechanism (34-2) shown in FIG. 3 is mounted around the container in a jacket shape. Inside the heating mechanism (34-2), hot water (56) sent from the constant temperature bath (57) flows. The warm water used for heating is supplied to the cleaning tower (5) in the heat exchanger (55).
Heat exchange with the water from 3). Thereby, the energy efficiency of the entire device can be improved. The heat-exchanged hot water returns to the constant temperature bath (57). In the above-mentioned heating device, the swelling mixture is quickly and uniformly heated, and the polymer compound is dissolved in the solvent. The obtained solution was supplied to a heater (36) and a filter (3) by a liquid sending pump (35).
7) After passing through a pressure adjusting valve (38), temperature adjustment, filtration and pressure adjustment are performed.

The solution is further concentrated in a concentration tank (39). That is, the solution brought into a high temperature and high pressure state by the heater (36) and the pressure regulating valve (38) is rapidly reduced in the concentration tank (39), whereby the solvent is evaporated and concentrated. The evaporated solvent is sent to a cooling stock tank (49) via a liquefaction device (48). The liquefied solvent is sent again to the container of the cooling device (33) by the pump (50) together with the replenishing solvent (S2). The concentrated solution is fed by a liquid sending pump (40).
After the temperature controller (41), the stock tank (42)
Sent to The apparatus shown in FIG. 1 further includes an apparatus for producing a polymer film by a solvent casting method. The solution in the stock tank (42) is sent to the slit die (45) via the filter (44) by the liquid sending pump (40). The solution is extruded into a film by a die (45), cast on a band-shaped support (46), dried, and stripped to produce a film (47). The film (47) is further dried and wound up.

[0048]

【Example】

Example 1 A methyl acetate solution of cellulose triacetate was produced using the apparatus shown in FIG. First, 15 parts by weight of cellulose triacetate and 85 parts by weight of methyl acetate were charged into a stirring tank (1) and stirred. Then 3
The mixture was allowed to stand for 0 minutes to swell. After swelling, the stirring tank (1) was pressurized to ² kg / cm ² with nitrogen gas and sent to the inlet (2) of the cooling unit. The inner diameter of the cooling unit container (3) is 3
It was 0 mm. In addition, a single screw extruder having a screw (4) lead length of 1000 mm, a screw groove depth of 3 mm, and a screw pitch of 30 mm was used. This device does not have a compression unit.
The refrigerant at -30 ° C was passed through the refrigerant jacket (7). In the heating section, the partition element (13) is placed in the container (12).
Are provided. The inner diameter of the container (12) in the heating section was 22 mm, and the length of the container was 1300 mm. Hot water at 55 ° C. was passed through the heating jacket (14). Observation of the obtained solution confirmed that a transparent and uniform solution was obtained.

The specific processing conditions are as follows. Throughput: 5.4 kg / h Screw rotation speed: 30 rpm Refrigerant temperature: -56 ° C Cooling inlet (2) temperature of mixture: 26 ° C Cooling outlet (10) temperature of mixture: -55 ° C Cooling rate: 29 ° C / minute Mixture Heating outlet (17) temperature: 52 ° C. Heating rate: 12 ° C./min Pressure loss in the heating step: 2 kg / cm ²

Example 2 Using the apparatus shown in FIG. 1, a methyl acetate solution of cellulose triacetate was produced.
First, 15 parts by weight of cellulose triacetate and 85 parts by weight of methyl acetate were charged into a stirring tank (1) and stirred. Thereafter, the mixture was allowed to stand for 30 minutes to swell the mixture. After swelling, the stirring tank (1) was pressurized to ² kg / cm ² with nitrogen gas and sent to the inlet (2) of the cooling unit. The inner diameter (D _{b in} each of the above formulas) of the container (3) in the cooling section was 30 mm. Further, the length of the lead of the screw (4) (L in each formula described above) is 1000 mm, the depth of the groove of the screw (H in each formula described above) is 3 mm, and the screw pitch (W in each formula described above) is used. Used a 30 mm single screw extruder. This device does not have a compression unit.
A refrigerant at 56 ° C (Fluorinert FC77, 3M) was passed through the refrigerant jacket (7). In the heating section, 39 partition elements (13) are provided in the container (12). The inside diameter of the container (12) of the heating section is 13 mm
The length of the container was 925 mm. Hot water at 55 ° C. was passed through the heating jacket (14). Observation of the obtained solution confirmed that a transparent and uniform solution was obtained.

The specific processing conditions are as follows. Throughput: 5.4 kg / h Screw rotation speed: 30 rpm Refrigerant temperature: -56 ° C Cooling inlet (2) temperature of mixture: 26 ° C Cooling outlet (10) temperature of mixture: -55 ° C Cooling rate: 29 ° C / minute Mixture Heating outlet (17) temperature: 52 ° C. Heating rate: 12 ° C./min Pressure loss in the heating step: 16 kg / cm ²

Example 3 Using the apparatus shown in FIG. 1, a methyl acetate solution of cellulose triacetate was produced.
First, 15 parts by weight of cellulose triacetate, 2 parts by weight of triphenyl phosphate, 66 parts by weight of methyl acetate, and 17 parts by weight of ethanol were charged into a stirring tank (1) and stirred. Thereafter, the mixture was allowed to stand for 30 minutes to swell the mixture.
After swelling, the stirring tank (1) was filled with nitrogen gas at 2 kg / cm ^2.
And sent to the inlet (2) of the cooling section. The inner diameter of the container (3) in the cooling section was 30 mm. A single screw extruder having a screw (4) lead length of 870 mm and a screw pitch of 30 mm was used. As the screw (4), a taper with a groove depth of 4.5 mm from the inlet to a length of 540 mm, a groove depth of 4.5 mm to 1.5 mm from a length of 540 mm to 690 mm, a length of 690 mm to
A triple compression screw having a groove depth of 1.5 up to 870 mm was used. -45 for refrigerant jacket (7)
° C refrigerant. In the heating section, 39 partition elements (13) are provided in the container (12). The inner diameter of the container (12) of the heating section is 22 mm, and the length of the container is 13 mm.
00 mm. 55 ° C for the heating jacket (14)
Hot water. Observation of the obtained solution confirmed that a transparent and uniform solution was obtained.

The specific processing conditions are as follows. Throughput: 9.4 kg / h Screw rotation speed: 60 rpm Refrigerant temperature: -45 ° C Cooling inlet (2) temperature of mixture: 26 ° C Cooling outlet (10) temperature of mixture: -40 ° C Cooling rate: 40 ° C / minute Mixture Heating outlet (17) temperature: 50 ° C. Heating rate: 18 ° C./min Pressure loss in the heating step: 5 kg / cm ²

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a preferred embodiment of a cooling / heating device.

FIG. 2 is a schematic view showing a combination of partition elements.

FIG. 3 is a flowchart showing a combination of each step and apparatus of the manufacturing method.

FIG. 4 is a view showing a screw shape of a cooling device.

FIG. 5 is a graph showing a relationship between a change in the calorific value of the screw / a change in the calorific value of the dope, the rotational speed of the screw, and the depth of the screw groove.

FIG. 6 is a graph showing a relationship between a change in the calorific value of the screw / a change in the calorific value of the dope and the inner diameter of the cylinder.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Stirring tank 2 Cooling container inlet part 3 Cooling container 4 Spiral conveyance mechanism 5 Drive motor 6 Speed controller 7 Jacket-shaped cooling mechanism 8 Refrigerant inlet 9 Refrigerant outlet 10 Cooling container outlet part 11 Heating container inlet Unit 12 heating vessel 13 partition element 14 jacket-like heating mechanism 15 heating medium inlet 16 heating medium outlet 17 heating vessel outlet 21 clockwise element 22 counterclockwise element S1 solvent P polymer compound S2 replenishing solvent Reference Signs List 31 Stirring tank 32 Liquid feed pump 33 Cooling device 33-1 Spiral transfer mechanism 33-2 Jacket-like cooling mechanism 34 Heating device 34-1 Partition element 34-2 Jacket-like heating mechanism 35 Liquid sending pump 36 Heater 37 Filter 38 Pressure control valve 39 Concentration tank 40 Liquid feed pump 41 Temperature control device 4 Stock tank 43 Liquid feed pump 44 Filter 45 Die 46 Belt-like support 47 Film 48 Liquefaction unit 49 Cooling stock tank 50 Liquid feed pump 51 Refrigerant tank 52 Refrigerator 53 Cooling tower 54 Refrigerant 55 Heat exchanger 56 Hot water 57 Constant temperature bath W Screw groove ( Width of flow path e Width of flight end L Length of screw Point shown by triangle in FIG. 5 Result of using screw with groove depth of 7.0 mm Point shown by square in FIG. 5 Screw with groove depth of 5.5 mm Result of use Point indicated by rhombus in FIG. 5 Result using screw with groove depth of 3.0 mm Point indicated by white circle in FIG. 5 Result using screw with groove depth of 1.5 to 4.5 mm Resulted by black circle in FIG. Point shown Result of using screw with groove depth 1.5mm

Claims (5)

[Claims] 1. A cylindrical cooling container, a cooling container inlet provided in the container, a rotatable spiral transport mechanism provided in the container, and a cooling mechanism provided around the container. A cooling device including: a cooling container outlet provided in the container; a cylindrical heating container; a heating container inlet provided in the container; and a plurality of containers provided in the container. A dividing element for dividing the flow of the substance in the container into a plurality of parts, and rotating the flow of the divided substance in the container; a heating mechanism provided around the container; and a heating mechanism provided in the container. A cooling / heating device comprising a heating device including a heating container outlet portion, wherein the cooling container outlet portion and the heating container inlet portion are connected to each other. 2. A partitioning element for dividing a flow of a substance in a heating vessel into two, and a clockwise element for rotating the flow clockwise in the vessel, and a clockwise element in the heating vessel. It consists of a counterclockwise element that divides the flow of material into two and rotates the flow counterclockwise in the heating vessel, where clockwise and counterclockwise elements are alternately arranged in the vessel with a shift of about 90 degrees. The cooling / heating device according to claim 1, wherein 3. The shape of the cylindrical cooling container and the spiral transfer mechanism of the cooling mechanism is designed such that the heat value defined by the following equations (1) and (2) is as low as possible. The cooling / heating device according to claim 1, wherein (Equation 1) Where E _v is the viscous heating value (unit: W) between the screw groove and the cylinder; μ is the viscosity (P
a · S); N is the screw rotation speed (S ⁻¹ ); D _b is the cylinder (barrel) inner diameter (m);
Is the width (m) of the screw groove (flow path); L is the length (m) of the screw; θ is the average advance angle of the screw; H is the depth (m) of the screw groove; θ _b is the average advance angle at the tip of the screw flight; Q is the feed flow rate (kg / s); and Q _d is the traction flow rate (k
g / s). (Equation 2) In the formula, E _f is the viscous heating value (unit: W) between the screw groove and the cylinder; μ _f is the viscosity (Pa · S) of the material at the tip of the flight; and N is the screw rotation speed (S).
It is ^-1); D _b is a cylinder inner diameter (m); e is the flight tip width (m); [delta] _f is a feeler (m) between the flight tip and the cylinder; and L is a screw Length (m). 4. A step of mixing a polymer compound and a solvent and swelling the polymer compound with the solvent;
A process for cooling the swelled mixture to a temperature of 0 to 120 ° C. to dissolve the polymer in a solvent, the method comprising: In the heating step, the swelling mixture is introduced into a cylindrical container, the flow of the swelling mixture is divided into a plurality of parts in the container, and the direction of the flow of the divided mixture is rotated in the container. A method for producing a polymer compound solution, wherein the swollen mixture is heated from around the container while repeating rotation. 5. The method for producing a polymer compound solution according to claim 4, wherein the swelling mixture is heated at a rate of 1 ° C./min or more in the heating step.