JP2002275213A - Method and device for producing chlorinated vinyl chloride-based resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a chlorinated vinyl chloride-based resin by a gas-solid reaction method having excellent post treatment simplicity and an excellent installation cost property, by which the chlorinated vinyl chloride-based resin allowing a simple removal of hydrogen chloride from the polymer, and having an inherent heat resistance and excellent heat stability can be produced. SOLUTION: This method for producing the chlorinated vinyl chloride-based resin comprises using a rotary reaction device or a stirring reaction device, supplying chlorine in or on the powder layer of a vinyl chloride-based resin in a fluidized state and simultaneously irradiating the powder layer with light from a light source disposed outside the powder layer, thereby rapidly and uniformly chlorinating the vinyl chloride-based resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technology for producing a chlorinated vinyl chloride resin by using light to promote the reaction by using a gas-solid contact field composed of powder of chlorine and vinyl chloride resin as a reaction field. About.

[0002]

2. Description of the Related Art A chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin has excellent heat resistance, flame retardancy, mechanical strength, and electrical properties, and is used in various industries. I have. For example, the glass transition temperature of a normal vinyl chloride resin is about 80 ° C., but the glass transition temperature of a chlorinated vinyl chloride resin increases with an increase in the chlorine content.
Reaches 20-130 ° C. The Vicat softening temperature also shows a high value of about 120 ° C. Due to such high heat resistance, chlorinated vinyl chloride resins are used for heat-resistant pipes, heat-resistant joints, heat-resistant valves, heat-resistant sheets and the like.

[0003] In the synthesis of conventional chlorinated vinyl chloride resins, the water suspension method has been mainly used. In the water suspension method, an aqueous suspension of a vinyl chloride resin having a solid content concentration of several percent to several tens percent is filled in a reaction vessel, and the water suspension is stirred while supplying chlorine. How to do. Furthermore, since the reaction does not proceed at all or is very slow, light, heat, a catalyst, and the like for promoting the reaction are added to the aqueous suspension. In the water suspension method, particles are easily stirred and mixed, the reaction control is easy because low-concentration chlorine dissolved in water is used, and vinyl chloride resin is plasticized with water to form chlorine. There are various advantages such as easy penetration into the resin. For this reason, it has been adopted in many chlorinated vinyl chloride-based resin production facilities.

[0004] However, the water suspension method has a problem that cannot be essentially solved. In a reaction in which a chlorinated vinyl chloride resin is formed from a vinyl chloride resin and chlorine, hydrogen chloride is generated as shown in the following equation. Therefore, the chlorinated vinyl chloride resin after the completion of the reaction is in a state of being suspended in a high-concentration hydrochloric acid solution.

[0005]

Embedded image For a normal chlorinated vinyl chloride resin, the final shipping form needs to be in a powder state, and it is necessary to remove hydrogen chloride as an impurity. Therefore, the aqueous suspension of the chlorinated vinyl chloride resin after the reaction needs to be dehydrated, washed and dried, and the entire process requires large equipment costs for the post-treatment step and running costs associated with drying and washing. Becomes Moreover, since water and hydrogen chloride are in an azeotropic state, hydrogen chloride cannot be removed from the product until it is finally completely dried.

Further, in the water suspension method, at the end of the reaction, the reaction solution becomes a high-concentration hydrochloric acid solution of about 10% by weight. For this reason, in the water suspension method, it is necessary to use an expensive corrosion-resistant metal material such as a titanium-based or titanium-palladium-based material, or to use a device that has been subjected to a surface treatment such as glass lining or fluorine lining. Further, since the reaction solution is carried into the post-treatment step, it is necessary to use an expensive corrosion-resistant material also in the post-treatment step.

As described above, the reaction apparatus of the water suspension method is relatively simple in itself and easy to control. However, considering the entire process including the post-treatment step, the equipment cost and the running cost are low. The device has a disadvantage that a large load is imposed on the cost.

On the other hand, in order to make up for such a drawback of the water suspension method, a chlorinated vinyl chloride-based resin is produced by a gas-solid reaction method using a gas-solid contact field between powder particles of vinyl chloride resin and chlorine as a reaction field. Resin synthesis methods have also been proposed. In the gas-solid reaction method, the generated hydrogen chloride is discharged from the system as a gas, so that the remaining hydrogen chloride after the reaction is completed is separated from the powder existing in the gaps between the powder particles and the chloride adsorbed on the surface of the powder particles. Only hydrogen. Such residual hydrogen chloride can be easily removed by flowing a gas such as air or nitrogen, or by degassing the system with a vacuum pump. Therefore, a product having a low content of hydrogen chloride as an impurity can be obtained without passing through complicated steps such as washing, dehydration, and drying in the post-treatment step of the gas-solid reaction method.

Further, in the gas-solid reaction method, the reaction is carried out in a state where water does not exist in the reaction system or a small amount of water is adsorbed on the powder particles. In such an anhydrous or slightly water-based system, the corrosiveness of chlorine and hydrogen chloride to the metal material is weak, and a relatively inexpensive corrosion-resistant metal material such as a nickel system can be used for the reactor. Further, since only trace amounts of chlorine and hydrogen chloride remain in the powder particles brought into the post-processing step, an inexpensive metal material can be used in the post-processing step.

As described above, the gas-solid reaction method for reacting chlorine with a powder layer of a vinyl chloride resin has excellent features in terms of equipment cost, wastewater treatment, and safety.

However, the gas-solid reaction method has a quality problem. That is, the gas-solid reaction method has a drawback that it is difficult to make the reaction proceed uniformly, and the quality is lower than that of a chlorinated vinyl chloride resin having the same conversion obtained by the water suspension method. Deterioration in quality means that the Vicat softening temperature or Tg decreases and the heat resistance decreases, the resin after heat molding becomes colored and the initial colorability deteriorates, and the heat when the resin after molding is exposed to high temperatures. There are problems such as decomposition progressing easily and thermal stability decreasing. It is believed that such degradation is due to non-uniformity of the reaction. Here, that the reaction is non-uniform means that the reaction rate is different for each individual particle, and that the reaction is different between the surface and the inside of one particle. Both non-uniformities. Furthermore, in the gas-solid reaction method using light to promote the reaction, it is pointed out that the resin is deteriorated by the heat generated from the light source, and the initial coloring property and the thermal stability are deteriorated. Thus, the resin obtained by the gas-solid reaction method has quality problems such as heat resistance, initial coloring property, and thermal stability.

Several means have been proposed for solving the drawbacks of such a gas-solid reaction method. For example, the non-uniformity of the reaction in the gas-solid reaction method is caused by the fact that the light which is the radical generation source is not uniformly irradiated on the vinyl chloride resin. Is the way. JP-A-59-24705 is a method in which a small amount of oxygen is mixed into chlorine to promote chlorination of a vinyl chloride resin in the absence of light. Japanese Patent Publication No. 60-2322 discloses that a vinyl chloride resin is impregnated with chlorine under high pressure and low temperature and then heated to generate thermal radicals in the vinyl chloride resin to obtain a chlorinated vinyl chloride resin. Is the way. However, in these methods, the reaction time is long, and the obtained chlorinated vinyl chloride resin has a low reaction rate and the quality problems have not been sufficiently solved. On the other hand, also in a method using light as a radical generation source, a method for improving the quality of a chlorinated vinyl chloride resin has been proposed. Tokunosho 5
In 4-39878, a light source is inserted into a powder bed of a fluidized-bed reactor, and a solution that blocks light in a wavelength region that does not participate in the reaction is circulated around the light source, and a vinyl chloride resin is generated by heat of the light source There has been proposed a method for preventing the deterioration of the material. However, in such a method, since the light source is inserted into the powder layer of the vinyl chloride resin, light is irradiated only to the vicinity of the light source, and the powder layer is hard to be uniformly chlorinated. In particular, in order to improve the chlorination non-uniformity in a production-scale apparatus, it is necessary to insert a large number of light sources into the powder layer, which is impractical. In Japanese Patent Publication No. 52-15638, the powder layer, in which a light source is inserted, is fluidized with chlorine gas at a constant flow rate or more to widen the powder particle interval, thereby making the powder layer opaque and reaching the inside of the powder layer. Light is allowed to reach. However, even with such a method, it is necessary to insert a large number of light sources into the powder layer, and the powder layer scatters at the superficial velocity at which the powder layer becomes opaque, and a powder layer recovery facility is installed. In addition, equipment for supplying a large amount of toxic and highly corrosive chlorine gas is required. Such a device has disadvantages that the equipment cost is high, the maintainability is low, and the reaction rate of passing chlorine is extremely low.

As described above, in the prior art, the water suspension method has a problem of post-treatment equipment and equipment corrosion, and the gas-solid reaction method has a problem of quality deterioration due to non-uniform reaction.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for obtaining a chlorinated vinyl chloride resin having high heat resistance and heat stability in a gas-solid reaction method excellent in simplicity of post-treatment and equipment cost. And to provide a device.

[0015]

Means for Solving the Problems As a result of intensive studies made by the present inventors, it has been found that a reaction promoting light source is installed at a specific position and a vinyl chloride resin is reacted with chlorine by a gas-solid reaction method. Allows the chlorination reaction to proceed quickly and uniformly,
The inventors have found that the amount of residual hydrogen chloride can be reduced by a simple post-treatment, and that a chlorinated vinyl chloride resin having high heat resistance and high thermal stability can be produced, and the present invention has been completed.

That is, the present invention relates to (1) a method in which chlorine is supplied into and / or out of a powder layer of a vinyl chloride resin in a fluidized state while a chlorine source is provided outside the powder layer. A method for producing a chlorinated vinyl chloride resin, which comprises irradiating the surface of the powder layer with light for accelerating the reaction and chlorinating the vinyl chloride resin (claim 1), (2) a rotary reactor The method for producing a chlorinated vinyl chloride resin according to claim 1, wherein the powder of the vinyl chloride resin is brought into a fluidized state by using a stirring type reactor (claim 2). The method for producing a chlorinated vinyl chloride resin according to claim 1 or 2, wherein the light source is installed inside the reactor (claim 3), and (4) the light source is a low-pressure mercury lamp or a high-pressure mercury lamp. , Ultra-high pressure mercury lamp, metal halide lamp The method of producing a chlorinated vinyl chloride resin according to claim 1, 2 or 3 (claim 4),
(5) The method for producing a chlorinated vinyl chloride resin according to (2), (3) or (4), wherein the chlorine supply position is in the powder bed, (6) the vinyl chloride resin in a fluidized state. While supplying chlorine into and / or outside the powder layer, the surface of the powder layer is irradiated with light for accelerating the reaction from a light source installed outside the powder layer, and the vinyl chloride resin is removed. A chlorinated vinyl chloride resin manufacturing apparatus characterized in that it is chlorinated (claim 6), and (7) the powder of the vinyl chloride resin is brought into a fluid state using a rotary reactor or a stirring reactor. The apparatus for producing a chlorinated vinyl chloride resin according to claim 6 (claim 7), (8) the reaction apparatus is a rotary reaction apparatus, and the light source is installed inside the reaction apparatus. Or 7
(9) The light source is at least one selected from a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp. The apparatus for producing a chlorinated vinyl chloride resin according to claim 8, wherein the supply port of the chlorine gas supply nozzle is disposed so as to discharge chlorine gas downward. (11) The chlorinated vinyl chloride resin according to claim 8, 9 or 10, wherein a chlorine gas supply nozzle is provided inside the powder layer. The apparatus for producing a chlorinated vinyl chloride resin according to claim 8, 9, 10 or 11, wherein the gas discharge port is provided outside the powder layer. Item 12),
(13) A cylindrical non-rotating tube arranged on the rotation axis of the reaction vessel is inserted into the reaction vessel, the space between the non-rotating pipe and the reaction vessel is sealed using a rotating gas seal, and inserted into the reaction vessel. The at least one component selected from the group consisting of a light source, a chlorine gas supply nozzle, a gas discharge nozzle, and a thermocouple is provided on the non-rotating tube of the portion.
2. The apparatus for producing a chlorinated vinyl chloride resin according to claim 2 (claim 13), (14) a disc-shaped non-rotating plate arranged on a plane perpendicular to the rotation axis of the reaction vessel, covering the opening of the reaction vessel; The non-rotating plate and the reaction vessel are hermetically sealed using a rotary seal, and the non-rotating plate is provided with at least one component selected from a light source, a chlorine gas supply nozzle, a gas discharge nozzle, and a thermocouple. The apparatus for producing a chlorinated vinyl chloride resin according to claim 8, 9, 10, 11, or 12, (claim 14), (15)
15. The cooling medium or the heating medium is supplied to the jacket via a rotary joint having a double circular tube structure mounted on the rotation axis of the reaction vessel and opposite to the non-rotating tube or the non-rotating plate. (Claim 15).

[0017]

DETAILED DESCRIPTION OF THE INVENTION A powder referred to in the present invention is an aggregate of particles that can move alone in a gas phase, and the size of each particle is in the range of about 10 μm to 2000 μm. . In the present invention, each of the particles that can move alone in the gas phase is referred to as a powder particle, an aggregate of the powder particles is referred to as a powder layer, and a liquid in which particles corresponding to the powder particles are dispersed in water. Is referred to as an aqueous suspension and is distinguished.

The installation position of the light source is the most important factor in the present invention. That is, in the present invention, it is essential that the light source is provided outside the powder layer and the surface of the powder layer is irradiated with light. The reasons for installing the light source outside the powder layer are firstly that the high-temperature light source does not directly contact the resin, secondly that light is widely dispersed and irradiated, and thirdly that various types of reactors are used. Can be selected.

The first reason, that the high-temperature light source does not directly contact the powder layer, is to reduce resin quality deterioration. The reaction rate of the chlorination reaction of a vinyl chloride resin is significantly improved when the temperature of the reaction field is set at 60 to 80 ° C. However, the glass transition temperature of the vinyl chloride resin as a raw material is about 80 to 85 ° C., and when the reaction temperature is set higher than this, the physical properties of the resin change, and the thermal stability and the coloring property during molding deteriorate. Would. However, since the chlorination reaction of the vinyl chloride resin is a strongly exothermic reaction, it is necessary to perform a heat removal operation at the same time as the reaction starts. Thus, the chlorination reaction of the vinyl chloride resin requires strict temperature control. When the light source is installed inside the powder layer, the temperature of the powder layer around the light source partially rises significantly due to the heat generated by the light source and a large amount of reaction heat, causing the resin to change its physical properties and reduce the quality. to degrade. In particular, in the gas-solid reaction method, thermal conductivity is poor, and it is difficult to remove heat, so that the gas-solid reaction method has a more adverse effect than the suspension method. On the other hand, in the present invention in which the light source is installed outside the powder layer, the light source does not directly contact the resin, the light is dispersed, and a gentle reaction proceeds over a wide range. Can be done.

The second reason for dispersing light is that the reaction rate can be made uniform and the reaction area can be increased by reducing the reaction rate in each powder particle.

In the case of reacting vinyl chloride resin with chlorine using light, the reaction speed increases as the intensity of the light applied to the individual powder particles increases. At first glance, a faster reaction rate seems to be advantageous, but in the chlorination reaction of vinyl chloride resin, diffusion of chlorine into the powder particles is also an important factor. Is weaker.

If the temperature and the chlorine concentration in the gas phase are constant,
The diffusion rate of chlorine gas into the powder particles is constant. Figure 1
As shown in a, when strong light is applied to the powder particles, the chlorine gas reacts only with the resin near the surface of the powder particles and cannot diffuse to the inside. In this case, a large difference occurs in the reaction rate between the surface portion and the central portion of the powder particles. Conversely, when light is dispersed as in the present invention, the chlorination reaction rate in the powder particles decreases as shown in FIG. 1b, so that chlorine is easily diffused into the powder particles, The reaction rates at the surface portion and the central portion of the powder particles are more uniform. A resin having a uniform reaction rate inside each powder particle becomes a resin having excellent heat resistance, heat stability, and initial coloring properties.

On the other hand, when the reaction rate in individual powder particles is reduced, the reaction rate of the entire powder layer is reduced unless the number of reacting powder particles is increased. Therefore, it is necessary to irradiate as large a surface area of the powder layer as possible with light and to give all the powder particles an opportunity to irradiate light uniformly.

When the light source is installed outside the powder as in the present invention, the area irradiated with light is the surface of the powder layer as shown in FIG. 2A. The surface area of the powder layer depends on the shape of the device,
A large surface area can be obtained relatively easily. Conversely, when a light source is installed in the powder layer, the portion irradiated with light is limited to the vicinity of the light source as shown in FIG. 2B. As described above, in the present invention, the reaction rate in each of the powder particles is made uniform and the reaction rate of the entire powder layer is not reduced by a very simple operation of installing the light source outside the powder layer. It is a technique that can be.

The third reason, the advantage of being able to use various reactors, will be described. In the present invention, in which the light source is installed outside the powder, flowing the powder and exposing all the powder particles to the powder surface is performed by a rotary powder device or a mechanical stirring type powder as described later. Can use the device,
Relatively easy. Because all powder particles can be exposed on the surface of the powder layer by gentle mixing and stirring,
There is little scattering of powder particles, and a dust collection device is not required.

On the other hand, in the method of installing the light source in the powder,
As in Japanese Patent Application Laid-Open No. 52-15638, it is necessary to insert a large number of light sources into the powder layer, and it is impossible to rotate the apparatus or mechanically agitate the powder layer to make it flow. .
Therefore, the use of a fluidized bed reactor is the only method. However, in the case of using a fluidized bed type reaction apparatus, in order to move all the powder particles evenly on the light source surface, light sources should be installed at a plurality of locations in the powder bed and a large amount of chlorine gas should be used. Need to fluidize the powder. In this case, since a large amount of particles are scattered, a dust collecting device must be installed, and further, the collected powder particles must be returned to the reaction tank.

As described above, the present invention in which the light source is installed outside the powder layer is a very rational and effective method for chlorinating a vinyl chloride resin by utilizing a photoreaction with chlorine gas. It turned out that.

The vinyl chloride resin used in the present invention needs to be a powder. The powder referred to in the present invention is an aggregate of particles that can move alone in the gas phase as described above,
As a standard of the particle size of each particle, it is about 10 μm to 20 μm.
It is within a range of 00 μm or less (average particle size is 50 to 500 μm). In the present invention, each of the particles that can move alone in the gas phase is referred to as a powder particle, and an aggregate of the powder particles is referred to as a powder layer and distinguished.

The particle size distribution of the powder particles is preferably uniform from the viewpoint of enhancing the fluidity of the powder and allowing the reaction to proceed uniformly, and the absolute value of the particle size also has a preferable range. is there. Therefore, the powder layer of the vinyl chloride resin used in the present invention has powder particles mainly having a particle diameter of 50 μm or more and 500 μm or less (the average particle diameter is 100 to 30 μm).
(0 μm). Individual powder particles may consist of a continuous phase of vinyl chloride resin,
An aggregate of smaller primary particles may be used.

There are various methods for producing a vinyl chloride resin, such as a suspension polymerization method, a bulk polymerization method, a gas phase polymerization method, and an emulsion polymerization method. Any of those obtained in can be used arbitrarily. Further, a copolymer of vinyl chloride and an unsaturated hydrocarbon compound such as vinyl acetate may be used. If the vinyl chloride resin obtained after the polymerization reaction is a water suspension, it is necessary to dry the resin, and if it is a lump, it is necessary to perform an operation such as pulverization. The vinyl chloride resin obtained by bulk polymerization is difficult to pulverize,
Vinyl chloride resins synthesized by gas phase polymerization are usually difficult to obtain. The vinyl chloride resin obtained by the emulsion polymerization method contains a large amount of an emulsifier. Therefore, the vinyl chloride resin used in the present invention is preferably obtained by a suspension polymerization method. In the present invention, if the vinyl chloride resin is a flowable powder layer, it can be used even if it contains water, but if the water content is too large, as described in the description of the water suspension method, the reaction is carried out. It is difficult to remove the generated hydrogen chloride from the resin. Therefore, the water content in the powder layer is preferably less than 5% by weight. Further, in order to prevent aggregation of the powder particles due to static electricity and to prevent the powder particles from adhering to the container, the vinyl chloride resin powder may intentionally contain less than 5% by weight of water.

When a vinyl chloride resin is synthesized by a suspension polymerization method or an emulsion polymerization method, fine particles of the vinyl chloride resin are dispersed in water, so that powder particles can be obtained only by drying. However, in this case, a continuous layer called a skin layer is formed on the surface of the powder particles, which impedes the penetration of chlorine gas into the inside, and reduces the reaction rate or the reaction rate in the radial direction of the powder particles. It may be uneven. Therefore, it is also effective that the powder particles of the vinyl chloride resin used in the present invention are pulverized in advance before the chlorination reaction to break the skin layer before use.

The chlorine used in the present invention is not particularly limited as long as it is generally used industrially. However, if oxygen is contained in chlorine, the resulting chlorinated vinyl chloride resin deteriorates in thermal stability and colorability at the time of molding. Therefore, the concentration of oxygen contained in chlorine is 100 p.
pm or less, and most preferably 20 ppm or less. In addition, if water is contained in chlorine, hydrogen chloride generated by the reaction becomes difficult to remove from the resin, or may cause corrosion of the device,
It is preferably at most 1000 ppm. Further, chlorine may be diluted with an inert gas such as nitrogen or argon in order to adjust the reaction rate or the reaction temperature.

The method for supplying chlorine gas in the present invention will be described. In the present invention, the state of chlorine supplied into the reactor may be gas or liquid. Generally, industrially used chlorine is liquid chlorine sealed in a high-pressure cylinder. Therefore, in the case of supplying gaseous gas, the liquid chlorine removed from the liquid chlorine cylinder may be vaporized in another container and then supplied to the reaction container. When supplying liquid chlorine into the reaction vessel, the liquid chlorine removed from the liquid chlorine cylinder may be vaporized in the reactor. The method of vaporizing chlorine in the reactor is preferable because it has the effect of heat of vaporization depriving the heat of reaction and mitigating a rise in temperature in the reactor. However, if liquid chlorine comes into direct contact with the vinyl chloride resin, the surface structure and internal structure of the vinyl chloride resin will change, so the liquid chlorine will not come into contact with the vinyl chloride resin before vaporizing in the reaction vessel. It needs to be devised.

The supply position of chlorine in the reaction vessel is arbitrary. Chlorine may be supplied to the vinyl chloride resin powder layer as shown in FIG. 3B, or may be supplied to the gas phase as shown in FIG. 3A. When supplied to the position a, chlorine sufficiently penetrates the powder particles and then reaches the surface of the powder layer to which the light is irradiated, so that the reaction efficiency is high. Further, the shape of the supply port is preferably such that chlorine is discharged downward from the powder layer. When supplying chlorine to the gas phase, chlorine is efficiently supplied to the surface of the powder layer by discharging chlorine downward. When supplying chlorine into the powder layer, the chlorine gas is uniformly diffused into the powder layer by releasing chlorine downward, thereby preventing the chlorine supply port from being clogged with powder particles. You. Further, since it is not desirable that the liquid chlorine and the powder layer come into contact with each other as described above, when chlorine is supplied to the inside of the powder layer as in the position a, it is not until the chlorine comes into contact with the powder layer. It is desirable to vaporize.

The method for discharging hydrogen chloride gas in the present invention will be described. In the suspension method conventionally used for the production of chlorinated vinyl chloride resins, hydrogen chloride generated during the reaction dissolves in the aqueous phase, so that it is not necessary to consider the discharge of hydrogen chloride. However, in the present invention in which the reaction is carried out in a gas-solid contact field, unless the same amount of hydrogen chloride as the supplied chlorine is discharged from the inside of the apparatus, the pressure inside the apparatus will increase extremely. Any method of releasing hydrogen chloride may be used, but if chlorine is also discharged at the same time as discharging hydrogen chloride, it is inefficient, so
Preferably, the outlet for hydrogen chloride is as far as possible from the inlet for chlorine.

Most preferably, the outlet for hydrogen chloride is located outside the powder layer. Also, as the powder adhering to the wall of the reaction vessel falls from the upper part of the outlet with the rotation of the reaction vessel, the outlet may be clogged. It is preferred that

Next, the flow method of the powder layer in the present invention will be described. The fluid state referred to in the present invention refers to all states in which the powder particles are moving or moving continuously or intermittently and continuously. Therefore, the present invention is not limited to a fluidized state using a fluidized bed in which particles are moved by flowing a gas through the powder bed. The fluidization method in the present invention may use a method in a conventionally used powder reactor, or may be used in a mixing device, a stirring device, a combustion device, a drying device, a crushing device, a granulation device, and the like. May be applied. Specifically, a container rotating type device such as a horizontal cylindrical type, a V type, a double cone type, a swing rotary type, a single-shaft ribbon type, a double-shaft paddle type, a rotary plow type, a twin-shaft planetary stirring type, It is preferable to use a mechanical stirring type device such as a conical screw type. The specific shapes of these devices are described in Chemical Engineering Handbook (edited by the Society of Chemical Engineers, 6th revised edition, p. 876). Among these apparatuses, for example, a rotating vessel type reactor as shown in FIGS. 4, 5 and 6 can ensure that all the powder particles flow and can be uniformly exposed to the surface of the powder layer. Thus, the present invention is more effective for the present invention than a mechanical stirring type device or a fluidized bed type device.

The light irradiation method of the present invention can be any method as long as the light source exists outside the powder layer and the surface of the powder layer is irradiated with light. As shown in FIG. 4, a light source may be provided outside a transparent reaction vessel such as glass, or light may be transmitted from the light source provided outside the reaction vessel to the inside of the reaction vessel using an optical fiber, a reflecting mirror, or a prism. You may guide me.

The method of installing the light source outside the reaction vessel as described above can minimize bringing the heat of the light source into the reaction vessel. Further, a light source can be installed inside the reaction vessel as shown in FIGS. When a large-sized reaction vessel is manufactured, a method of installing a light source inside the reaction vessel as shown in FIGS. 5 and 6 is preferable because light can be used efficiently.

The type of light source used in the present invention will be described. The role of light in the present invention is to excite chlorine to generate chlorine radicals and promote the chlorine addition reaction to the vinyl chloride resin. Since chlorine has an energy absorption band in a wide wavelength range from the visible region to ultraviolet light, various light sources such as sunlight and artificial light can be used in the present invention. Since chlorine has the strongest absorption band for ultraviolet light having a wavelength of 320 to 360 nm, it is preferable to use a light source containing a large amount of this wavelength range. Specifically, a light source that emits a large amount of ultraviolet light, such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp, may be used. The light source can be covered with a transparent cover according to purposes such as protection of the light source and cooling. In this case, the material of the transparent cover is quartz,
Pyrex (registered trademark), hard glass, soft glass tube, etc. can be used, but quartz or Pyrex (registered trademark) is used in order to effectively use the wavelength in the ultraviolet region effective for the chlorination reaction. Preferably, quartz is most preferably used.

When a rotary reaction vessel is used, a light source, a chlorine supply nozzle, a gas discharge nozzle, a thermocouple, and the like are fixed, and only the reaction vessel and the jacket are rotated. It is necessary to prevent leakage into the reaction vessel and leakage of external gas such as air into the reaction vessel. As one method of satisfying this condition, a cylindrical non-rotating tube to which the above-mentioned parts to be fixed were attached was arranged on the rotation axis of the reaction vessel, and the non-rotating tube and the reaction vessel or the reaction vessel were attached. This is a method of attaching a rotary gas seal between the lid and the lid. Another method is a method in which a lid to which the above-mentioned parts to be fixed are attached is arranged and fixed perpendicular to the rotation axis of the reaction vessel, and a rotary gas seal is attached between the lid and the reaction vessel. In these methods, the dust particles may enter the gap of the rotary gas seal and cause gas leakage. Therefore, it is preferable to attach a dust seal inside the gas seal.

Since the chlorination reaction of the vinyl chloride resin is an exothermic reaction, it is necessary to remove heat from the powder layer. on the other hand,
In order for the reaction to start, it is necessary to heat the powder layer to about 40 to 60 ° C. Therefore, in the present invention, it is effective to attach a jacket for flowing a refrigerant and a heat medium to the reaction vessel. Common materials such as water, steam, and silicone oil can be used as the refrigerant and the heat medium. When a rotary reaction vessel is used, the jacket also rotates together with the reaction vessel. Therefore, it is preferable to arrange a rotary joint having a double circular tube structure on the rotation axis of the reaction vessel and allow the heat medium and the refrigerant to flow through the jacket. Further, the rotary joint is preferably installed on a side opposite to a non-rotating tube or a fixed lid to which a light source, a chlorine supply nozzle, a gas discharge nozzle, a thermocouple, and the like are attached. The rotary joint referred to here is a joint that combines a double pipe and a rotary seal, and by attaching it on one rotation axis of a rotary container,
This is a device that simultaneously achieves inflow and outflow of fluid. Specific products include RXE3015 manufactured by Showa Kogyo Co., Ltd.
And AC series.

The present invention can be widely applied to photoreaction between powder and gas. For example, if fluorine is used instead of chlorine, the vinyl chloride resin can be fluorinated by a photoreaction. It is also possible to chlorinate or fluorinate resins other than vinyl chloride resins such as polypropylene, polyethylene, polystyrene and polyisobutylene.

[0044]

EXAMPLES Next, the method of the present invention will be specifically described with reference to examples. However, the present embodiment does not limit the present invention.

Example 1 A reaction was carried out using the reaction apparatus shown in FIG. A polymerization degree of 1 was added to a reaction vessel (a Pyrex (registered trademark) eggplant-shaped flask having a capacity of 1000 ml).
000 vinyl chloride resin (Kanebuchi Chemical Industry Co., Ltd., S
187.78 g = 3 mol of the powder (1001M). The vinyl chloride resin is synthesized by a suspension polymerization method, and has an average particle size of 210 μm measured according to JIS-Z8801.
m, and has a particle size distribution shown in Table 1. 6 reaction vessels
While immersing in a hot bath at 0 ° C., 200
Nitrogen gas was passed at a flow rate of ml / min for 60 minutes, and chlorine gas was passed at a flow rate of 200 ml / min for 30 minutes. Thereafter, the chlorine gas was increased to 600 ml / min, and the chlorine gas was set at a position 35 cm away from the upper surface of the powder layer.
The surface of the powder layer was irradiated with ultraviolet rays using a 0 W high-pressure mercury lamp. The reaction starts when the mercury lamp is turned on, and a mixed gas of chlorine and hydrogen chloride is discharged from the gas outlet. Also,
When a thermocouple was inserted into the powder layer and the temperature of the powder layer was measured, the reaction started and the reaction heat was generated after the mercury lamp was turned on. After 5 minutes, the temperature of the powder layer was 80 ° C. Reached.
Since the reaction rate decreases as the reaction proceeds, the temperature of the powder layer gradually decreases, and after the reaction is continued for 200 minutes,
It was about 3 ° C. 180 minutes after the start of the reaction, the mercury lamp was turned off to terminate the reaction. After completion of the reaction, nitrogen gas was passed through the reaction vessel at a flow rate of 600 ml / min to replace chlorine gas. Sample 1 was obtained by continuing nitrogen replacement for 100 minutes.

The final chlorine content of Sample 1 was calculated from the change in weight before and after the reaction. That is, the chlorine content of the vinyl chloride resin was set to 56.8% by weight, and the change in weight of the powder resin before and after the reaction was calculated on the assumption that hydrogen in the vinyl chloride resin was replaced by chlorine. As a result, sample 1
Is 187.78 g to 244.40 g before and after the reaction
And the chlorine content was calculated to be 67.5% by weight.

The amount of hydrogen chloride remaining in Sample 1 was calculated by a neutralization titration method. A precisely weighed sample was dissolved in tetrahydrafuran, and then extracted with a mixed solution of methanol and water, and the amount of hydrochloric acid in the extract was subjected to neutralization titration. From the difference between the neutralization titration value of Sample 1 and the neutralization titration value of the mixture, the amount of hydrochloric acid contained in Sample 1 was calculated. As a result, the amount of residual hydrogen chloride in Sample 1 was 87 ppm.

The glass transition temperature of Sample 1 was determined according to JIS-
It measured by the method according to K7121. As a result, the glass transition temperature of Sample 1 was 133 ° C.

For 100 parts by weight of sample 1, MB
10 parts by weight of S (Kanebuchi Chemical Industry B31), 2 parts by weight of a tin-based stabilizer, and 1.7 parts by weight of a lubricant were blended and kneaded with an 8-inch roll at 195 ° C. for 3 minutes. The obtained sheet was pressed at 200 ° C. for 10 minutes to obtain a test piece. JIS
The Vicat softening temperature of the test piece measured by a method according to -K7206 was 113.4 ° C.

The thermal stability of Sample 1 was measured by a gear oven method. For 100 parts by weight of sample 1, MBS
10 parts by weight (Kanebuchi Chemical Industries B31), 2 parts by weight of a tin-based stabilizer, and 1.7 parts by weight of a lubricant were blended and kneaded with an 8-inch roll at 195 ° C. for 3 minutes. The obtained sheet was pressed at 200 ° C. for 10 minutes and cut into a size of 1 cm to obtain a test piece. The test piece was heated in a gear oven at 200 ° C., the test piece was taken out every 10 minutes, and the blackening time of the test piece was visually judged. As a result, the test piece was 60
Blackening took ~ 70 minutes. This is an evaluation method showing that the longer the blackening time, the better the thermal stability. (Example 2) Using the same vinyl chloride resin (polymerized by the suspension polymerization method) as in Example 1, a reaction was carried out using the reaction apparatus shown in FIG. A reaction vessel (pyrex (registered trademark) eggplant-shaped flask having a capacity of 1000 ml) was charged with 38.7 mol of 187.70 g of vinyl chloride resin powder. While immersing the reaction vessel in a warm bath at 50 ° C., nitrogen gas was introduced into the space of the reaction vessel at a flow rate of 200 ml / min.
And then flowed chlorine gas at a flow rate of 200 ml / min for 30 minutes. The flow rate of chlorine gas is 600ml / m
After increasing to in, the surface of the powder layer was irradiated with ultraviolet rays using a 400 W high-pressure mercury lamp installed at a position 35 cm away from the upper surface of the powder layer. The reaction was performed for 350 minutes from the start of the reaction, and the mercury lamp was turned off to terminate the reaction. After completion of the reaction, nitrogen gas was passed through the reaction vessel at a flow rate of 600 ml / min to replace chlorine gas. Sample 2 was obtained after continuous nitrogen replacement for 100 minutes.

In the same manner as in Example 1, the chlorine content, residual hydrochloric acid content, glass transition temperature, Vicat softening temperature, and blackening time of Sample 2 were measured. As a result, the chlorine content is
67.2% by weight, residual hydrogen chloride amount 82 ppm, glass transition temperature 132 ° C, Vicat softening temperature 113.3.
C. and the blackening time was 70 minutes. (Example 3) Using the same vinyl chloride resin (polymerized by the suspension polymerization method) as in Example 1, a reaction was carried out using the reaction apparatus shown in FIG. In a reaction vessel (pyrex (registered trademark) eggplant-shaped flask having a capacity of 1000 ml), 187.82 powder of a vinyl chloride resin synthesized by a suspension polymerization method was added.
g = 3 mol was charged. While immersing the reaction vessel in a 60 ° C. warm bath, nitrogen gas was passed through the space portion of the reaction vessel at a flow rate of 200 ml / min for 60 minutes, and further 200 ml / m 2.
At a flow rate of in, chlorine gas was passed for 30 minutes. After increasing the flow rate of chlorine gas to 600 ml / min, the surface of the powder layer was irradiated with ultraviolet rays using a 400 W high-pressure mercury lamp installed at a position 35 cm away from the upper surface of the powder layer. A thermocouple was inserted into the powder layer, and the temperature of the powder layer was measured. Since the reaction started after the lighting of the mercury lamp and the reaction heat was generated, the temperature of the powder layer reached 80 ° C. after 5 minutes. Thereafter, the temperature of the warm bath was gradually increased and controlled so that the temperature of the powder layer became constant at 80 ° C. The reaction was carried out for 155 minutes from the start of the reaction, and the mercury lamp was turned off to terminate the reaction. After completion of the reaction, nitrogen gas was passed through the reaction vessel at a flow rate of 600 ml / min to replace chlorine gas. Sample 3 was obtained by continuously purging with nitrogen for 100 minutes.

In the same manner as in Examples 1 and 2, the chlorine content, residual hydrochloric acid content, glass transition temperature, Vicat softening temperature, and blackening time of Sample 3 were measured. As a result, the chlorine content was 67.9% by weight, and the residual hydrogen chloride amount was 89 pp.
m, glass transition temperature is 136 ° C, Vicat softening temperature is 1
At 13.6 ° C., the blackening time was 50 minutes. (Comparative Example 1) 15 kg of the same vinyl chloride resin as used in Examples 1 and 2 and 35 kg of water were charged into a 50 L reaction vessel to form an aqueous suspension. 450W in water suspension
, Two vacuum mercury lamps were inserted, and vacuum degassing and nitrogen replacement were performed. While stirring the water suspension with a stirring blade, chlorine gas was introduced, and a mercury lamp was turned on to start the reaction. The starting temperature of the reaction was 50 ° C., and the reaction temperature was linearly increased so as to be 85 ° C. after one hour, and was kept constant after 60 minutes. Total 1
The reaction was continued for 00 minutes, and the reaction was terminated by stopping the chlorine gas and the mercury lamp. Neutralization titration of the aqueous suspension after the reaction is completed,
When the chlorine content was measured from the amount of generated hydrogen chloride,
It was 68.2% by weight. The cake obtained by filtering the aqueous suspension using a filter paper and a Nutsche was washed with water, and the washing liquid and the cake were separated by filtration. The obtained cake was dried at 55 ° C. for 24 hours or more using a shelf type drier to obtain Comparative Sample 1.

The amount of residual hydrogen chloride, glass transition temperature, Vicat softening temperature, and blackening time were measured in the same manner as in Examples 1 to 3. As a result, the amount of residual hydrogen chloride was 85 ppm, the glass transition temperature was 137 ° C., and the vicat The softening temperature was 113.8 ° C. The blackening time measured by the same gear oven test as in Example 3 was 40 to 50 minutes.

Example 1, Example 2, Example 3, Comparative Example 1
Table 2 shows the evaluation results of the samples obtained in the above. Table 2
According to the results, the chlorinated vinyl chloride-based resin synthesized by the gas-solid reaction method of the present invention was subjected to a simple post-treatment of flowing nitrogen for a short time of 100 minutes. It can be seen that the amount of residual hydrogen chloride is equivalent to that of a chlorinated vinyl chloride resin that has undergone complicated post-treatment steps of dehydration, washing, and drying for 24 hours or more after synthesis by a suspension method. The chlorinated vinyl chloride resin synthesized by the gas-solid reaction method of the present invention has a glass transition temperature and a Vicat softening temperature equivalent to those of the chlorinated vinyl chloride resin obtained by the water suspension method.
It turns out that it has sufficient heat resistance. Further, chlorinated vinyl chloride resin synthesized by the gas-solid reaction method of the present invention,
The blackening time in the gear oven test was longer than that of the chlorinated vinyl chloride resin obtained by the water suspension method, indicating that it had excellent thermal stability.

Example 4 400 parts of ion-exchanged water, 0.005 parts by weight of polyethylene oxide having an average molecular weight of 2,000,000, and 0.04 parts by weight of hydroxypropyl methylcellulose were placed in a stainless steel autoclave equipped with a stirring blade. Parts, 70 parts by weight of di-2-ethylhexylperoxydica carbonate in 0.05 parts by weight of isoparaffin solution, and the autoclave was degassed under vacuum, and then 100 parts by weight of vinyl chloride monomer. The department was charged. Thereafter, suspension polymerization was performed with stirring to obtain a vinyl chloride resin having a polymerization degree of about 1,000. The suspension of the vinyl chloride resin was dehydrated and dried to obtain a vinyl chloride resin A.

The chlorination reaction was carried out using the reactor shown in FIG. Powder of vinyl chloride resin A was placed in a reaction vessel (a reaction vessel made of Hastelloy C22 having a capacity of 10 L).
50 g = 12 mol was charged. Since the bulk density of the vinyl chloride resin A is 0.5 g / cm ³ , the powder layer is filled to a position lower than the rotation axis of the reaction vessel, and the light source is inside the reaction apparatus and outside the powder layer ( So that it is located outside the powder layer in the upper part of the container). The reaction container was placed on two rubber rollers installed in a direction parallel to the rotation axis of the reaction container, and the rubber roller was rotated, whereby the reaction container was rotated in the direction of the arrow in FIG. While flowing warm water of 40 ° C. through the jacket of the reaction vessel, nitrogen gas was flowed at a flow rate of 5000 ml / min for 30 minutes from a gas supply port provided inside the powder layer, and then 2500 ml / m 2.
At a flow rate of in, chlorine gas was passed for 30 minutes. Then, using a high-pressure mercury lamp of 100 W installed inside the reaction vessel,
The surface of the powder layer was irradiated with ultraviolet rays. The reaction starts when the mercury lamp is turned on, and a mixed gas of chlorine and hydrogen chloride is discharged from the gas outlet. Also, insert a thermocouple into the powder layer,
When the temperature of the powder layer was measured, the reaction started after the mercury lamp was turned on and the reaction heat was generated.
After 0 minutes, the temperature rose to 48 ° C. Further, the temperature of the hot water flowing through the jacket was raised to 60 ° C., and the temperature of the powder layer was set to about 80 ° C. 60 minutes after the start of the reaction. Then, the temperature of the hot water flowing through the jacket was adjusted, and the temperature of the powder layer was adjusted to 80.
The chlorination reaction was continued while the temperature was kept at ° C., and the mercury lamp was turned off 220 minutes after the start of ultraviolet irradiation to terminate the reaction. After the completion of the reaction, nitrogen gas was passed through the reaction vessel at a flow rate of 5000 ml / min to replace the gas with chlorine gas. 9 nitrogen substitutions
The sample that continued for 0 min was designated as Sample 4. Sample 4 was a white fluid powder.

The chlorine content of the resin during the reaction was calculated from the amount of hydrogen chloride contained in the reaction gas. That is, a mixed gas of chlorine and hydrogen chloride discharged from the gas outlet was passed through 10 L of water, and the amount of hydrogen chloride absorbed in the water was determined by neutralization titration every 10 minutes. Since a small amount of chlorine dissolved in the hydrogen chloride absorbing solution affects the neutralization titration value, add an aqueous solution of potassium iodide and sodium thiosulfate in advance,
Neutralization titration was performed so that chlorine did not affect the neutralization titration value. The calculation was performed on the assumption that the chlorine content of the vinyl chloride resin as the raw material was 56.8% by weight, and the chlorine in the same amount as the generated hydrogen chloride was replaced by hydrogen in the vinyl chloride resin.

In the same manner as in Example 1, the Vicat softening temperature and blackening time of Sample 4 were measured. As a result, the Vicat softening temperature was 113.5 ° C., and the blackening time was 60 to 70 minutes. Example 5 Using the same vinyl chloride resin A as in Example 4, a reaction was carried out using the reactor shown in FIG. In a reaction vessel (a reaction vessel made of Hastelloy C22 having a capacity of 10 L), 2500 g of powder of vinyl chloride resin A was added.
mol. The bulk density of the vinyl chloride resin A is
Since it is 0.5 g / cm ³ , the powder layer is filled up to the position of the rotation axis of the reaction vessel. As in Example 4, the light source is installed inside the reactor and outside the powder layer (located at the top of the container and outside the powder layer). The reaction container was placed on two rubber rollers installed in a direction parallel to the rotation axis of the reaction container, and the rubber roller was rotated, whereby the reaction container was rotated in the direction of the arrow in FIG. While circulating warm water at 40 ° C. through the jacket of the reaction vessel, nitrogen gas was circulated at a flow rate of 5000 ml / min for 30 minutes through the space in the reaction vessel, and further 5,000 ml / mi.
At a flow rate of n, chlorine gas was passed for 30 minutes. Thereafter, the surface of the powder layer was irradiated with ultraviolet rays by using the installed high-pressure mercury lamp of 100 W. The reaction starts when the mercury lamp is turned on, and a mixed gas of chlorine and hydrogen chloride is discharged from the gas outlet. In addition, when a thermocouple was inserted into the powder layer and the temperature of the powder layer was measured, the reaction started after the mercury lamp was turned on and reaction heat was generated. ° C
Rose. Further, when the temperature of the hot water flowing through the jacket was raised to 60 ° C., the temperature of the powder layer became about 80 ° C. 50 minutes after the start of the reaction. Then, the temperature of the powder layer was set at 8
The chlorination reaction was continued while controlling the temperature of the hot water flowing through the jacket to maintain the temperature at 0 ° C.
After 0 minute, the mercury lamp was turned off to terminate the reaction. After completion of the reaction, nitrogen gas was passed through the reaction vessel at a flow rate of 5000 ml / min to replace the gas with chlorine gas. 90m nitrogen replacement
The sample that was continued during the period in was designated as Sample 5. Sample 5
Was a white fluid powder.

In the same manner as in Example 1, the chlorine content, Vicat softening temperature and blackening time of Sample 5 were measured. As a result, the Vicat softening temperature was 113.4 ° C., and the blackening time was 60 to 70 minutes. (Comparative Example 2) Using the same vinyl chloride resin A as in Example 4, a reaction in which the fixed part holding tube, light source, gas supply port, and gas discharge port of the reactor shown in FIG. 7 were connected upside down. The reaction was performed using the apparatus. in this case,
The light source is installed at a position lower than the rotation axis of the reaction vessel (at the lower part in the vessel and in the powder layer). A reaction vessel (a reaction vessel made of Hastelloy C22 having a capacity of 10 L) was charged with 2500 g = 40 mol of powder of vinyl chloride resin A. The bulk density of the vinyl chloride resin A is 0.5 g / cm ³
Therefore, the powder layer is filled up to the position of the rotation axis of the reaction vessel. In this case, the light source is installed inside the reactor and inside the powder layer. The reaction container was placed on two rubber rollers installed in a direction parallel to the rotation axis of the reaction container, and the rubber roller was rotated, whereby the reaction container was rotated in the direction of the arrow in FIG. While circulating warm water at 40 ° C. through the jacket of the reaction vessel, nitrogen gas was circulated at a flow rate of 5000 ml / min for 30 minutes through the space of the reaction vessel, and chlorine gas was circulated at a flow rate of 5000 ml / min for 30 minutes. Then, the 1 set inside the reaction vessel
The inside of the powder layer was irradiated with ultraviolet rays using a 00 W high-pressure mercury lamp. The reaction starts when the mercury lamp is turned on, and a mixed gas of chlorine and hydrogen chloride is discharged from the gas outlet. When a thermocouple was inserted into the powder layer and the temperature of the powder layer was measured, the reaction started after the mercury lamp was turned on and generated reaction heat. The temperature rose to 56 ° C. When the temperature of the hot water flowing through the jacket was increased to 60 ° C., the temperature of the powder layer became about 80 ° C. 50 minutes after the start of the reaction. After the start of the reaction, an attempt was made to adjust the temperature of the powder layer to about 80 ° C., but the temperature changed rapidly and it was difficult to adjust the temperature. Further, the powder temperature rose rapidly during 100 to 160 minutes after the start of the reaction, so that the powder resin was fused and the rotation of the reaction vessel was stopped. When the chlorine gas in the container was replaced with nitrogen gas, the resin was taken out. As a result, the resin became a mass of about 15 cm and was fixed around the light source, and the device was damaged.

Table 3 shows the transition of the chlorine content in the chlorinated vinyl chloride resin and the temperature of the powder layer when the reactions of Examples 4 and 5 and Comparative Example 1 were carried out. In Examples 4 and 5 in which the light source was installed inside the reaction vessel and outside the powder layer, the reaction temperature was controlled at about 80 ° C. while the chlorine content was increased, and the reaction proceeded smoothly. You can see that there is. On the other hand, in Comparative Example 2 in which the light source was installed inside the reaction vessel and inside the powder layer, the temperature of the powder layer rapidly increased and decreased repeatedly despite the slow rise in the chlorine content. This indicates that the reaction was unstable. In addition, the rise in the temperature of the powder layer caused the resin to fuse and destroy the reactor.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

According to the present invention, light is radiated from a light source installed outside the powder layer to the vinyl chloride resin powder in a flowing state while supplying chlorine into and / or outside the powder layer. By chlorinating a vinyl chloride resin, hydrogen chloride can be easily removed, and a chlorinated vinyl chloride resin excellent in heat resistance and heat stability can be produced.

[Brief description of the drawings]

FIG. 1 is a model diagram of chlorination of powder particles of a vinyl chloride resin.

FIG. 2 is a schematic view showing a portion where a reaction proceeds when a light source is installed inside a powder layer and when it is installed outside a powder layer.

FIG. 3 is a schematic diagram showing a portion where a reaction proceeds when a position for supplying chlorine is changed.

FIG. 4 shows an experimental apparatus of a rotary reactor in which a light source is installed outside a reaction vessel in the present invention.

FIG. 5 is an example of the apparatus of the present invention, and shows a rotary reaction apparatus when a light source is installed inside a reaction vessel. The white body in the figure rotates, and the hatched parts are fixed by the non-rotating tube. The powder layer can be filled to a position where the light source does not contact.

FIG. 6 is another example of the apparatus of the present invention, and is a view of a rotary type reaction apparatus when a light source is installed inside a reaction vessel. The white parts in the figure are rotating, and the hatched parts including the lid are stationary. The powder layer can be filled to a position where the light source does not contact.

FIG. 7 is a diagram of a rotary type reaction apparatus when a light source is installed inside a reaction vessel. The white parts in the figure rotate, and the hatched parts are fixed by the non-rotating tube. The powder layer is
It can be filled to the position where the light source does not touch.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 light source 2 powder layer 3 part reacting in powder layer 4 light source 5 chlorine gas supply port 6 powder layer 7 light source 8 chlorine gas supply port 9 powder layer 10 constant temperature bath 11 gas flow meter 12 chlorine cylinder 13 rotary type Reaction vessel and lid 14 Refrigerant / heat medium jacket 15 Rotary joint 16 Refrigerant / heat medium inlet / outlet 17 Rotating shaft holder 18 Chlorine gas supply port 19 O-ring 20 Dust seal 21 Rotary gas seal 22 Non-rotating pipe 23 To exhaust gas treatment device 24 Chlorine gas To the supply device 25 Powder layer 26 Light source 27 Thermocouple 28 Gas outlet 29 Rotary reaction vessel 30 Refrigerant / heat medium jacket 31 Rotary joint 32 Refrigerant heat medium inlet / outlet 33 Rotation shaft holder 34 Chlorine gas supply port 35 O-ring 36 Lid Retaining ring 37 Rotating gas seal 38 To chlorine gas supply device 39 To exhaust gas treatment device 40 Light source 41 Gas discharge port 42 Powder layer 43 Thermocouple 44 Non-rotating plate and support rod 45 Reaction vessel 46 Refrigerant heat medium jacket 47 Refrigerant heat medium flow pipe 48 Rotary joint 49 Refrigerant heat medium inlet / outlet 50 Chlorine gas supply port 51 O-ring 52 Lid 53 Rotating seal 54 Non-rotating pipe 55 To exhaust gas treatment device 56 To chlorine gas supply device 57 Light source 58 Gas outlet 59 Powder layer

Claims (15)

[Claims] Claims: 1. While supplying chlorine into and / or out of a powder layer of a vinyl chloride resin in a fluidized state, a reaction is accelerated on a surface of the powder layer by a light source installed outside the powder layer. Chlorinating the vinyl chloride resin by irradiating light for the purpose of the present invention. 2. The method for producing a chlorinated vinyl chloride resin according to claim 1, wherein the powder of the vinyl chloride resin is brought into a fluidized state using a rotary reactor or a stirring reactor. 3. The method for producing a chlorinated vinyl chloride-based resin according to claim 1, wherein the reactor is a rotary reactor and a light source is installed inside the reactor. 4. The method for producing a chlorinated vinyl chloride resin according to claim 1, wherein the light source is at least one selected from a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp. 5. The method for producing a chlorinated vinyl chloride resin according to claim 2, wherein the position for supplying chlorine is in the powder bed. 6. The reaction of a light source installed outside the powder layer on the surface of the powder layer while supplying chlorine into and / or outside the powder layer of the vinyl chloride resin in a fluidized state, to promote a reaction on the surface of the powder layer. Chlorinating vinyl chloride resin by irradiating it with light for chlorination. 7. The apparatus for producing a chlorinated vinyl chloride-based resin according to claim 6, wherein the powder of the vinyl chloride-based resin is brought into a fluidized state using a rotary reactor or a stirring reactor. 8. The apparatus for producing a chlorinated vinyl chloride resin according to claim 6, wherein the reactor is a rotary reactor and a light source is installed inside the reactor. 9. The apparatus for producing a chlorinated vinyl chloride resin according to claim 6, wherein the light source is at least one selected from a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp. 10. The apparatus for producing a chlorinated vinyl chloride resin according to claim 8, wherein the supply port of the chlorine gas supply nozzle is disposed so as to discharge the chlorine gas downward. 11. The apparatus for producing a chlorinated vinyl chloride resin according to claim 8, wherein a chlorine gas supply nozzle is provided inside the powder layer. 12. The apparatus for producing a chlorinated vinyl chloride resin according to claim 8, wherein the gas outlet is provided outside the powder layer. 13. A non-rotatable cylindrical tube arranged on the rotation axis of the reaction vessel is inserted into the reaction vessel, and the space between the non-rotational pipe and the reaction vessel is sealed with a rotary gas seal. 10. The non-rotating tube of the inserted portion is provided with at least one component selected from a light source, a chlorine gas supply nozzle, a gas discharge nozzle, and a thermocouple.
13. The apparatus for producing a chlorinated vinyl chloride resin according to 11 or 12. 14. A disk-shaped non-rotating plate arranged on a plane perpendicular to the rotation axis of the reaction vessel is covered as a lid over the opening of the reaction vessel, and the space between the non-rotating plate and the reaction vessel is sealed using a rotary seal. The non-rotating plate is provided with at least one component selected from a light source, a chlorine gas supply nozzle, a gas discharge nozzle, and a thermocouple.
2. The apparatus for producing a chlorinated vinyl chloride resin according to item 1. 15. A cooling medium or a heating medium is supplied to the jacket via a rotary joint having a double circular tube structure mounted on the rotation axis of the reaction vessel and opposite to the non-rotating tube or the non-rotating plate. An apparatus for producing a chlorinated vinyl chloride resin according to claim 13.