JPS612701A - Polymerization apparatus and its use - Google Patents

Abstract

PURPOSE:To produce a highly transparent polymer free from dust and thermal decomposition product, in high efficiency, by using a transportable and closable polymerization vessel free from stirring means, connecting the vessel to a polymer transfer apparatus with a connector, and transferring a polymerized monomer to the transfer apparatus. CONSTITUTION:A transportable and closable polymerization vessel 1 having no stirring means is furnished with a connector 28 for connecting the vessel to a polymer transfer apparatus. Monomer is charged to the vessel through the inlet 2, and polymerized. While the polymer is still in fluid state, the connection part 28 of the polymerization vessel is attached to the polymer transfer apparatus, and the polymer is transferred to the transfer apparatus. It is preferable to use a polymerization vessel 1 having an inner diameter of <=15cm and a length of <=100cm, and furnished with smallest possible number of openings, i.e. 2-4 openings, and to close said openings to obtain a highly transparent polymer. EFFECT:The apparatus is compact and transportable.

Description

DETAILED DESCRIPTION OF THE INVENTION A. TECHNICAL FIELD OF THE INVENTION The present invention relates to a portable and sealable polymerization apparatus and method of using the same.

B. Prior art and its problems Recently, highly transparent polymers are in demand in fields such as optical fibers and optical lenses. It is necessary to minimize the amount of additives that impede the transmission of light, or to make them virtually non-existent.

Conventional polymerization equipment usually has a stirring mechanism, as well as pumps and valves for feeding monomers and polymers, which can introduce optical foreign substances and make it difficult to obtain highly transparent polymers. there were. In addition, the conventional batch method (monomer purification and polymerization is performed each time) for producing highly transparent polymers has poor production efficiency. This was a problem from an industrial standpoint.

Recently, in the field of optical fibers, where the transparency of a polymer has a large effect on light-transmitting performance, a method has been proposed in which a highly transparent polymer is made and then spun to obtain an optical fiber with good light-transmitting performance.

For example, Japanese Patent Publication No. 53-42260 and Special Publication No. 58-
Publication No. 171405 discloses that a highly transparent PMMA thread polymer is obtained by a continuous bulk polymerization method, and in these methods, pumps, valves, etc. are inserted in the middle of piping.
Since the monomers and polymers are continuously flowed, the negative effects of their presence are relatively small, but it is essential to install a stirrer in the polymerization container, so there is an opportunity for foreign substances or heat-degraded substances to enter from the outside. In many cases, the level of light transmission performance when made into optical fibers deteriorates.

On the other hand, in Japanese Patent Publication No. 57-51645, after a purified monomer is charged into a polymerization container, the polymerization is conducted in a substantially closed state.
Next, the polymerization container is cooled to solidify the polymer and taken out.
Next, after filling this solidified polymer into a spinning device,
It is heated and melted and spun.

However, with this method, when taking out the solidified polymer or feeding it to a spinning device, it is unavoidable that dust etc. are mixed in, and when the solidified polymer is melted, it is not affected by oxidative deterioration. The light transmission performance of the optical fiber is poor.

Furthermore, in JP-A-58-68003, after charging a purified monomer into a polymerization vessel, polymerization is carried out in a substantially closed state, and this polymer is composite-spun, and the optical fiber obtained by this method has a light-transmitting property. However, since it is necessary to perform monomer purification, polymerization, and spinning each time, there is a problem that production efficiency is inferior.

C9 Purpose of the Present Invention The present invention was devised in view of the various drawbacks of the prior art, and its purpose is to make the polymerization apparatus itself portable and compact, and to prevent contamination by dust, heat-degraded substances, etc. It is an object of the present invention to provide a polymerization apparatus and a method for using the same, which can significantly improve production efficiency.

D9 Structure of the present invention That is, the present invention consists of the following configuration.

(11) A polymerization device that is portable, airtight, and does not have a stirring mechanism, and furthermore, the polymerization container is provided with an engaging portion for connection to a polymer transfer device.

(2) After polymerizing the monomer in a polymerization container that is portable, airtight, and does not have a stirring mechanism, the polymerization container is attached to a polymer transfer device while the polymer is in a fluid state, and then the above-mentioned A method of using a polymer, comprising transferring the polymer to a transfer device.

The present invention will be explained in detail below with reference to the drawings.

FIG. 1 shows an example of a polymerization apparatus according to the present invention, in which a polymerization container 1 is made of stainless steel with a mirror-finished inner surface (surface roughness of 28 or more) and has a stirring mechanism. . If the surface of the container or inner surface is rough, it is difficult to clean it even by washing, and it is difficult to obtain a highly transparent polymer. A monomer charging port 2 is attached to the polymerization container 1.
A purified monomer containing a polymerization catalyst is charged through a valve 3 provided in the tank. The lower part of the polymerization container 1 has an engaging part 4 made of a flange so that it can be detachably attached to a polymer transfer device.
A blind plate 5 is brought into contact with this flange portion 4, and a bolt 6 is attached.
to maintain airtightness.

After charging the monomer from the charging port 2, a camp 26 is attached to the tip of the charging port 2 to prevent the tip of the charging port 2 from getting dirty. After the monomer charged from the charging port 2 is polymerized at a predetermined polymerization temperature and polymerization time, it is transported to the polymer transfer device while the polymer in the polymerization container 1 is still in a fluid (molten) state, and is transferred to the polymerization container 1. Remove the blind plate 5 at the bottom of 1 and attach the polymerization device.

Note that the polymer transfer device here refers to a molding device, a demonomer device, a spinning device, etc. for the next process to be connected to the polymerization device, and a demonomer tank for demonomizing unreacted monomers in the polymer. This includes things like polymer storage tanks.

In the apparatus of the present invention, there is no stirring blade or the like, and since the apparatus has good airtightness, no dust or the like is taken in from the outside, so that a highly transparent polymer can be easily obtained. Furthermore, since the apparatus of the present invention is portable, it is possible to prepare a plurality of polymerization apparatuses in advance, perform polymerization separately, and sequentially charge these polymers to a polymer transfer apparatus, thereby increasing production efficiency. .

FIG. 2 shows another embodiment of the polymerization apparatus according to the present invention, in which the inner surface of the polymerization vessel 1 is plated with chrome or the like to have a mirror surface. 27 is a valve with good airtightness added to the lower part of the polymerization container 1, 28 is a connection engagement part having a threaded part on the circumference, and the camp 7 is fitted into this engagement part 28 to make it airtight. Gender is preserved.

A piston 8 for transferring the polymer is attached to the upper part of the polymerization container 1, and a gasket 9 made of Teflon or the like is fitted to the lower part of the piston 8 to maintain airtightness. After the monomer charged from the charging port 2 is polymerized in the same manner as in the case shown in Fig. 1, the polymerization device is transported to the polymer transfer device while the polymer in the polymerization container 1 is in a fluid (melted) state. Then, the engaging portion 28 of the polymerization device is attached to the engaging portion of the polymer transfer device.

FIG. 3 illustrates another polymerization apparatus according to the present invention,
The entire polymerization container 10 is made of glass. Reference numeral 11 designates a charging port, and reference numerals 12 and 13 designate sealing portions and connecting engagement portions formed at the top and bottom of the polymerization container, respectively. After the polymerization container 10 is washed and dried, the melt-sealing parts 12 and 13 are melt-sealed, respectively.
Next, after charging purified monomer containing a polymerization catalyst through the monomer charging port 11, the charging port 11 is sealed to maintain airtightness. After a given polymerization, the polymer is still flowing (
Cut the lower part 12 and the upper part 13 while it is in a molten state,
The lower end engaging part engages with a polymer transfer device, and the upper end engaging part engages, for example, a hose to supply the polymerization container 1 with pressurized gas such as N2 gas.
0 polymer to a polymer transfer device.

In this case, in order to engage the polymerization container IO with the polymer transfer device with good airtightness, it is desirable that the lower part 12 of the polymerization container 10 has substantially the same diameter and its length is at least 3 CI11 or more.

Although it is possible to obtain a highly transparent polymer using such a simple device, it is difficult to reuse this polymerization device.

Figure 4 is a schematic diagram showing the state in which the polymerization apparatus shown in Figure 1 is attached to a polymer transfer apparatus/spinning apparatus. 1 to the location of the polymer transfer device 16 and the flange 15.1
4 are firmly joined with bolts to maintain airtightness.

Next, N2 gas is supplied from the charging port 2, and the polymer is transferred to the polymer transfer device 16 under the pressure thereof, and then transferred by the extrusion screw 18 to be used as the core component of the optical fiber. During this transfer, unreacted monomer is removed from the vent 17 and then sent to the gear pump section 19 for metering the polymer. On the other hand, the polymer that becomes the cladding component of the optical fiber is produced in an extruder 21.
It is supplied to the hopper 20 of 20 so that no dust is mixed in, and then heated and melted in the extruder 21 while being fed to the metering gear pump part 2.
The liquid is sent to 2. The polymers measured by each gear pump are combined in a composite bank part 23, composited in a spinneret 24, and spun as an optical fiber 25. The obtained optical fiber 25 has excellent optical transmission performance and can be effectively used for optical communication applications.

The polymerization apparatus of the present invention is preferably portable, and in order to obtain a highly transparent polymer having uniform physical properties, the polymerization vessel preferably has an inner diameter of 15 cm or less and a length of 100 cm or less. If the inner diameter and length of the polymerization container do not satisfy the above-mentioned conditions, the obtained polymer will not only be non-uniform, but also difficult to transport, install, etc., which is not preferable.

In order to obtain a highly transparent polymer, the polymerization apparatus of the present invention preferably has as few openings as possible, and is preferably provided with two to four openings. If there is only one opening, it will be difficult to transfer the polymer, and if there are five or more openings, the opening will become a dead space, which will impede cleaning of the apparatus, which is not preferable. Furthermore, in order to obtain a highly transparent polymer in the polymerization apparatus of the present invention, it is preferable that the opening is substantially sealed during polymerization.

Although the polymerization apparatus of the present invention can be used as a polymerization apparatus for all types of polymers, it is preferable to use it as a polymerization apparatus for polymerizing highly transparent polymers (in particular, by bulk polymerization method. Preferred polymers for application include:
Examples include polymers mainly composed of methyl methacrylate, polymers mainly composed of styrene, polymers mainly composed of deuterated methyl methacrylate, and polymers mainly composed of deuterated styrene.

E. Effect of the present invention Since the polymerization apparatus of the present invention has the configuration as described above, it is possible to achieve 1.
In general, it is compact and can prevent dust, heat-degraded substances, etc. from entering as much as possible. Furthermore, according to the present invention, it is possible to prepare a plurality of polymerization apparatuses and handle them at the same time, which is particularly useful, for example, when polymerizing expensive monomers or when polymerizing a wide variety of products. Further, a small amount of the polymer can be sent to the next step substantially continuously intermittently, which is also useful from the viewpoint of productivity.

The present invention will be explained below with reference to Examples.

Example 1 Two polymerization apparatuses as shown in FIG. 1 were used.

The polymerization vessel has an inner diameter of 40 parts mφ and is made of stainless steel, the inner surface being polished (surface roughness=38). The blind plate at the bottom of the polymerization vessel was removed, washed twice with n-hexane, and then three times with 50% acetate, and then the polymerization vessel was heated and dried. After attaching a blind plate to this polymerization container and confirming that the airtightness is sufficient, 95 parts of purified methyl methacrylate, 5 parts of methyl acrylate, and 0.002 parts of ditertiary butyl peroxide as a polymerization initiator were added.
400 cc of a mixed solution containing 0.01 part of L-butyl mercaptan as a chain transfer agent were charged, and the valve at the charging port was closed to seal the inside of the container.

The two polymerization apparatuses charged with the monomers in this manner were placed in a dryer and polymerized at 100°C-180°C for 20 hours.

While the obtained polymer was still in a molten state, the blind plate was removed and the device was placed on the flange of a polymer transfer device as shown in Figure 4. A heater was attached to the polymerization container to ensure that the polymer in the polymerization container was Heat to 200°C to maintain a molten state. Thereafter, 10 kg/cJ of N2 gas was supplied from the charging port to transfer the polymer to a polymer transfer device heated to 220°C. Approximately 3% of the monomer present in the polymer is vacuum degassed from the hentro of the polymer transfer device.

Immediately after transferring the polymer from the first polymerization device, the next polymerization device is attached to the polymer transfer device and the polymer is transferred. This polymer is used as the core component of the optical fiber. A copolymer of vinylidene fluoride and tetrafluoroethylene is used as the cladding component. The Krat component is heated and melted at 210°C in an extruder. Weigh both the core component and cladding component using a gear pump so that the volume ratio is 90:10, and combine them at the mouthpiece.
20m/min from a single hole base as an optical fiber with a diameter of 00μ
Spun with.

Transmission loss of the optical fiber thus obtained → 570 parts m
It was 88 dB/km. Optical fibers made from polymers polymerized in a conventional polymerization tank with a stirrer had a power of 200 dB/km.

According to the present invention, the obtained polymer is highly transparent and can be easily attached to a polymer transfer device for the next step with good airtightness. It is also understood that the polymerization apparatus of the present invention can send polymers from a plurality of (in this case two) polymerization apparatuses almost continuously to the polymer transfer apparatus for the next step.

Example 2 A polymerization apparatus as shown in FIG. 2 was used. The polymerization vessel had an inner diameter of 35 m1φ and was made of chrome-plated stainless steel. The piston at the top of the polymerization vessel is also made of chrome-plated stainless steel, and a Teflon gasket is used to maintain airtightness between the piston and the polymerization vessel. This polymerization vessel was washed twice with n-hexane and then three times with distilled acetone. Thereafter, the polymerization apparatus is heated and dried. After attaching a cap to the bottom of this polymerization container, 100 parts of purified methyl methacrylate,
Ditertiary butyl peroxide 0 as polymerization initiator
．． 0.001 part of a chain transfer agent and 0.001 part of a chain transfer agent, 200 cc of a mixed solution was charged, and the valve at the charging port was closed to seal the inside of the container. This polymerization apparatus was placed in a dryer, and polymerization was carried out at 130°C to 180°C for 25 hours. While the polymer polymerized in this manner remained in a molten state, the lower cap of the polymerization device was removed, and the polymerization device was attached to the threaded portion of the polymer transfer device. A heater is installed to keep this polymer in a molten state in the polymerization container.
Heat to ℃. Thereafter, the piston of the polymerization device is pressurized with a hydraulic cylinder to transfer the polymer to a polymer transfer device heated to 240°C.

Approximately 4% of the monomer present in the polymer is vacuum degassed from the hentro of the polymer transfer transfer device. The polymer was injected into a mold attached to the tip of this polymer transfer device, and the diameter was 30 mm.
Pressure mold it into a cylinder with a length of 20n. When the transmitted light of this molded product was detected using a laser diode having a main wavelength of 660 nm, the transmitted light was 99%. When the transmitted light was detected for a molded product of the same shape of a polymer polymerized in a conventional polymerization tank equipped with stirring blades, the result was 96%.

With the polymerization apparatus of the present invention, highly transparent polymers can be easily obtained,
Moreover, it can be seen that it can be easily and airtightly installed for transferring the polymer in the next step.

Example 3 Four polymerization apparatuses (containers) as shown in FIG. 3 were used.

This polymerization container is made of “Pyrex” glass,
The inner diameter is 30 mm. There are three openings. This glass polymerization container is washed three times with distilled acetone and then dried in a dryer.

The upper and lower openings of this polymerization container are sealed.

The upper and lower parts of the sealed polymerization container had a straight part of 6 cm with an outer diameter of 10 iris layers φ. After charging a small amount of purified styrene from the charging section and washing the inside of the polymerization container, styrene 10
0 parts, polymerization initiator ditertiary butyl peroxide O
, 2 parts OO, chain transfer agent n-octyl mercaptan 0.
Pour 150 cc of the 01 part mixed solution, and then seal the charging port. Place this polymerization container in a dryer at 100℃~
Polymerize at 180°C. While this polymer is in a molten state, the top and bottom tips of the polymerization container are cut off, and the bottom of the polymerization container is tightly engaged with the attachment port of the polymer transfer device using an engaging member using a Teflon ferrule. , the upper part is engaged with an engagement member similar to a Teflon hose for N2 gas. A heater was wound around the polymerization vessel to heat it to 210°C, and at the same time, N2 gas was introduced into the upper part of the polymerization vessel and the pressure was increased to 23 kg/cnl.

The polymer is sent to a measuring section using a polymer transfer device heated to 220° C., and this component is used as a core component of an optical fiber. 411
Immediately after the transfer of the polymer in one polymerization container is completed, the connection is changed, and the polymer is transferred substantially continuously. The Kuranodo component is melted and heated with polytrifluoroethyl methacrylate in an extruder heated to 220°C, and then sent to the measuring section. The capacitance ratio of the core component and cladding component is set to 85:15, and the fiber is composited at the base and is made into a 500μ optical fiber.
Spun with win.

The optical fiber thus obtained has a transmission loss of 610r+n
+ was 125 dB/kI11. The light transmission loss of the optical fiber from the polymer layered in a conventional stirrer-equipped polymerization tank was 280 dB/kI11 at the same wavelength.

It was found that the polymer obtained by the apparatus of the present invention has high transparency and can be easily attached to the polymer transfer apparatus for the next step. Furthermore, it has been found that the polymerization apparatus of the present invention can send polymers from a plurality of polymerization apparatuses (four in this case) almost continuously to the polymer transfer apparatus for the next step.

[Brief explanation of drawings]

1, 2, and 3 are schematic diagrams each illustrating a polymerization device according to the present invention, and FIG. 4 is a schematic diagram showing a state in which the polymerization device according to the present invention is attached to a polymer transfer device. . ■... Metal polymerization container, 2.11... Feeding port, 3゜27... Valve, 4, 14... Flange, 5...
Blind plate, 6.15... Bolt, 7.26... Cap, 8... Piston, 9... Gasket, 10...
Glass 11 container, 12.13...Installation port, 16...
・Polymer transfer device, 17...Hentro, 1st...Screw, 19.22...Gear pump, 20...Hopper, 21...Extruder, 23...Composite pack section, 24 ...Base, 25...Optical fiber.

Claims (2)

[Claims] (1) A polymerization device that is a portable, sealable polymerization container that does not have a stirring mechanism, and that the polymerization container is provided with an engaging portion for connection to a polymer transfer device. (2) After polymerizing the monomer in a polymerization container that is portable, airtight, and does not have a stirring mechanism, the polymerization container is attached to a polymer transfer device while the polymer is in a fluid state, and then the above-mentioned A method of using a polymer, comprising transferring the polymer to a transfer device.