JP2003277497A - Method of producing ethylene oxide-based resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing a new ethylene oxide-based resin that can readily control the moisture content less than a certain quantity without use of an antistatic agent, further inhibits the resin from being damaged with heat and can realize cost saving. <P>SOLUTION: In the method of producing ethylene oxide-based resin, the ethylene oxide-based resin is obtained by evaporation of the solvent from a solution of polymerization reaction mixture. In this case, the concentration of the solvent and the water content remaining in the resin after the evaporation are controlled in a range of from 0.01-30 wt.% and ≤2,000 ppm, respectively. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an ethylene oxide resin. Specifically, it relates to a method for producing an ethylene oxide resin, which includes a step of devolatilizing the resin reaction solution obtained by a polymerization reaction.

[0002]

2. Description of the Related Art Conventionally, ethylene oxide resins have been
In addition to polyurethane resins such as adhesives, paints, sealing agents, elastomers, flooring agents, hard, soft or semi-hard polyurethane resins, as well as surfactants, sanitary products, deinking agents, lubricating oils, hydraulic fluids, etc. It is useful as a polymer material in applications, and in recent years, in view of its versatility, it is being considered for use in various other new applications (for example, see Non-Patent Document 1). For the method for producing the ethylene oxide resin, particularly for the method for purifying and recovering the resin after the polymerization reaction, conventionally, the polymerization reaction solution after the solution polymerization is poured into a large amount of a poor solvent to precipitate the resin, and filtration or A method of centrifuging and then drying to obtain a powder, and a method of drying a resin obtained by filtering or centrifuging a polymerization reaction solution after precipitation polymerization to obtain a powder are generally known.

However, in these methods,
There is a risk of explosion due to electrification and heating of the resin due to static electricity generated at that time because the process of heating and drying the resin to powderize it for the reason of obtaining high-purity resin etc. . Therefore, considering its prevention and safety,
It was usually essential to add a sufficient amount of antistatic agent. Addition of this antistatic agent increases the dielectric constant of the obtained resin more than necessary, and causes a decrease in the degree of crosslinking and an increase in hygroscopicity, increasing the swelling ratio of the resin more than necessary and reducing the strength. It causes such as. Therefore, it is very difficult to use an ethylene oxide resin containing an antistatic agent as a protective film of a color filter in terms of an increase in dielectric constant, and in terms of strength reduction, a flexographic printing plate material and an electrolyte layer of a polymer battery. It was very inappropriate to use it for etc.

Further, the ethylene oxide resin is a resin having an ether bond in the main chain and has a weak molecular structure (the portion of the ether bond) with respect to strong heating (high heat). There was a problem that the resin decomposes during drying. In addition, in the above method, in addition to heating and drying, new additional elements such as a poor solvent are required, and it is necessary to consider the increase in equipment costs associated with a plurality of steps and the cost increase. It was a problem. Furthermore, the ethylene oxide resin is often used in the form of a solution or a paste at the time of use.
Once powdered like the above method,
When a solvent is newly added to form a solution or a paste, the treatment becomes very difficult, which is a problem in terms of usability.

On the other hand, when the ethylene oxide resin is used as a protective film of a color filter or a polymer electrolyte of a polymer battery, for example, it is required to keep the water content of the resin to a certain level or lower. But,
In the conventional general method, it was not easy to obtain the resin while satisfying various conditions for obtaining the desired resin and controlling the water content to be low. If the water content cannot be controlled below a certain level, the dielectric constant of the resin will be unnecessarily high, and, for example, when used as a protective film for a color filter, the protective film will become a conductor and cause functional deterioration. There was a problem that it would end up. Further, if it is not possible to control in the same manner, this water reacts with a metal ion component to generate a hydroxide or the like. Therefore, for example, when the resin is used for an electrolyte layer of a polymer battery, the metal-electrolyte layer is used. Since an insulating layer is formed at the interface, the voltage under a constant current continues to rise, and the cycle characteristics of the battery deteriorate.

[0006]

[Non-Patent Document 1] Herman F. Mark, Norbert M. Bikale
s, Charles G. Overberger, edited by Georg Menges, “Encyc
lopedia of Polymer science and engineering '', volum
e6, (US), Wiley Interscience, 1986, p.225-32
2

[0007]

Therefore, the problem to be solved by the present invention is to easily control the water content to a certain level or less while not containing an antistatic agent in obtaining an ethylene oxide resin. And, and
It is an object of the present invention to provide a novel method for producing an ethylene oxide resin, which can prevent thermal damage to the resin and realize cost reduction.

[0008]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems. In the process, attention was focused on a treatment method for purifying and recovering the resin by devolatilization, which was conventionally known as a step in a general resin production method, and the effects obtained by this treatment method were examined. Heretofore, in obtaining an ethylene oxide resin, there has been no knowledge that the resin is synthesized by polymerization using a solvent, and then purified / collected through a devolatilization treatment, which has not been actually carried out. In view of various effects obtained by the devolatilization treatment, the present inventor considered that, in order to solve the above problems, the treatment step by devolatilization should be included only when an ethylene oxide resin is obtained. is there.

That is, according to the devolatilization treatment, there is no need to add an antistatic agent because purification / collection by heating and drying is not carried out, and there is no problem of cost increase mentioned above.
It was speculated that the water content of the resin could be easily adjusted during the devolatilization treatment. Therefore, when actually producing an ethylene oxide resin, when a polymerization reaction liquid is obtained by polymerization using a solvent and subsequently a devolatilization treatment of the reaction liquid is performed in combination, the above problems can be solved at once. It was confirmed that the present invention was completed.

That is, the method for producing an ethylene oxide resin according to the present invention is a method for obtaining an ethylene oxide resin by devolatilizing the solvent from a polymerization reaction solution containing a solvent, wherein The solvent concentration is 0.01 to 30% by weight, the water content is 200 ppm or less, and the resin does not contain an antistatic agent. Further, in the method for producing an ethylene oxide resin according to the present invention, in the above, the devolatilization temperature can be 40 to 300 ° C., and the pressure can be 13 to 100,000 Pa, and the devolatilization is stirring. It can be carried out using at least one device selected from the group consisting of a tank evaporator, a downstream liquid column evaporator, a thin film evaporator, a surface renewal type polymerization device, an extruder and a kneader.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an ethylene oxide resin according to the present invention (hereinafter sometimes referred to as the production method of the present invention) will now be described in detail, but the scope of the present invention is restricted by these explanations. However, other than the following examples, appropriate modifications may be made without departing from the spirit of the present invention. The production method of the present invention is a method of obtaining an ethylene oxide resin by devolatilizing the solvent from a polymerization reaction liquid containing a solvent, and the residual solvent concentration in the ethylene oxide resin after the devolatilization is 0.01. ~ 3
The content of water is 0 wt% and the content of water is 200 ppm or less, and the ethylene oxide resin does not contain an antistatic agent.

The polymerization reaction liquid to be subjected to the devolatilization treatment and the devolatilization treatment for carrying out the present invention will be described in detail below, and the use of the ethylene oxide resin obtained by the present invention will also be described. [Polymerization reaction liquid] The polymerization reaction liquid containing a solvent in the production method of the present invention is an ethylene oxide resin (ethylene oxide copolymer), which is obtained after polymerization by a polymerization method using a solvent, and the resin and the solvent. It refers to a reaction solution after polymerization containing, and a resin solution to be subjected to a devolatilization treatment (devolatilization treatment of a solvent component) subsequent to this polymerization.

The content ratio of the ethylene oxide resin component in the polymerization reaction liquid is not particularly limited, but is 20 to 7
It is preferably 0% by weight, more preferably 25 to
It is 65% by weight, more preferably 30 to 60% by weight. When the content of the resin component is less than 20% by weight,
The productivity of the resin may be extremely reduced, and if it exceeds 70% by weight, the viscosity of the polymerization reaction liquid may increase and stirring may be difficult. The content ratio of the solvent component in the polymerization reaction liquid is not particularly limited, but is preferably 30 to 80% by weight, more preferably 35 to 75.
%, And more preferably 40 to 70% by weight. When the content ratio of the solvent component is less than 30% by weight, the viscosity of the polymerization reaction liquid increases, which makes it difficult to stir, and it may be difficult to perform liquid sending / transfer to a devolatilizer or devolatilization itself. If it exceeds 80% by weight, the productivity of the resin may be extremely reduced.

The above-mentioned polymerization reaction liquid may contain other components in addition to the ethylene oxide resin component and the solvent component. For example, a reaction initiator, an antioxidant and a solubilizing agent generally used in the polymerization reaction. Agents and the like.
Examples of the reaction initiator include sodium hydroxide,
Alkaline catalysts such as potassium hydroxide, potassium alcoholate, sodium alcoholate, potassium carbonate and sodium carbonate, and metals such as metal potassium and sodium, for example, aluminum hydroxide / magnesium fired products (Japanese Patent Laid-Open No. 8-268919, etc.). ), Magnesium oxide added with metal ions (Japanese Patent Publication No. 6-1
No. 5038, JP-A-7-227540, etc.) and calcined hydrotalcite (JP-A-2-718441).
Al-Mg-based composite oxide catalysts such as those disclosed in JP-A-6-334782) or catalysts obtained by surface-modifying them (JP-A-6-334782), barium oxides and barium hydroxides (JP-A-5)
4-75187, etc.), layered compound (Tokuhyo Hyo 6-5)
No. 05986), strontium oxide, strontium hydroxide (Japanese Patent Publication No. 63-32055, etc.), calcium compound (JP-A-2-134336, etc.), cesium compound (JP-A-7-70308, etc.). , Complex metal cyanide complex (Japanese Patent Application Laid-Open No. 5-339361)
(Japanese Patent Laid-Open Publication No. 1989), acid catalysts such as Lewis acids and Friedel-Crafts catalysts, and the like. These reaction initiators may be contained alone or in combination of two or more in the polymerization reaction liquid and are not particularly limited.

The viscosity of the above polymerization reaction liquid is not particularly limited, but it is preferably 1,000 to 60,000 centipoise at 95 ° C., and more preferably 1 at 95 ° C.
50,000-45,000 centipoise, more preferably 15,000-35,000 centipoise at 95 ° C. If the viscosity is less than 1,000 centipoise at 95 ° C., the productivity of the resin may be extremely lowered, and if it exceeds 60,000 centipoise at 95 ° C., the viscosity becomes high even during polymerization. If it is too much, stirring or the like may be difficult. The polymerization method using the solvent is not particularly limited, but, for example, a solution polymerization method and a precipitation polymerization method can be preferably mentioned, and among them, a solution polymerization method is more preferable because of excellent productivity, The solution polymerization method in which the polymerization is carried out while feeding the monomer component to the solvent charged in advance is particularly preferable because of safety such as easy removal of reaction heat. In addition, the solvent component in the polymerization reaction liquid usually refers to a solvent used in a polymerization method using the above solvent, but after this polymerization, other solvents not used in the polymerization were included in the polymerization reaction liquid. In some cases, the other solvent may be considered to be included in the solvent component in the polymerization reaction solution.

Examples of the above-mentioned solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene; heptane, octane, n-hexane and n.
-Aliphatic hydrocarbon solvents such as pentane and 2,2,4-trimethylpentane; Alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; Ether solvents such as diethyl ether, dibutyl ether and methyl butyl ether A solvent of ethylene glycol dialkyl ethers such as dimethoxyethane; a cyclic ether solvent such as THF (tetrahydrofuran) and dioxane; an organic solvent containing no active hydrogen such as a hydroxyl group, and the like, of which toluene and xylene are particularly preferable. . The solvent is further the organic solvent, and,
Those containing no water are preferred.

The ethylene oxide-based resin (ethylene oxide-based copolymer) contained in the above-mentioned polymerization reaction liquid is a resin which mainly contains a constituent component derived from an ethylene oxide monomer in its molecular structure and has an ether bond in its main chain. , But is not particularly limited, specifically,
For example, as a raw material monomer, ethylene oxide and the following structural formula (1):

[0018]

[Chemical 1] (However, R ₁ is Ra (Ra is an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, (meth))
Any of the groups) or -CH ₂ -O-Re-Ra group in the acryloyl group and an alkenyl group (Re _{has, - (CH 2 -CH 2 -O} ) having a p- in structure (p is 0 Preferred are those obtained by polymerizing a comonomer group containing a substituted oxirane compound represented by an integer from 10 to 10))). This polymerization is preferably ring-opening polymerization of the oxirane group of each raw material monomer.

The R ₁ group in the above structural formula (1) is a substituent in the above substituted oxirane compound. The substituted oxirane compound used as the raw material monomer may be only one type of the substituted oxirane compound represented by the structural formula (1) or may be a compound containing two or more types. Examples of the substituted oxirane compound represented by the structural formula (1) include propylene oxide, butylene oxide,
1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyoctane, cyclohexene oxide and styrene oxide, or methyl glycidyl ether, ethyl glycidyl ether and ethylene glycol methyl glycidyl ether, and the like, Further, when the substituent R ₁ is a crosslinkable substituent, that is, the substituent R ₁ is an aryl group, an alkenyl group,
In the case of having an acryloyl group and a methacryloyl group, epoxybutene, 3,4-epoxy-1-pentene, 1,2-epoxy-5,9-cyclododecadiene, 3,4-epoxy-1-vinylcyclohexene,
1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate and glycidyl-4-hexanoate, or
Vinyl glycidyl ether, allyl glycidyl ether, 4-vinylcyclohexyl glycidyl ether, α
There may also be mentioned terpenyl glycidyl ether, cyclohexenyl methyl glycidyl ether, 4-vinylbenzyl glycidyl ether and 4-allylbenzyl glycidyl ether. As described above, these may be used alone or in combination of two or more kinds.

The above-mentioned substituted oxirane compound is as described above.
Having a crosslinkable substituent (substituent R ₁Is a crosslinkable substituent
The essential use of a substituted oxirane compound is
Tylene oxide resin (ethylene oxide copolymer)
Is preferred for use as a crosslinked product. Ethylene
The weight average molecular weight (Mw) of the oxide resin is particularly limited.
Although it is not measured, it must be 20,000 to 300,000.
And more preferably, more preferably 30,0
00-200,000, more preferably 40,000
˜150,000. The weight average molecular weight is 20,
If it is less than 000, the molded product may be tacky.
Yes, if it exceeds 300,000, molding becomes difficult
Processability and handling may deteriorate.
It

The molecular weight distribution (Mw / Mn) of the ethylene oxide resin is not particularly limited, but is preferably 3 or less, more preferably 2 or less. If the molecular weight distribution is more than 3, tack may occur when a molded product is formed and handling may be poor. [Devolatization] In the production method according to the present invention, an ethylene oxide resin is obtained by devolatilizing a solvent component (volatilizing a solvent component) from a polymerization reaction liquid after polymerization containing an ethylene oxide resin and a solvent. I am
The ethylene oxide resin to be obtained is not limited to one containing no solvent component, and is usually one which is adjusted by devolatilization to reduce the polymerization reaction liquid to a desired solvent concentration. Suppose there is.

As the devolatilization method, the equipment used for devolatilization and various conditions, a usual devolatilization method, usable equipment and set conditions may be adopted. Details are shown below. As a devolatilization method, there are usually two stages of pre-volatilization and main volatilization, and as the volatilization procedure, it is preferable to carry out main volatilization after pre-volatilization, but there is no particular limitation. Alternatively, the pre-volatilization and the main volatilization may be carried out as a single step without distinction. It is preferable to perform it in two stages because it makes it possible to improve the efficiency of devolatilization (cost reduction, processing time reduction, resin quality, etc.). The amount of solvent contained in the liquid can be rapidly reduced to such an amount that the devolatilization process can be carried out efficiently, and then the devolatilization process can be performed slowly.The former stage is atmospheric devolatilization and the latter stage is vacuum (pressure reduction) devolatilization. The reason is that by volatilizing, the equipment size can be made smaller than in the case of treating in a single step, and in the case of devolatilizing, the viscosity may rise rapidly in a certain concentration range, and the drive system can be made smaller than in the case of treating in a single step. Although it is theoretically preferable, depending on the type of the polymerization reaction liquid to be devolatilized (particularly, the type of resin in the polymerization reaction liquid), etc., even the above-mentioned one-step treatment is the same as the two-step treatment. Can be done (two-step processing Since there is a case where the same effect is obtained) may be appropriately selected.

The device used for devolatilization (devolatilizer) is not particularly limited, but may be a stirring tank evaporator,
A downstream liquid column evaporator, a thin film evaporator, a surface renewal type polymerization device, a kneader, a roll mixer, an intensive mixer (so-called Banbury mixer), an extruder and the like are preferably mentioned, and at least one of these devices is used. Is preferred. In addition, the usage conditions can be set appropriately depending on the device used. Stirring tank evaporators are excellent in that they can handle a wide range of viscosities and a wide range of residual solvent concentrations. For example, stirring tanks equipped with helical blades, stirring tanks equipped with double helical ribbon blades, super blend blades (inner blades) : Vertical blended biaxial stirring tank equipped with Maxblend blade, outer blade: spirally deformable baffle (for example, product name:
Super blend, Sumitomo Heavy Industries, Ltd., VCR
An inverted cone ribbon blade type reactor (manufactured by Mitsubishi Heavy Industries, Ltd.) and the like are preferable. These can be used for both batch processing and continuous processing, but are preferably used for batch processing. In addition, because of the characteristics of the device, it takes a long time to discharge after processing, and therefore, it is preferably applicable to a process of accurately processing a small amount of a resin rather than a process of processing a large amount of resin or the like.
Further, when these are used, the evaporation process is performed by updating the heat transfer surface.

Among the above various stirred tank evaporators, in particular,
The vertical concentric biaxial stirring tank has the following excellent features. The processing viscosity range is wide, and excellent mixing performance can be exhibited in the viscosity range of 1 to 10,000 poise. Following the rapid viscosity change in the tank, the mixing function of the inner and outer blades is natural. It is possible to maintain a good flow state because
Since the liquid flow velocity (flow velocity of the polymerization reaction liquid) can be made uniform on the inner wall surface of the tank and in the center of the tank, high temperature uniformity can be maintained and deterioration of resin quality can be reduced. Adhesion to the tank wall and baffle part during high-concentration slurry processing, which can eliminate slipping and retention of low-viscosity liquid and improve the dispersibility of reflux reflux liquid and various additives after polymerization. Due to the stable wall flow velocity due to the rotation of the outer blades in close proximity to the tank wall surface, which can eliminate the accumulation and exhibit good slurry dispersibility,
It is possible to reduce the adhesion of the inner wall portion and the time and number of cleanings in the tank.

As the downstream liquid column evaporator, a multi-tube heat exchanger type (for example, product name: Sulzer mixer, manufactured by Sumitomo Heavy Industries, Ltd .; product name: static mixer, manufactured by Noritake Co., Ltd.), plate heat Exchanger type (for example, product name: HIVI
scous Evaporator, Mitsui Engineering & Shipbuilding Co., Ltd.
Preferred). These can be used for both batch-type treatment and continuous-type treatment, and both treatments can be favorably performed. Also, due to the characteristics of the device, the devolatilization by these is performed by sensible heat,
After that, to convert sensible heat into latent heat and evaporate under reduced pressure,
The amount that can be devolatilized depends on the amount of sensible heat (the amount of heat that can be transferred as latent heat). Therefore, it is preferable to use a process in which the amount of treatment corresponds to the amount of sensible heat, but in the multi-tube heat exchanger type, since heat transfer can be promoted by a stick mixer, it is possible to handle a wide range of processes. . Further, in the case of the multi-tube heat exchanger type, the evaporation process is carried out by expanding the boundary area, and the corresponding maximum processing viscosity is 5
It is preferably 000 poise, and in the case of the plate heat exchanger type, the evaporation process is carried out by expanding the heat transfer area, and the corresponding maximum processing viscosity is preferably 10,000 poise.

The thin film evaporator is excellent in that a centrifugal force acts by the blade to form a uniform liquid film.
Horizontal thin-film evaporator (for example, product name: Evariactor, manufactured by Kansai Kagaku Kikai K.K.), fixed blade type vertical thin-film evaporator (for example, product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), movable Blade type vertical thin film evaporator (for example, product name: Wiprene, manufactured by Shinko Pantech Co., Ltd.),
A tank type (mirror type) thin film evaporator (for example, product name: recovery, manufactured by Kansai Kagaku Kikai Seisakusho Co., Ltd.) and the like are preferable. Regarding these, in batch type processing,
Horizontal and tank types are possible, although not common
Vertical type is impossible regardless of fixed blade type or movable blade type. In addition, continuous processing is possible in all cases. Due to the characteristics of the equipment, all of these are devolatilized by heating with sensible heat and then converting the sensible heat to latent heat under reduced pressure to evaporate. It depends on the amount of heat obtained). Therefore, a process in which the amount of treatment corresponds to the amount of sensible heat is preferable. Also, all of these, the evaporation process is carried out by updating the transfer surface.

The horizontal thin-film evaporator is more difficult to deal with high viscosity than the vertical type in terms of discharge surface. Therefore, it is possible to use high-viscosity blades by using blades with excellent discharge effect. The maximum processing viscosity is preferably 500 poise. Since the vertical thin-film evaporator descends by its own weight, it can be said that a high viscosity liquid is more suitable than a low viscosity liquid, but the movable blade type corresponding maximum processing viscosity is preferably 1,000 poise. Further, in the fixed blade type, the fixed blade has a scraping effect so as to cope with high viscosity, and the corresponding maximum processing viscosity is preferably 10,000 poise. The tank type thin film evaporator can suppress the short pass of the low-viscosity liquid by using a mirror, and the corresponding maximum processing viscosity is preferably 1,000 poise.

The surface renewal type polymerizer (horizontal thin film polymerizer) is
It is excellent in that it shows high devolatilization performance by renewing the gas-liquid surface. Co., Ltd .; Product name: Hitachi Megane Tsubasa Polymerizer, Inc.
Hitachi, Ltd .; Product name: Hitachi lattice blade polymerization machine, Hitachi, Ltd .; Product name: SC processor, Kurimoto Iron Works Co., Ltd.)
And the like are preferable. These are not possible for batch-wise processing and are all possible for continuous processing. Due to the characteristics of the device, in all of these, the amount of devolatilization treatment depends on the moving speed of the substance in the device,
The evaporation process is performed by renewing the gas-liquid level.

Like the extruder, the kneader, roll mixer, and intensive mixer (so-called Banbury mixer) are suitable for mixing the high-viscosity melt and the like, and have a devolatilizing ability as an additional function. All of these can be processed in a batch system or a continuous system. For these, the corresponding maximum processed viscosity is preferably 10,000 poise. The uniaxial type exhibits a high devolatilization performance because an efficient surface area can be secured, and the corresponding maximum processing viscosity is preferably 10,000 poise. Further, the biaxial type is excellent in self-cleaning property and suppression of liquid retention due to the absence of dead space in the container and the high piston flow property, and the corresponding maximum processing viscosity is preferably 10,000 poise. .

The extruder is suitable for mixing high viscosity melts,
It has a devolatilizing ability as an additional function together with heating, melting, and kneading. For example, a single-screw extruder, a twin-screw extruder (for example, product name: SUPERTEX αII, manufactured by Japan Steel Works; product name: BT-30 -S2, manufactured by Plastic Engineering Laboratory), SCR self-cleaning reactor (manufactured by Mitsubishi Heavy Industries, Ltd.) and the like are preferable. These cannot be processed in a batch system, and all processes in a continuous system are possible. Due to the characteristics of the device, these are suitable for the process of devolatilizing a substance having a very high viscosity as described above, and the evaporation process is performed by kneading, evaporation or the like.

In the extruder, both the single-screw type extruder and the twin-screw type extruder, the corresponding maximum processing viscosity is preferably 100,000 poise. As described above, as a preferable devolatilization method, a method of performing main devolatilization after pre-volatilization can be mentioned. Among the various devolatilization devices, those which can be preferably used for pre-volatilization are not particularly limited. However, a stirring tank equipped with a double helical ribbon blade, a vertical concentric biaxial stirring tank equipped with a super blend blade, a plate heat exchanger type downstream liquid column evaporator, and a fixed blade type vertical thin film evaporator are included. Can be mentioned. In addition, what can be preferably used for this devolatilization is not particularly limited, and examples thereof include a fixed blade type vertical thin film evaporator, a biaxial type surface renewal type polymerization device, a kneader, and a biaxial type extruder. .

In carrying out the devolatilization of the polymerization reaction solution in the production method of the present invention, various devolatilizers listed above are directly connected to a so-called pre-stage device which has been used for the step of polymerization using the above-mentioned solvent. It may be volatilized, or may be volatilized by various devolatilizers after liquid feeding or transfer from the preceding apparatus. Regarding the latter, for example, a form in which the upstream device and the devolatilizer are connected by a liquid feed line, or an intermediate tank equipped with a jacket and a stirrer between the upstream device and the devolatilizer. Examples include a mode in which a tank (cushion tank) is provided. In the production method of the present invention, the residual solvent concentration in the devolatilized ethylene oxide resin is set to 0.01 to 30% by weight by devolatilization, preferably 0.05 to 20
%, More preferably 0.1 to 10% by weight. When the residual solvent concentration is less than 0.01% by weight, the devolatilization conditions need to be excessively strict, which may lead to thermal deterioration of the ethylene oxide resin, resulting in performance deterioration. When the content exceeds the weight%, tack may occur in the ethylene oxide resin after devolatilization, and blocking or the like may occur.

In the production method of the present invention, it is preferable that the water content in the ethylene oxide resin after devolatilization is adjusted at the same time when the solvent is devolatilized. Moisture is, for example,
It is included in the solvent and monomers used during the polymerization. The production method of the present invention is characterized in that the water content is 200 ppm or less by the above adjustment. If the water content exceeds 200 ppm, the dielectric constant of the resin becomes unnecessarily large. For example, when the obtained ethylene oxide resin is used for a protective film of a color filter or the like, the resin becomes conductive. As a result, the protective film may cause a fatal decline in function, and since water reacts with metal ion components to form a hydroxide or the like, for example, an ethylene oxide resin is used as a polymer. When used as an electrolyte layer of a battery, an insulating layer may be formed at the metal-electrolyte layer interface, the voltage under a constant current may continue to rise, and the cycle characteristics of the battery may deteriorate.

As means for adjusting the above-mentioned water content,
Although not particularly limited, specifically, it is preferable to increase the devolatilization temperature and / or increase the decompression degree of the devolatilization (increasing the decompression degree lowers the pressure. Means to reduce the degree of reduced pressure means to increase the pressure). When adjusting the moisture content by increasing the devolatilization temperature, the temperature is not particularly limited, but if it is too low, it is not efficient because the degree of pressure reduction must be excessively increased, and if it is too high,
Since there is a possibility that heat deterioration of the resin will occur, these should be taken into consideration and set appropriately. Further, when adjusting the water content by increasing the degree of depressurization for devolatilization, the degree of depressurization is not particularly limited, but if it is too high, it is considered difficult in consideration of the sealing property of the devolatilization device. However, if it is too small, the water content may not be controlled to 200 ppm or less unless the devolatilization temperature is raised to a considerable extent.

According to the production method of the present invention, it is possible to prevent the ethylene oxide resin after devolatilization from containing an antistatic agent. The reason is, as described above, in the present invention, since the ethylene oxide resin is obtained by devolatilization instead of heating and drying after polymerization, it is necessary to consider charging of the resin caused by friction between the resins under heating and drying. Because there is no. When the ethylene oxide resin obtained contains an antistatic agent, the dielectric constant of the resin is increased more than necessary, or the strength of the resin is increased by increasing the swelling ratio of the resin more than necessary by causing a decrease in the degree of crosslinking and an increase in hygroscopicity. It will be lowered. Therefore, for example, when the obtained ethylene oxide-based resin is used for a protective film of a color filter or the like, the resin becomes conductive, which causes a fatal deterioration of the function of the protective film. Further, when the resin is used in a flexographic printing plate material or the like, it is difficult to maintain a desired shape and impact resilience, resulting in poor image reproducibility. Furthermore, when the resin is used for a separator of a polymer battery, an electrode, an electrolyte layer, etc.,
The desired shape cannot be maintained.

When the solvent is devolatilized from the polymerization reaction solution under heating using the devolatilizer described above, the temperature is 40 to 30.
It is preferably 0 ° C., more preferably 60 to 25
The temperature is 0 ° C, more preferably 90 to 200 ° C. By performing devolatilization within this temperature range, the ethylene oxide resin having the desired residual solvent concentration and water content described above can be obtained after devolatilization. If the temperature is lower than 40 ° C., the amount of remaining solvent may increase.
If it exceeds 0 ° C, the polyether itself may be thermally decomposed. Here, the above temperature is the temperature of the ethylene oxide resin in the devolatilization device.

Similarly, when devolatilizing the solvent using the devolatilizer, the pressure is 13 to 100,000 Pa.
It is preferable to carry out in the range of, and more preferably 133-
70,000 Pa, more preferably 1,333-4
It is 30,000 Pa. By satisfying this pressure range, it is possible to obtain an ethylene oxide resin having a solvent concentration and a water content as described above after devolatilization. If the pressure is less than 13 Pa, the solvent may be flushed and forming may occur, and if it exceeds 100,000 Pa, it may be necessary to apply a temperature until the polyether is decomposed. Here, the above-mentioned pressure is the pressure in the tank of the devolatilization device.

In the manufacturing method of the present invention, the viscosity of the ethylene oxide resin after devolatilization is 50 to 10 at 100 ° C.
The porosity is preferably 50,000 poise, more preferably 100 to 80,000 poise at 100 ° C, and further preferably 220 to 60,000 poise at 100 ° C.
If the viscosity is less than 50 poises at 100 ° C., the amount of residual solvent is large, and foaming and tacking may occur when forming a molded product. If it exceeds 100,000 poises, devolatilization with a devolatilizer is carried out. May be difficult. [Use of ethylene oxide-based resin] The ethylene oxide-based resin obtained by the production method of the present invention includes, for example, polyurethane resins such as adhesives, paints, sealing agents, elastomers and flooring agents, as well as hard, soft or semi-rigid polyurethane resins. , And even surfactants, sanitary products,
High performance for a wide range of applications such as deinking agents, lubricating oils, hydraulic fluids, separators used in polymer batteries, electrodes and polymer electrolyte layers, and photosensitive resins that can be used in color filter protective films, resists, flexographic printing plate materials, etc. It can be preferably used as a molecular material.

[0039]

[Measurement of the amount of residual solvent in the resin after devolatilization]

High Performance Liquid Chromatography (Column: ODS-3 (G
L Science), column temperature: 40 ° C., flow rate: 1.
0 mL / min, injection volume: 5 μL, UV detector: 210 n
m, eluent: mixed solution of “acetonitrile / 0.1 wt% phosphoric acid aqueous solution” (volume ratio: acetonitrile / 0.1 wt
% Phosphoric acid aqueous solution = 85/15)), the residual solvent amount (wt%) in the sample sample is measured. Sample As a sample, the resin after the devolatilization to be measured has a solid content of 1.0
The one diluted with the above-mentioned eluent is used so as to be wt%. A specific measuring method is as follows: first, a predetermined solvent (for example,
A calibration curve sample is prepared using a calibration curve sample for (toluene), then the sample sample is measured, and the residual solvent amount is determined using the calibration curve. [Measurement of water content in resin after devolatilization] In a glove box, the following, namely, ethylene oxide resin obtained by devolatilization, under a dry atmosphere, at the time of heating (resin near devolatilization temperature Samples that have been sampled and naturally cooled in a fluid state while maintaining the temperature, toluene as a solvent (previously molecular sieves (manufactured by Union Showa, product name: molecular sieve 3A1.6 or molecular sieve 4A1.6)) The water content was reduced as much as possible), put a glass container and a syringe, and dry for 2 hours or more.

After drying, 2 g of ethylene oxide resin and 18 g of toluene were put into a glass container and sufficiently dissolved by a magnetic stirrer to obtain a resin solution. Then, the entire resin solution was collected with a syringe. At the same time, collect 18 g of toluene only with another syringe. Take each syringe after collection out of the glove box and use AQUA
COUNTERQ-7 (a moisture content measuring device manufactured by HIRANUMA) is used to measure the moisture content of each of the resin solution and toluene alone. From the value of water content (ppm) obtained by this measurement, the weight (mg) of water contained in the resin solution and toluene alone was calculated, and from the difference, the weight of water contained in the ethylene oxide resin (mg) Ask for. Therefore, the water content (ppm), which is the difference, is calculated by dividing the water content (mg) of the ethylene oxide resin by the weight (2 g) of the initially dissolved ethylene oxide resin. [Weight average molecular weight (Mw) of ethylene oxide resin,
Measurement of molecular weight distribution (Mw / Mn)] GP having a calibration curve prepared using a standard molecular weight sample of polyethylene oxide
It was measured by a C device. The polymerization reaction liquid (including polymer) obtained after the reaction was dissolved in a predetermined solvent and then measured.

Example 1 (Thin film evaporator) Polymerization reaction solution (a) in which the weight% ratio of ethylene oxide resin (a) to toluene (resin / toluene) is 50% by weight / 50% by solution polymerization. ) Got. In the ethylene oxide resin (a), a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from methyl glycidyl ether are in the order of 180 parts by weight, 12 parts by weight, and 8 parts by weight. Which has a weight average molecular weight Mw of 100,0.
It was 00.

The polymerization reaction liquid (a) was previously added to 50 to 10
After heating with steam of a heating medium at 0 ° C and charging the raw material tank, a gear pump was used from this raw material tank at a supply rate of 46 kg / h to produce a thin film evaporator (product name:
EXEVA, manufactured by Shinko Pantech Co., Ltd., and the polymerization reaction solution (a) was concentrated by devolatilization. The thin film evaporator has a stirring blade motor rotation speed of 300 rpm, a discharge screw rotation speed of 90 to 100 rpm, a jacket temperature of 180 ° C.,
The pressure was set to 50 Torr (6,666 Pa) and used. The resin temperature at the outlet of the thin film evaporator was 178 ° C.
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (a) and toluene of 9
The content was 9.79% by weight / 0.21% by weight, and the water content was 35 ppm.

Example 2- (Thin Film Evaporator) Polymerization reaction solution (b) in which the weight% ratio (resin / toluene) of ethylene oxide resin (b) and toluene was 50% / 50% by solution polymerization. ) Got. The ethylene oxide-based resin (b) contains a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from methylglycidyl ether in the order of 378 parts by weight, 25.2 parts by weight, 16.8 parts by weight. It was a resin having a ratio of parts by weight, and had a weight average molecular weight Mw of 90,000.

The polymerization reaction liquid (b) was previously added to 50 to 10
After heating with steam of a heat medium at 0 ° C and charging the raw material tank, a gear pump was used from this raw material tank at a supply rate of 30 kg / h to produce a thin film evaporator (product name:
EXEVA, manufactured by Shinko Pantech Co., Ltd., and the polymerization reaction liquid (b) was concentrated by devolatilization. The thin film evaporator has a stirring blade motor rotation speed of 300 rpm, a discharge screw rotation speed of 90 to 100 rpm, a jacket temperature of 180 ° C.,
The pressure was set to 50 Torr (6,666 Pa) and used. The resin temperature at the outlet of the thin film evaporator was 173 ° C.
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (b) and toluene of 9
It was 9.83% by weight / 0.17% by weight, and the water content was 28 ppm.

Example 3- (Twin-screw extruder) Polymerization reaction solution in which the weight% ratio of ethylene oxide resin (c) to toluene (resin / toluene) is 50% by weight / 50% by solution polymerization ( c) was obtained. The ethylene oxide-based resin (c) contains a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from methylglycidyl ether in the order of 378 parts by weight, 25.2 parts by weight, 16.8 parts by weight. It was a resin having a ratio of parts by weight, and had a weight average molecular weight Mw of 95,000.

After the polymerization reaction liquid (c) is melted in advance, it is placed in a raw material tank and heated to 80 ° C. At the same time, the jacket of a 30φ twin-screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratory Co., Ltd.) was heated to 180 ° C for the back vent and 150 ° C for all of the supply vent and the first to fifth vents. Heat, 20
Rotate at 0 rpm. Then, 14.4 kg / of polymerization reaction liquid (c) was used from the raw material tank using a gear pump.
30φ twin screw extruder (Product name: BT-3
0-S2, manufactured by Plastic Engineering Laboratory Co., Ltd., and at the same time as the supply, a back vent of 100 Torr (13, 3).
32 Pa), the first vent is 70 Torr (9,333)
Pa), 70T from the 2nd vent to the 4th vent
The polymerization reaction liquid (c) was concentrated by devolatilization by reducing the pressure to orr (9,333 Pa) or less (the supply vent and the fifth vent were not particularly reduced in pressure). The resin temperature at the outlet of the 30φ twin-screw extruder was 208 ° C.

The resin obtained after devolatilization had a weight% ratio of ethylene oxide resin (c) to toluene (resin / toluene) of 99.83% by weight / 0.17% by weight and a water content of 30 ppm. there were. -Example 4- (Twin-screw extruder) Polymerization reaction liquid (d) having a weight% ratio (resin / toluene) of ethylene oxide resin (d) to toluene of 50% by weight / 50% by solution polymerization Obtained. The ethylene oxide resin (d) comprises a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from methyl glycidyl ether in the order of 378 parts by weight, 25.2 parts by weight and 16.8 parts by weight. It was a resin having a ratio of parts by weight, and had a weight average molecular weight Mw of 84,000.

After the polymerization reaction liquid (d) is melted in advance, it is charged in a raw material tank and heated to 80 ° C. At the same time, a jacket of a 30φ twin-screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratory Co., Ltd.) is used for the back vent, the supply vent, the first vent and the second vent.
The temperature is raised to 20 ° C., the third vent to 80 ° C., the fourth vent to the fifth vent to 100 ° C., and the two shafts are rotated at 80 rpm. Then, the polymerization reaction liquid (d) was supplied from the raw material tank to the 30φ twin-screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratory) at a supply rate of 4.8 kg / h using a gear pump. And at the same time as supply,
Back vent 110 Torr (14,665 Pa)
The first vent to 70 Torr (9,333 Pa),
70T for 2nd vent, 3rd vent and 5th vent
The polymerization reaction liquid (d) was concentrated by devolatilization by reducing the pressure to orr (9,333 Pa) or lower (the supply vent and the fourth vent were not particularly reduced). The resin temperature at the outlet of the 30φ twin-screw extruder was 95 ° C.

The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (d) to toluene of 99.25% by weight / 0.75% by weight and a water content of 125 ppm. there were. -Example 5- (stirred tank evaporator) Similar to Example 4 by solution polymerization,
A polymerization reaction liquid (d) having a weight% ratio of the ethylene oxide resin (d) to toluene (resin / toluene) of 50% by weight / 50% by weight was obtained.

A vertical concentric biaxial stirring tank (product name: 45 kg of polymerization reaction liquid (d)) equipped with a super blend blade (inner blade: Maxblend blade, outer blade: spiral deformable baffle)
Super Blend, manufactured by Sumitomo Heavy Industries, Ltd.), with the jacket temperature heated to 160 ° C., the Max Blend blade was 16 rpm, and the spiral deformation baffle was 1
The mixture was stirred at 7 rpm in a forward rotation and devolatilized with toluene under atmospheric pressure for 3 hours, and then 410 Torr (54,6) at maximum.
The polymerization reaction liquid (d) was concentrated by devolatilizing toluene under a reduced pressure of 62 Pa) for 1.5 hours. The resin obtained after devolatilization had a weight% ratio of ethylene oxide resin (d) and toluene (resin / toluene) of 92.4% by weight / 7.6.
% By weight, and the water content was 200 ppm.

Example 6 (Stirring tank evaporator) By solution polymerization, the weight% ratio of ethylene oxide resin (e) and toluene (resin / toluene).
To obtain a polymerization reaction liquid (e) having a content of 50% by weight / 50% by weight. The ethylene oxide resin (e) contains a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from methyl glycidyl ether in the order of 378 parts by weight, 25.2 parts by weight, 16.8 parts by weight. It was a resin having a ratio of parts by weight, and had a weight average molecular weight Mw of 103,000.

A vertical concentric biaxial stirring tank (product name: 45 kg of polymerization reaction liquid (e)) equipped with a super blend blade (inner blade: Maxblend blade, outer blade: spirally deformable baffle)
Super blend, manufactured by Sumitomo Heavy Industries, Ltd.), with the jacket temperature heated to 160 ° C., the Max Blend blade is 75 rpm, and the spiral deformation baffle is 3
The mixture was stirred at 0 rpm in forward rotation, and devolatilized with toluene under atmospheric pressure for 3.5 hours, and then, up to 50 Torr (6,6).
The polymerization reaction solution (e) was concentrated by devolatilizing toluene under a reduced pressure of 66 Pa) for 1.5 hours. The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (e) to toluene of 99.60% by weight / 0.
It was 40% by weight, and the water content was 89 ppm.

Example 7 (Thin film evaporator) Polymerization reaction solution (f) in which the weight% ratio of ethylene oxide resin (f) to toluene (resin / toluene) was 50% / 50% by solution polymerization. ) Got. The ethylene oxide-based resin (f) contains a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from allyl glycidyl ether in the order of 378 parts by weight, 25.2 parts by weight, 16.8 parts by weight. It was a resin having a ratio of parts by weight, and had a weight average molecular weight Mw of 97,000.

The polymerization reaction liquid (f) was previously added to 50 to 10
After heating with steam of a heat medium at 0 ° C and charging the raw material tank, a gear pump was used from the raw material tank at a supply rate of 33 L / h to produce a thin film evaporator (product name: E
XEVA, manufactured by Shinko Pantech Co., Ltd., and the polymerization reaction liquid (f) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa).
The resin temperature at the outlet of the thin film evaporator was 175 ° C. The resin obtained after devolatilization had a weight% ratio of ethylene oxide resin (f) to toluene (resin / toluene) of 99.84 wt% / 0.16 wt% and a water content of 27 ppm.
Met.

Example 8 (Thin film evaporator) Polymerization reaction solution (g) in which the weight% ratio of ethylene oxide resin (g) to toluene (resin / toluene) is 50% by weight / 50% by solution polymerization. ) Got. The ethylene oxide resin (g) comprises a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from allyl glycidyl ether in the order of 378 parts by weight, 25.2 parts by weight and 4 parts by weight. A resin having a weight average molecular weight Mw of 97,
It was 000.

The polymerization reaction liquid (g) was previously added to 50 to 10
After heating with steam of a heat medium at 0 ° C and charging the raw material tank, a gear pump was used from the raw material tank at a supply rate of 33 L / h to produce a thin film evaporator (product name: E
XEVA, manufactured by Shinko Pantec Co., Ltd., and the polymerization reaction liquid (g) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa).
The resin temperature at the outlet of the thin film evaporator was 175 ° C. The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (g) to toluene of 99.83% by weight / 0.17% by weight and a water content of 29 ppm.
Met.

Example 9 (Thin film evaporator) Polymerization reaction solution (h) in which the weight% ratio (resin / toluene) of ethylene oxide resin (h) and toluene was 50% by weight / 50% by weight by solution polymerization. ) Got. The ethylene oxide resin (h) contains ethylene oxide-derived structural units, butylene oxide-derived structural units, and allyl glycidyl ether-derived structural units in the order of 378 parts by weight, 15 parts by weight, and 16 parts by weight. Which has a weight average molecular weight Mw of 110,
It was 000.

The polymerization reaction liquid (h) was previously added to 50 to 10
After heating with steam of a heat medium at 0 ° C and charging the raw material tank with a gear pump, a thin film evaporator (product name:
EXEVA, manufactured by Shinko Pantec Co., Ltd., and the polymerization reaction solution (h) was concentrated by devolatilization. The thin film evaporator has a rotation speed of a stirring blade motor of 600 rpm, a rotation speed of a discharge screw of 90 to 100 rpm, a jacket temperature of 150 ° C.,
The pressure was set to 500 Torr (66,661 Pa) and used. The resin temperature at the outlet of the thin film evaporator was 138 ° C. The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (h) and toluene of 9
It was 0.10% by weight / 9.90% by weight, and the water content was 190 ppm.

Example 10 (Thin film evaporator) Polymerization reaction solution (i) in which the weight% ratio of ethylene oxide resin (i) to toluene (resin / toluene) was 50% / 50% by solution polymerization. ) Got. In the ethylene oxide resin (i), a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from allyl glycidyl ether are in the order of 378 parts by weight, 40 parts by weight, and 16 parts by weight. Which has a weight average molecular weight Mw of 110,
It was 000.

The polymerization reaction liquid (i) was previously added to 50 to 10
After heating with steam of a heat medium at 0 ° C and charging the raw material tank with a gear pump, a thin film evaporator (product name:
EXEVA, manufactured by Shinko Pantech Co., Ltd., and the polymerization reaction solution (i) was concentrated by devolatilization. The thin film evaporator has a rotation speed of a stirring blade motor of 600 rpm, a rotation speed of a discharge screw of 90 to 100 rpm, a jacket temperature of 150 ° C.,
The pressure was set to 500 Torr (66,661 Pa) and used. The resin temperature at the outlet of the thin film evaporator was 138 ° C. The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (i) and toluene of 9
It was 0.10% by weight / 9.90% by weight, and the water content was 180 ppm.

-Example 11- (Thin film evaporator) Polymerization reaction solution (j) in which the weight% ratio of ethylene oxide resin (j) to toluene (resin / toluene) was 50% by weight / 50% by solution polymerization. ) Got. The ethylene oxide resin (j) has a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from epoxybutene, in that order.
It is a resin having a ratio of 378 parts by weight, 25.2 parts by weight, and 16.8 parts by weight, and has a weight average molecular weight Mw of 26,000.
It was 0.

The polymerization reaction liquid (j) was previously added to 50 to 10
After heating with steam of a heat medium at 0 ° C and charging the raw material tank, a gear pump was used from this raw material tank at a supply rate of 30 kg / h to produce a thin film evaporator (product name:
EXEVA, manufactured by Shinko Pantec Co., Ltd., and the polymerization reaction liquid (j) was concentrated by devolatilization. The thin film evaporator has a stirring blade motor rotation speed of 300 rpm, a discharge screw rotation speed of 90 to 100 rpm, a jacket temperature of 180 ° C.,
The pressure was set to 50 Torr (6,666 Pa) and used. The resin temperature at the outlet of the thin film evaporator was 173 ° C.
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (j) and toluene of 9
It was 9.83% by weight / 0.17% by weight, and the water content was 25 ppm.

Example 12 (Thin film evaporator) Polymerization reaction solution (k) in which the weight% ratio of ethylene oxide resin (k) and toluene (resin / toluene) was 50% / 50% by solution polymerization. ) Got. The ethylene oxide resin (k) is a resin having a structural unit derived from ethylene oxide and a structural unit derived from butylene oxide in the order of 257 parts by weight and 16.8 parts by weight, and has a weight average molecular weight Mw. 80,0
It was 00. The polymerization reaction liquid (k) is preliminarily 50 to 1
After heating with steam of a heat medium at 00 ° C and charging it into a raw material tank, a thin film evaporator (product name: EXEVA, Shinko Pantech Co., Ltd.) was supplied from this raw material tank with a gear pump at a supply rate of 30 kg / h. (Made by the company) and the polymerization reaction liquid (k) was concentrated by devolatilization. The thin film evaporator has a stirring blade motor rotation speed of 300 rpm, a discharge screw rotation speed of 90 to 100 rpm, and a jacket temperature of 180.
The temperature was set to 50 ° C. and the pressure was set to 50 Torr (6,666 Pa). The resin temperature at the outlet of the thin film evaporator was 173 ° C.

The resin obtained after devolatilization had a weight% ratio of ethylene oxide resin (k) and toluene (resin / toluene) of 99.83% by weight / 0.17% by weight and a water content of 26 ppm. there were. -Example 13- (Thin-film evaporator) Solution polymerization was carried out to obtain a polymerization reaction liquid (l) having a weight% ratio of ethylene oxide resin (l) and toluene (resin / toluene) of 50% by weight / 50% by weight. It was The ethylene oxide resin (l) is a resin having a structural unit derived from ethylene oxide and a structural unit derived from butylene oxide in the order of 378 parts by weight and 26 parts by weight, and has a weight average molecular weight Mw of 110, 00
It was 0.

The polymerization reaction liquid (l) was previously added to 50 to 10
After being heated by steam of a heat medium at 0 ° C and charged into a raw material tank, a thin film evaporator (product name: E
XEVA, manufactured by Shinko Pantech Co., Ltd., and the polymerization reaction solution (l) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa).
The resin temperature at the time of supply to the thin film evaporator was 69 ° C, and the resin temperature at the outlet of the thin film evaporator was 175 ° C.

The resin obtained after devolatilization had a weight% ratio of ethylene oxide resin (l) to toluene (resin / toluene) of 99.53% by weight / 0.47% by weight and a water content of 78 ppm. there were. -Example 14- (Thin-film evaporator) By solution polymerization, a polymerization reaction liquid (m) having a weight% ratio (resin / toluene) of ethylene oxide resin (m) and toluene of 50% by weight / 50% by weight was obtained. It was The ethylene oxide resin (m) is a resin having a structural unit derived from ethylene oxide and a structural unit derived from butylene oxide in the order of 200 parts by weight and 25 parts by weight, and has a weight average molecular weight Mw of 105, 00
It was 0.

The polymerization reaction liquid (m) was previously set to 50 to 10
After heating with steam of a heat medium at 0 ° C and charging the raw material tank, a gear pump was used from this raw material tank at a supply rate of 39 L / h to produce a thin film evaporator (product name: E
XEVA, manufactured by Shinko Pantec Co., Ltd., and the polymerization reaction solution (m) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa).
The resin temperature at the outlet of the thin film evaporator was 176 ° C. The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (m) to toluene of 99.74% by weight / 0.26% by weight and a water content of 43 ppm.
Met.

Example 15 (Thin film evaporator) Polymerization reaction solution (n) in which the weight% ratio (resin / toluene) of ethylene oxide resin (n) and toluene was 33% by weight / 67% by weight by solution polymerization. ) Got. The ethylene oxide resin (n) is a resin having structural units derived from ethylene oxide and structural units derived from butylene oxide in the order of 378 parts by weight and 29 parts by weight, and has a weight average molecular weight Mw of 175. 00
It was 0. Polymerization reaction liquid (n) is previously 50 to 10
After heating with steam of heat medium at 0 ° C and charging it into a raw material tank, a gear pump was used from this raw material tank at a feed rate of 11.4 L / h, and a thin film evaporator (product name: EXEVA, Shinko Supplied to Pantec Co., Ltd., and the polymerization reaction liquid (n) was concentrated by devolatilization. The thin film evaporator has a stirring blade motor rotation speed of 300 rpm, a discharge screw rotation speed of 90 to 100 rpm, and a jacket temperature of 180.
The temperature was set to 50 ° C. and the pressure was set to 50 Torr (6,666 Pa). The resin temperature at the time of supply to the thin film evaporator was 74 ° C, and the resin temperature at the outlet of the thin film evaporator was 180 ° C.

The resin obtained after devolatilization had a weight% ratio of ethylene oxide resin (n) to toluene (resin / toluene) of 99.70% by weight / 0.30% by weight and a water content of 50 ppm. there were. -Example 16- (Thin-film evaporator) By solution polymerization, a polymerization reaction liquid (o) having a weight% ratio of ethylene oxide resin (o) and toluene (resin / toluene) of 33% by weight / 67% by weight was obtained. It was The ethylene oxide resin (o) is a resin having a structural unit derived from ethylene oxide and a structural unit derived from butylene oxide in the order of 200 parts by weight and 26 parts by weight, and has a weight average molecular weight Mw of 180, 00
It was 0.

The polymerization reaction liquid (o) was previously added to 50 to 10
After heating with steam of heat medium at 0 ° C and charging it into a raw material tank, a thin film evaporator (product name: EXEVA, Shinko Co., Ltd.) was supplied from this raw material tank with a gear pump at a supply rate of 22.1 L / h. Supplied by Pantec Co., Ltd., and the polymerization reaction liquid (o) was concentrated by devolatilization. The thin film evaporator has a stirring blade motor rotation speed of 300 rpm, a discharge screw rotation speed of 90 to 100 rpm, and a jacket temperature of 180.
The temperature was set to 50 ° C. and the pressure was set to 50 Torr (6,666 Pa). The resin temperature at the time of supply to the thin film evaporator was 74 ° C, and the resin temperature at the outlet of the thin film evaporator was 182 ° C.

The resin obtained after devolatilization had a weight% ratio of ethylene oxide resin (o) to toluene (resin / toluene) of 99.39% by weight / 0.61% by weight and a water content of 102 ppm. there were. -Example 17- (Twin-screw extruder) Same as Example 16 by solution polymerization,
A polymerization reaction liquid (o) having a weight% ratio of the ethylene oxide resin (o) and toluene (resin / toluene) of 33% by weight / 67% by weight was obtained.

After the polymerization reaction liquid (o) is melted in advance, it is placed in a raw material tank and heated to 80 ° C. At the same time, the jacket of the 30φ twin-screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratory Co., Ltd.) was set to 180 ° C for the back vent, the supply vent, and the first to fourth vents, and the fifth vent. Then, it is heated to 100 ° C. and the two shafts are rotated at 100 rpm. Then, a 30φ twin-screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratories) at a supply rate of 8.5 kg / h of the polymerization reaction liquid (o) from a raw material tank using a gear pump.
Back vent to 150 Tor at the same time
r (19,998 Pa), the first vent is 80 Torr
At (10,666 Pa), the pressure from the second vent to the fourth vent is reduced to 80 Torr (10,666 Pa) or less (the supply vent and the fifth vent are not particularly depressurized).
Thus, the polymerization reaction liquid (o) was concentrated by devolatilization.

The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (o) to toluene of 99.24% by weight / 0.76% by weight and a water content of 127 ppm. there were.

[0074]

EFFECTS OF THE INVENTION According to the present invention, when an ethylene oxide resin is obtained, it is easy to control the water content to a certain level or less without containing an antistatic agent, and the resin is thermally damaged. It is possible to provide a novel method for producing an ethylene oxide-based resin, which can prevent the above-mentioned phenomenon and can realize cost reduction.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Nishiura Saint             6-3-107 Hanazonocho, Nishinomiya City, Hyogo Prefecture (72) Inventor Fumihide Tamura             5-8 Nishiomitabicho Suita City, Osaka Prefecture             Within Nippon Shokubai (72) Inventor Shigetaka Takamiya             Hyogo prefecture Himeji city             1 Within Nippon Shokubai Co., Ltd. (72) Inventor Kento Toba             5-8 Nishiomitabicho Suita City, Osaka Prefecture             Within Nippon Shokubai F-term (reference) 4J005 AA04 BC00

Claims (3)

[Claims] 1. A method for obtaining an ethylene oxide resin by devolatilizing the solvent from a polymerization reaction liquid containing a solvent, wherein the solvent concentration of the devolatilized resin is 0.01 to 30% by weight, A method for producing an ethylene oxide resin, characterized in that the water content is 200 ppm or less, and the resin does not contain an antistatic agent. 2. The temperature at the time of devolatilization is set to 40 to 300 ° C.,
The method for producing an ethylene oxide resin according to claim 1, wherein the pressure is 13 to 100,000 Pa. 3. The devolatilization is performed using at least one device selected from the group consisting of a stirring tank evaporator, a downstream liquid column evaporator, a thin film evaporator, a surface renewal type polymerizer, an extruder and a kneader. Item 3. A method for producing an ethylene oxide resin according to Item 1 or 2.