JPH0827266A - Production unit for of hydrophilic thermoplastic resin and production of the same - Google Patents

Abstract

PURPOSE:To efficiently obtain a high-molecular weight polydioxorane in high yield by polymerizing 1,3-dioxorane under mild conditions. CONSTITUTION:This production unit has the following components: a kneader 1 made up of a kneading section 11 to knead a polymerization initiator and a monomer containing >=60wt.% of a compound having 1,3-dioxorane ring in the molecule and a kneaded product discharge section 6 to discharge a kneaded product kneaded in the kneading section 11; a twin-screw extruder 2 connected to the kneaded product discharge section 6 and to conduct a twin-screw extrusion processing after receiving a kneaded product from the kneader 1; a monomer feed section 3 connected to the kneader 1 and to feed the monomer to the kneading section 11; a polymerization initiator feed section 4 connected to the kneader 1 and to feed the polymerization initiator to the kneading section 11; and a neutralizing agent feed section 5 connected to the kneader 1 and to feed a neutralizing agent to a kneaded product.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an apparatus and method for producing a hydrophilic thermoplastic resin, and more particularly to an apparatus and method for producing a hydrophilic thermoplastic resin from a compound having a 1,3-dioxolane ring in its molecule. .

[0002]

2. Description of the Related Art The ring-opening polymerization reaction of 1,3-dioxolane is extremely vigorous, and when the polymerization is carried out with stirring in an ordinary reaction vessel, the temperature rises sharply due to insufficient heat removal rate. It may cause sudden boiling or the contents may gush out from the cooler. Therefore, it is generally difficult to polymerize a high concentration of 1,3-dioxolane. Further, the obtained polymer has a very high viscosity, so that it is difficult to remove it from the kettle.

When producing a polyacetal, a device such as a KRC kneader having a high self-cleaning property and capable of continuously treating a highly viscous liquid is used, and 1,3-dioxolane is added to improve the stability of the polyacetal. It is known to add a small amount as a polymerization component. In the production of polyacetal, the polymerization initiator is uniformly mixed with the monomer.
When it is applied to the polymerization of 3-dioxolane, a large amount of polymerization initiator is required, and the polymerization reaction proceeds all at once in the whole monomer, resulting in intense heat generation, which makes it difficult to remove heat.
Therefore, with the conventional constitution, it is very difficult to polymerize 1,3-dioxolane to obtain a high molecular weight polydioxolane in high yield.

[0004]

The problem to be solved by the invention is to efficiently obtain a high molecular weight polydioxolane in a high yield. Another problem to be solved by the invention is to mildly polymerize 1,3-dioxolane.

[0005]

[Means for Solving the Problems]

(1) The apparatus for producing a hydrophilic thermoplastic resin according to the present invention,
A kneader having a kneading section and a kneaded material discharging section, a twin-screw extruder, a monomer supplying section, a polymerization initiator supplying section, and a neutralizing agent supplying section are provided. The kneading section of the kneader,
A compound having a 1,3-dioxolane ring in the molecule 60
It is a method of kneading a monomer containing at least wt% and a polymerization initiator. The kneaded material discharging section of the kneading machine discharges the kneaded material kneaded in the kneading section. The twin-screw extruder is connected to the kneaded material discharge part, receives the kneaded material from the kneader, and performs a twin-screw extrusion process.
The monomer supply unit is connected to the kneading machine and supplies the monomer to the kneading unit. The polymerization initiator supply unit is connected to the kneading machine and supplies the polymerization initiator to the kneading unit. The neutralizing agent supply part is a part that is connected to the kneading machine and supplies a neutralizing agent to the kneaded product.

The apparatus for producing a hydrophilic thermoplastic resin according to the present invention may further include an auxiliary kneader arranged between the kneaded material discharge part of the kneader and the twin-screw extruder. The apparatus for producing a hydrophilic thermoplastic resin according to the present invention may have a devolatilization section in the twin-screw extruder.
The kneading machine has at least one selected from a first rotating shaft, a spiral blade provided on an outer peripheral portion of the first rotating shaft, and a group of a large number of blades arranged at intervals in the rotating shaft direction.
And a first blade of the seed.

The kneader includes a second rotary shaft arranged adjacent to and parallel to the first rotary shaft, a spiral blade provided on an outer peripheral portion of the second rotary shaft, and a gap in the rotary shaft direction. It may be further provided with a second blade which is at least one selected from a group of a large number of blades that are arranged openly and which is arranged with the first blade and a small gap therebetween.

(2) In the method for producing a hydrophilic thermoplastic resin according to the present invention, the first rotating shaft, the spiral blades provided on the outer peripheral portion of the first rotating shaft, and a space are provided in the rotating shaft direction. Using a kneader equipped with at least one first blade selected from a group of a large number of blades arranged as follows, a monomer supplying step, a polymerization initiator adding step, and an initiator deactivating step. including. The monomer supplying step is a step of supplying a monomer containing 60% by weight or more of a compound having a 1,3-dioxolane ring in the molecule into the kneader. The polymerization initiator addition step is a step of intermittently adding a polymerization initiator to the kneader in order to locally start the polymerization of the monomer. The neutralizing agent addition step, in order to deactivate the polymerization initiator contained in the polymer obtained in the kneader,
In this step, a neutralizer is added to the kneader.

The kneader comprises a second rotary shaft disposed adjacent to and parallel to the first rotary shaft, a spiral blade provided on the outer peripheral portion of the second rotary shaft, and a gap in the rotary shaft direction. It may be further provided with a second blade which is at least one selected from a group of a large number of blades that are arranged openly and which is arranged with the first blade and a small gap therebetween.

It is preferable that the step of adding the polymerization initiator is carried out at a reaction temperature in the range of 0 to 70 ° C. The neutralizing agent addition step is preferably performed within 1 hour from the start of the polymerization initiator addition step.

[0011]

Detailed Description of Means The kneading machine used in the manufacturing apparatus of the present invention has a single rotating shaft or a plurality of rotating shafts parallel to each other. Each rotary shaft includes at least one blade selected from a group of spiral blades provided on the outer peripheral portion of the rotary shaft and a large number of blades arranged at intervals in the rotary shaft direction. These blades are in contact with the inner wall of the reactor body with a small gap, and when the kneader has multiple rotating shafts, they are in contact with the blades attached to the adjacent rotating shafts with a small gap. ing.

The shape of the stirring blade provided on the outer peripheral portion of the rotary shaft of the kneading machine of the present invention is not particularly limited, but is, for example, a spiral shape, a spectacle blade, a lattice blade, or a petal shape. , Eccentric disc type self-cleaning type,
Of hollow disk blades, three-bladed blades, or "diaper-shaped" sections whose cross section perpendicular to the axis of rotation is convex, elliptical, eccentric, polygonal, or pseudotriangular. The thing etc. can be mentioned.

Such a kneader is generally a continuous kneader or a continuous reactor or extruder having a high self-cleaning property called a single-screw or twin-screw extruder.
For example, KRC kneader (manufactured by Kurimoto Iron Works), SCR kneader (manufactured by Mitsubishi Heavy Industries, Ltd.), Vivolac (manufactured by Sumitomo Heavy Industries, Ltd.), TEX-K (manufactured by Japan Steel Works, Ltd.) and plastic extrusion molding. Alternatively, a single-screw or twin-screw extruder widely used for devolatilization and the like can be mentioned.

An example of the manufacturing apparatus of the present invention is shown in FIG. This manufacturing apparatus includes a kneading machine 1 having a kneading section 11 and a kneaded material discharging section 6, and a twin-screw extruder 2 having a volatile matter removing section 8.
It has and. An auxiliary kneading machine 7 is further provided between the kneading machine 1 and the twin-screw extruder 2. Kneading section 11
Is a monomer supply unit 3 that supplies a constant amount of a monomer containing 60% by weight or more of a compound having a 1,3-dioxolane ring in the molecule to the kneading unit 11, and a polymerization initiator that supplies a constant amount of a polymerization initiator to the kneading unit 11. The polymerization initiator supply unit 4 is connected. Also,
The kneaded material discharge section 6 is connected to the neutralizing agent supply section 5.

As shown in FIG. 2, the kneading section 11 of the kneading machine 1
Is connected to a drive unit 9 including a motor and a speed reducer. As shown in FIG. 3, the kneading section 11 is divided into two troughs 10 and a driving section 9 rotatably supported by the troughs 10.
And a pair of rotating shafts 12 and 14 driven by. Both rotary shafts 12 and 14 have a convex lens-like first side view.
A large number of blades (paddles) 13 and 15 are arranged and fixed in the axial direction. The paddles 13 and 15 are arranged with their phases shifted by the number of sheets. As a result, even if the two kinds of raw materials supplied into the kneading section 11 have high viscosities, they are efficiently kneaded and transported in a short time.

The compounds having 1,3-dioxolane ring in the molecule used in the present invention include 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2-phenyl-1,3-diosisolane, 4-methyl-1,3-dioxolane, 4-ethyl-1,3-dioxolane and the like can be mentioned. You may use these 2 or more types in mixture. Among these compounds, 1,3-dioxolane has a feature that it has a particularly high reactivity and gives a high-molecular weight, highly hydrophilic polymer. On the other hand, other compounds are inferior to 1,3-dioxolane in terms of reactivity, but have a feature of giving a polymer having a high melting point and a little hydrophilicity, which cannot be obtained by polymerization of 1,3-dioxolane.

The monomer containing the compound having the 1,3-disoxolane ring in the molecule used in the present invention is a compound having the 1,3-dioxolane ring in the molecule and a monomer copolymerizable therewith. Mention may be made of mixtures with monomers. Examples of the copolymerizable monomer include styrene, (meth) acrylic acid, (meth) acrylic acid ester, unsaturated hydrocarbons such as ethylene and propylene, cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran, and γ- Examples thereof include lactones and lactams such as butyrolactone, glycolide, lactide, ε-caprolactone, ε-caprolactam. You may use 2 or more types of these.

The amount of these copolymerizable monomers used is
It is less than 40% by weight, preferably 10% by weight or less based on the total amount of the monomers. When the amount of the monomer used is 40% by weight or more, the polymerizability of the monomer may be lowered, and the resulting polymer may have a significantly low molecular weight or may have a very low polymerization rate. Furthermore, when an extremely high molecular weight polymer is to be obtained, it is desirable that the content of the copolymerization component is 10% by weight or less.

The polymerization according to the present invention is usually carried out without solvent. In particular, the solvent is used only when the use of the solvent is unavoidable due to the problem of heat removal or the compatibility of the monomers with each other, but the amount used is the minimum necessary. Suitable solvents include, for example, methyl ethyl ketone, acetone, ketones such as methyl isobutyl ketone, cyclic ethers such as dioxane, chloroform, dichloromethane, halogen-containing hydrocarbons such as trichloro-trifluoroethane, toluene,
Examples thereof include aromatic hydrocarbons such as xylene, and alcohols such as methanol, ethanol and 2-propanol. You may use these 2 or more types in mixture. However, it is desirable to select a solvent having no active hydrogen as much as possible among the above-mentioned solvents and dehydrate it before use. Specifically, the amount of active hydrogen and water is preferably 1 mol% or less, more preferably 0.1 mol% or less with respect to the monomer.

The polymerization initiator used in the present invention is 1,3
It is preferable to use a monomer having a very high activity such that a monomer containing a compound having a dioxolane ring in the molecule is polymerized at an extremely high speed. When the activity is low, the polymerization reaction starts after the polymerization initiator diffuses into the monomer, so that the local polymerization reaction cannot occur. Examples of highly active polymerization initiators include heteropolyacids, boron trifluoride etherate, boron tetrafluoride oxonium compounds such as triethyloxonium tetrafluoroborate, and aluminoxane / sulfuric acid mixtures. You may use 2 or more types of these. Examples of the heteropolyacid include phosphotungstic acid, silicotungstic acid, and phosphomolybdic acid. Among them, phosphotungstic acid is preferable in that a high molecular weight polydioxolane can be obtained and it is non-coloring. Among the polymerization initiators other than the heteropolyacid, triethyloxonium tetrafluoroborate and aluminoxane / sulfuric acid mixture are preferable because they give a highly active and high molecular weight polymer.

The amount of the polymerization initiator used in the present invention is preferably 0.0001 to 0.1 mmol based on 1 mol of the monomer. The amount of polymerization initiator used is 0.0
If it is less than 001 mmol, the polymerization rate becomes very slow, and the productivity is lowered. Further, it may be easily affected by water and active hydrogen in the monomer and the solvent, and the polymerization may not occur at all or may stop in the middle. On the other hand, when the amount of the polymerization initiator used is more than 0.1 mmol, the polymerization becomes too vigorous and the heat removal becomes difficult, and the molecular weight of the obtained polymer decreases.

When adding the polymerization initiator, the polymerization initiator may be used as it is, or may be used as a polymerization initiator solution which is dissolved in a solvent which does not inactivate the polymerization initiator so that the concentration is 1% by weight or more. When the polymerization initiator is added as a solution, if the concentration of the polymerization initiator solution is less than 1% by weight, the concentration is too low to start the reaction immediately. It diffuses throughout and the polymerization reaction proceeds at once in the whole monomer. In addition, a large amount of polymerization initiator is required to start the polymerization reaction, and once the reaction starts, the heat is generated violently, so that heat removal becomes very difficult.

Furthermore, the polymerization initiator (or polymerization initiator solution) must be added intermittently. The method of intermittently adding the polymerization initiator (or the solution of the polymerization initiator) is, for example, using a metering liquid feed pump, in which the supply nozzle is separated from the liquid surface of the monomer and added in a droplet form, Examples include a method of intermittently adding it in a state of being immersed in a polymer at regular intervals.

The solvent for dissolving the polymerization initiator is not particularly limited as long as it does not deactivate the polymerization initiator, and acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol dimethyl ether, dioxane, chloroform, dichloromethane, hexane, cyclohexane, Examples include toluene and xylene. You may use the mixed solvent of these 2 or more types. These solvents are usually used as they are, but in order to obtain a polymer having a very high molecular weight, water and impurities are distilled by preliminarily using an adsorbent such as molecular sieves or a desiccant such as calcium hydride. It is desirable to use after removing.

There are no particular restrictions on the timing of addition of the polymerization initiator and the number of times it is added, but it is usually added from the same supply port as the monomer or from another supply port provided immediately after that.
When a composite catalyst such as an aluminoxane / sulfuric acid-based catalyst is used or when two or more polymerization initiators are used,
The supply ports for the respective catalysts may be the same or different.

The reaction temperature in the polymerization of the present invention is not particularly limited, but is -10 ° C or higher and the boiling point of the monomer or lower, preferably 0 ° C or higher and 70 ° C or lower. Reaction temperature is -10 ℃
If it is lower, the polymerization reaction may be so slow that productivity may be significantly reduced. On the other hand, when the reaction temperature is higher than the boiling point of the monomer, bubbles are generated in the device,
Not only the liquid-feeding ability and self-cleaning property of the apparatus are lowered, but also the chain transfer reaction is promoted, so that the molecular weight of the obtained polymer is lowered. However, the boiling point here is not the boiling point under the atmospheric pressure, but the boiling point under the pressure in the apparatus, and when the reaction proceeds in a pressurized state, the boiling point is higher than the boiling point under the atmospheric pressure. Become. In addition, in order to safely and efficiently take out polydioxolane having a high polymerization rate, 0 ° C or higher and 70 ° C or higher
The following is desirable.

The hydrophilic thermoplastic resin obtained by the continuous polymerization method of the present invention may be decomposed if left as it is while keeping the activity of the polymerization initiator. It is preferable to deactivate the remaining polymerization initiator. Examples of the deactivator of the polymerization initiator include amines such as ammonia, triethylamine, ethylenediamine, aniline and pyridine, and basic compounds such as ammonia and sodium methylate. You may use 2 or more types of these. Among the above deactivators, amines are particularly preferably used because they have good diffusibility in the polymer and can rapidly deactivate the polymerization initiator.

The deactivation of the polymerization initiator is preferably carried out within 1 hour, more preferably within 30 minutes, from the time when the polymerization initiator is added. When the time from the addition of the polymerization initiator to the deactivation of the polymerization initiator is longer than 1 hour, the decomposition of the polymer proceeds, so that a high molecular weight polymer may not be obtained. The method for deactivating the polymerization initiator is not particularly limited, and it can be carried out using a batch-type or continuous-type device capable of kneading the high-viscosity polymer and the deactivator. Further, in the case of continuously deactivating the polymerization initiator, a method using a continuous kneader similar to the reactor used for the polymerization reaction of the polymer discharged from the polymerization reactor or the discharge of the polymerization reactor A method in which a deactivator charging port is provided immediately before the outlet to carry out polymerization and deactivation of the polymerization initiator in the same reactor, and the like can be mentioned.

Further, during the continuous polymerization of 1,3-dioxolane of the present invention, various additives (for example, fillers, dyes, pigments, stabilizers, lubricants, crystal nucleating agents) which do not inhibit the polymerization of monomers are added. You may.

[0030]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. <Calculation of reaction yield> <Example 1> Kurimoto Iron Works S2 type KRC kneader (L / D
= 13.2), the jacket temperature was set to 20 ° C., and the shaft rotation speed was set to 96 rotations / minute. 1,3-dioxolane was supplied at a rate of 10 kg / hr from the charging port, and 6 ml of a 5 wt% methyl ethyl ketone solution of phosphotungstic acid as a polymerization initiator was further supplied from a polymerization initiator supply nozzle provided 3 cm above the monomer liquid surface. It was added in a droplet form at a rate of hr. The polymerization was locally started immediately from the portion where the droplet of the polymerization initiator solution dropped. About 5 minutes after the introduction of the polymerization initiator solution was started, the valve at the outlet was opened, and polydioxolane with high viscosity was discharged. The discharged polymer was put into a batch type 2L kneader equipped with a Banbury type stirring blade every 10 minutes, and 1 wt% of triethylamine was added.
The polymerization initiator was deactivated by stirring with 100 g of the -1,3-dioxolane solution. About 10.1 kg of the pre-dried polymer obtained by continuing the operation for 1 hour was dried in a vacuum dryer at 100 ° C. for 5 hours, and as a result, about 8.2 kg of polydioxolane 1 was obtained. <Example 2> S2 type KRC kneader manufactured by Kurimoto Iron Works (L / D
= 13.2), the jacket temperature was set to 20 ° C., and the shaft rotation speed was set to 38 rotations / minute. 10 kg / hr of 1,3-dioxolane from the charging port, and 6 ml of a 5 wt% methyl ethyl ketone solution of phosphotungstic acid as a polymerization initiator.
/ Hr was added in the same manner as in Example 1. Polymerization was started immediately after adding 1,3-dioxolane and the polymerization initiator solution. After about 5 minutes, when the valve of the discharge port was opened, high viscosity polydioxolane was discharged. The discharged polymer was placed every 10 minutes in a batch type 2L kneader equipped with a Banbury type stirring blade, and triethylamine
The polymerization initiator was deactivated by stirring with 100 g of a wt% -1,3-dioxolane solution. Approximately 9.8 kg of the polymer before drying obtained by continuing the operation for 1 hour was dried in a vacuum dryer at 100 ° C for 5 hours.
As a result of drying over time, about 8.3 kg of polydioxolane 2 was obtained. <Example 3> S2 type KRC kneader manufactured by Kurimoto Iron Works (L / D
= 13.2), the jacket temperature was set to 40 ° C., and the shaft rotation speed was set to 38 rotations / minute. 7 kg / hr of 1,3-dioxolane from the charging port, 3 ml of 5 wt% phosphotungstic acid methyl ethyl ketone solution as a polymerization initiator
It was charged in the same manner as in Example 1 at a rate of hr. Polymerization
Immediately after the addition of 1,3-dioxolane and the polymerization initiator solution, the polymerization was started. After about 10 minutes, when the valve of the discharge port was opened, high-viscosity polydioxolane was discharged. The discharged polymer was put into a batch type 2L kneader equipped with a Banbury type stirring blade every 10 minutes, and 1 w of triethylamine was added.
The polymerization initiator was deactivated by stirring with 100 g of a t% -1,3-dioxolane solution. About 6.9 kg of the pre-drying polymer obtained by continuing the operation for 1 hour was dried in a vacuum dryer at 100 ° C. for 5 hours, and as a result, about 6.0 kg of polydioxolane 3 was obtained. <Example 4> S2 type KRC kneader manufactured by Kurimoto Iron Works (L / D
= 13.2), the jacket temperature was set to 40 ° C., and the shaft rotation speed was set to 45 rotations / minute. 10 kg / hr of 1,3-dioxolane and 10 m of a 5 wt% phosphotungstic acid methyl ethyl ketone solution as a polymerization initiator from the charging port
It was added in the same manner as in Example 1 at a ratio of 1 / hr. Polymerization was started immediately after adding 1,3-dioxolane and the polymerization initiator solution. After about 1 minute, when the valve of the discharge port was opened, highly viscous polydioxolane was discharged. The discharged polydioxolane was further charged into another S2 type KRC kneader (L / D = 7.6), and a 0.1 wt% -1,3-dioxolane solution of triethylamine was added to this solution.
The polymerization initiator was deactivated by charging from the same charging port at a rate of 5 kg / hr. About 9.5 kg of the pre-drying polymer obtained by continuing the operation for 1 hour was dried in a vacuum dryer at 100 ° C. for 5 hours, and as a result, about 8.4 kg of polydioxolane 4 was obtained. <Example 5> About 9.5 kg of a pre-dried polymer was obtained in the same manner as in Example 1 except that 1M-dichloromethane solution of triethyloxonium tetrafluoroborate was added as a polymerization initiator at a rate of 10 ml / hr. . Then, the polymer was dried in a vacuum dryer at 100 ° C. for 5 hours, and as a result, about 8.0 kg of polydioxolane 5 was obtained. <Example 6> 2M of triethylaluminum as a polymerization initiator
-Hexane solution and concentrated sulfuric acid, 3 ml / hr,
About 9.5 kg of a pre-dried polymer was obtained in the same manner as in Example 1 except that the amount was 1 ml / hr. Then, the polymer was dried in a vacuum dryer at 100 ° C. for 5 hours, and as a result, about 7.6 kg of polydioxolane 6 was obtained. <Example 7> The polymer before drying was dried in the same manner as in Example 3 except that a mixture of 80 parts by weight of 1,3-dioxolane and 20 parts by weight of ε-caprolactone was used as a monomer.
2 kg was obtained. Then, the polymer was dried in a vacuum dryer at 100 ° C. for 5 hours, and as a result, about 5.3 kg of polydioxolane 7 was obtained. <Example 8> About 7.0 kg of polymer before drying was carried out in the same manner as in Example 3 except that a mixture of 90 parts by weight of 1,3-dioxolane and 10 parts by weight of 2-methyl-1,3-dioxolane was used as a monomer. Got Then, the polymer is mixed with 10
As a result of drying in a vacuum dryer at 0 ° C. for 5 hours, about 4.
8 kg of polydioxolane 8 was obtained. <Example 9> About 7.2 kg of a polymer before drying was carried out in the same manner as in Example 3 except that a mixture of 98 parts by weight of 1,3-dioxolane and 2 parts by weight of 2-phenyl-1,3-dioxolane was used as a monomer. Got Then, the polymer is mixed with 10
As a result of drying in a vacuum dryer at 0 ° C. for 5 hours, about 4.
6 kg of polydioxolane 9 was obtained. <Example 10> 1,3-dioxolane 90 as a monomer
About 7.3 kg of a polymer before drying was obtained in the same manner as in Example 3 except that a mixture of 10 parts by weight of styrene and 10 parts by weight of styrene was used. Then, the polymer was dried in a vacuum dryer at 100 ° C. for 5 hours, and as a result, about 4.7 kg of polydioxolane 10 was obtained. <Comparative Example 1> 100 g of 1,3-dioxolane was placed in a 200 ml four-necked flask equipped with a condenser, a stirrer, a nitrogen introducing tube, and a thermometer, and cooled in a cold water bath at 0 ° C. 1,3-
When the temperature of dioxolane reached 3 ° C., 0.1 ml of a 5 wt% methyl ethyl ketone solution of phosphotungstic acid as a polymerization initiator was added with stirring. The polymerization started in the entire system immediately after the polymerization initiator was added, and although the reaction started at a low temperature of 3 ° C., the rapid heat generation caused 1,
3-Dioxolane was refluxed, and 1,3-dioxolane was partially ejected from the tip of the cooling tube unit. During this time,
The system rapidly thickens due to polymerization, and the exothermic peak 8 occurs in about 30 seconds.
It reached 2 degrees Celsius. Then, the reaction was continued for 3 minutes, and the polydioxolane of Comparative Example 1 was taken out. However, the viscosity was so high that about 25 g remained in the flask.

To about 75 g of the obtained polydioxolane, 5 g of a 0.1 wt% -1,3-dioxolane solution of triethylamine was added to deactivate the polymerization initiator, and thereafter 10
As a result of drying in a vacuum dryer at 0 ° C for 5 hours, about 65
g of polydioxolane (Comparative Example 1-a) was obtained. next,
75 g of 1,3-dioxolane was newly supplied to the flask, and 0.75 ml of a polymerization initiator was added to carry out polymerization.
The reaction was milder than that in the first batch, and almost no exotherm was observed for 5 minutes after the addition of the polymerization initiator. A temperature increase gradually accompanied by heat generation was observed from 5 minutes after the addition of the polymerization initiator, and an exothermic peak 4 occurred 13 minutes after the addition of the polymerization initiator.
It reached 5 ° C. Then, the reaction was continued for 3 minutes, and the produced polydioxolane was taken out. However, about 10 g remained in the flask due to the high viscosity.

To about 90 g of the obtained polydioxolane, 5 g of a 0.1 wt% -1,3-dioxolane solution of triethylamine was added to deactivate the polymerization initiator, and then 10
As a result of drying in a vacuum dryer at 0 ° C for 5 hours, about 60
g of polydioxolane (Comparative Example 1-b) was obtained. Comparative Example 2 Polymerization was carried out under the same conditions as in Example 1. However, the discharged polymer was not subjected to the operation of deactivating the polymerization initiator with a 2 L kneader every 10 minutes as in Example 1, but was left as it was in a 20 L kneader until the operation of the KRC kneader was completed. . The operation of the KRC kneader was completed in 1.5 hours, during which the polymer discharged in the 20 L kneader was stored at room temperature for another 30 minutes, and then 900 g of a 1 wt% -1,3-dioxolane solution of triethylamine was added. The polymerization initiator was inactivated at once. Subsequent drying was carried out in the same manner as in Example 1, and about 1 polymer before drying was used.
Obtained 5.2 kg. Then, the polymer was dried in a vacuum dryer at 100 ° C. for 5 hours, and as a result, about 12.1 kg of polydioxolane (Comparative Example 2) was obtained. <Comparative Example 3> The polymer before drying was dried in the same manner as in Example 3 except that a mixture of 40 parts by weight of 1,3-dioxolane and 60 parts by weight of ε-caprolactone was used as a monomer.
2 kg was obtained. Then, the polymer was dried in a vacuum dryer at 100 ° C. for 5 hours, and as a result, about 3.6 kg of polydioxolane (Comparative Example 3) was obtained. <Comparative Example 4> 5 of phosphotungstic acid as a polymerization initiator
Polymerization of 1,3-dioxolane was attempted in the same manner as in Example 1 except that a wt% methyl ethyl ketone solution was added at a rate of 0.6 ml / hr, but the polymerization reaction did not start, and the monomer was directly discharged. It was discharged from the outlet. <Comparative Example 5> 5 of phosphotungstic acid as a polymerization initiator
1,3-, except that the wt% methyl ethyl ketone solution was added at a rate of 1500 ml / hr, in the same manner as in Example 1.
An attempt was made to polymerize dioxolane, but the reaction proceeded extremely violently in the monomer supply port, the viscosity increased, and the foamed polymer rose to completely block the supply port, so that the reaction could be continuously performed. could not. <Comparative Example 6> A 0.5 wt% methyl ethyl ketone solution of phosphotungstic acid was used as a polymerization initiator at 60 ml / hr.
In the same manner as in Example 1 except that the components were added in the proportions of 1, 3
-The polymerization of dioxolane was tried, but the polymerization reaction did not start, and the monomer was discharged from the discharge port 6 as it was. <Results> Table 1 shows the reaction yield of the obtained polydioxolane and the polystyrene reduced number average molecular weight (measured by size exclusion chromatography).

[0033]

[Table 1]

According to the manufacturing apparatus and manufacturing method of the present invention,
Ring-opening polymerization of 1,3-dioxolane in bulk or at high concentration, which was difficult to carry out in the past, can be carried out mildly, and polydioxolane of high molecular weight and high viscosity can be continuously produced in high yield. You can get it. Further, the polydioxolane thus obtained is extremely useful for films and molded articles, like conventional thermoplastic resins.

[0035]

By using the manufacturing apparatus of the present invention,
High molecular weight polydioxolane can be efficiently obtained in high yield. By using the production method of the present invention, high-molecular-weight polydioxolane can be efficiently obtained in a high yield, and in addition, 1,3-dioxolane can be gently polymerized.

When the production method of the present invention is carried out at a reaction temperature within the range of 0 to 70 ° C., polydioxolane having a higher molecular weight can be obtained more efficiently and in high yield. In the production method of the present invention, a polydioxolane having a higher molecular weight can be obtained by adding the neutralizing agent within 1 hour from the time of introducing the polymerization initiator.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus of the present invention.

FIG. 2 is a perspective view of the kneading machine.

FIG. 3 is a vertical sectional view of a kneading section of the kneading machine.

[Explanation of Codes] 1 Kneader 2 2 Screw Extruder 3 Monomer Supply Section 4 Polymerization Initiator Supply Section 5 Neutralizer Supply Section 6 Kneaded Material Discharge Port 11 Kneading Section 12 1st Rotating Shaft 13 1st Blade 14th 2 rotating shaft 15 second blade

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiaki Kuriyama 5-8 Nishimitabicho, Suita City, Osaka Prefecture Japan Catalytic Polymer Research Institute Ltd. (72) Inventor Masashi Yukitake 5th Nishimitabicho, Suita City, Osaka Prefecture No. 8 Japan Catalyst Functional Development Laboratory

Claims (9)

[Claims] 1. A kneading section for kneading a monomer containing 60% by weight or more of a compound having a 1,3-dioxolane ring in its molecule and a polymerization initiator, and a kneaded product kneaded in the kneading section is discharged. A kneading machine having a kneading material discharging part, a twin-screw extruder connected to the kneading material discharging part, which receives the kneading material from the kneading machine and performs a twin-screw extrusion treatment, and is connected to the kneading machine, A monomer supply unit that supplies the monomer to the kneading unit, a polymerization initiator supply unit that is connected to the kneader and supplies the polymerization initiator to the kneading unit, and a connection to the kneader, and An apparatus for producing a hydrophilic thermoplastic resin, comprising: a neutralizing agent supply unit that supplies a neutralizing agent to a kneaded product. 2. A kneading machine further comprising an auxiliary kneader arranged between the kneaded material discharge part of the kneading machine and the twin-screw extruder.
The apparatus for producing a hydrophilic thermoplastic resin according to claim 1. 3. The apparatus for producing a hydrophilic thermoplastic resin according to claim 1, wherein the twin-screw extruder has a volatile matter removing section. 4. The kneader comprises a first rotating shaft, a spiral blade provided on an outer peripheral portion of the first rotating shaft, and a group of many blades arranged at intervals in the rotating shaft direction. 1. At least one selected first blade is provided.
3. The hydrophilic thermoplastic resin manufacturing apparatus according to any one of 3 above. 5. The kneading machine comprises a second rotating shaft arranged adjacent to and parallel to the first rotating shaft, a spiral blade provided on an outer peripheral portion of the second rotating shaft, and a rotating shaft direction. At least one selected from the group of a large number of blades spaced apart from each other, and further comprising a second blade arranged with the first blade and a small gap therebetween. Item 5. The apparatus for producing a hydrophilic thermoplastic resin according to Item 4. 6. A first rotating shaft, at least one selected from a group of a plurality of blades arranged at intervals in the rotating shaft direction and a spiral blade provided on an outer peripheral portion of the first rotating shaft. A monomer feeding step of feeding a monomer containing 60% by weight or more of a compound having a 1,3-dioxolane ring in its molecule to a kneading machine equipped with a first blade of a seed; A polymerization initiator addition step of intermittently adding a polymerization initiator to the kneader to start the polymerization of the monomer, and deactivate the polymerization initiator contained in the polymer obtained in the kneader. Therefore, a method for producing a hydrophilic thermoplastic resin, comprising a neutralizing agent addition step of adding a neutralizing agent to the kneader. 7. The kneader comprises a second rotary shaft arranged adjacent to and parallel to the first rotary shaft, a spiral blade provided on an outer peripheral portion of the second rotary shaft, and a rotary shaft direction. At least one selected from the group of a large number of blades spaced apart from each other, and further comprising a second blade arranged with the first blade and a small gap therebetween. Item 7. A method for producing a hydrophilic thermoplastic resin according to Item 6. 8. The method according to claim 6 or 7, wherein the step of adding the polymerization initiator is performed at a reaction temperature in the range of 0 to 70 ° C.
The method for producing the hydrophilic thermoplastic resin according to 1. 9. The neutralizing agent addition step is performed within 1 hour from the start of the polymerization initiator addition step.
5. The method for producing the hydrophilic thermoplastic resin according to any one of 1.