JPH0948845A - Production of high molecular weight polyalkylene oxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially effectively obtain the subject polymer in a short reaction time by using a reaction device for high viscosities. SOLUTION: This polymer having a number-average mol.wt. of 10000-10000000, preferably 60000-5000000, with a reaction device for high viscosities. The reaction method includes a ring-opening polymerization method comprising ring opening-polymerizing a 2-6C aliphatic cyclic ether in the presence of a catalyst such as dimethyl zinc, and a chain-extending method comprising reacting a chain extender such as a phosphate ester with a low mol.wt. polyalkylene oxide obtained from a 2-6C aliphatic glycol. The reaction device for high viscosities includes a self-cleaning type horizontal biaxial kneader having two stirring shafts 12, 12 arranged in the trough of the kneader main body in parallel and convex lens shape paddles 13 in which the stirring shafts 12, 12 are arranged in different phase angles.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a high molecular weight polyalkylene oxide. For more details,
The present invention relates to a method for producing a high molecular weight polyalkylene oxide having a number average molecular weight of 10,000 to 10,000,000.

[0002]

2. Description of the Related Art High molecular weight polyalkylene oxide is water-soluble and is used in various applications utilizing its characteristics. For example, a high molecular weight polyalkylene oxide, alone or in combination with various additives, is molded into a sheet or film, which can be used as a packaging material or the like.

As a method for producing a high molecular weight polyalkylene oxide, for example, ethylene oxide and / or propylene oxide is subjected to ring-opening polymerization using a strong base such as sodium hydroxide or potassium hydroxide or an organometallic complex as a catalyst. There is a way. There is also a method of obtaining a high molecular weight polyalkylene oxide by polymerizing a low molecular weight polyalkylene oxide having a low molecular weight obtained by ring-opening polymerization similar to the above with a chain extender.

Among the physical properties of the high molecular weight polyalkylene oxide, the mechanical properties in particular depend largely on the polymer molecular weight. Therefore, various methods for producing a polyalkylene oxide having a molecular weight as high as possible have been studied and proposed.

[0005]

When a high molecular weight polyalkylene oxide is produced only by ring-opening polymerization to obtain a polyalkylene oxide having a high molecular weight, the viscosity during the reaction increases and the stirring efficiency decreases. In order to require a solvent. Further, if solution polymerization or suspension polymerization is performed using a solvent to reduce the viscosity, a devolatilization / collection step of the solvent is required after the reaction, which is industrially inefficient.

When a polyalkylene oxide having a high molecular weight is produced by a high molecular weight reaction with a chain extender,
Although the viscosity is low in the initial stage of the reaction, the molecular weight increases as the reaction progresses, and the viscosity increases accordingly. Due to this increase in viscosity, the diffusivity of the reaction mixture is significantly lowered, and the reaction is stopped before the low molecular weight polyalkylene oxide is chain-extended to have a high molecular weight. If the reaction mixture is diluted with a solvent in order to avoid the termination of the reaction, industrial efficiency is poor as in the above case.

Therefore, the problem to be solved by the present invention is to make it possible to produce a high molecular weight polyalkylene oxide industrially efficiently with a short reaction time.

[0008]

The method for producing a high molecular weight polyalkylene oxide according to the present invention has a number average molecular weight of 10,000 to 10,000.
When producing 10 million high molecular weight polyalkylene oxides, a high viscosity reactor is used. The high molecular weight polyalkylene oxide may be produced by subjecting an aliphatic cyclic ether having 2 to 6 carbon atoms to ring-opening polymerization in the presence of a catalyst.

The high molecular weight polyalkylene oxide is obtained by reacting a low molecular weight polyalkylene oxide obtained from an aliphatic cyclic ether having 2 to 6 carbon atoms or an aliphatic glycol having 2 to 6 carbon atoms with a chain extender. It may be manufactured by In the above-mentioned method for producing a high molecular weight polyalkylene oxide, the high-viscosity reaction device may be a horizontal biaxial kneading device in which agitating shafts connecting deformation blades are arranged side by side.

The high-viscosity reaction apparatus has a self-cleaning horizontal biaxial kneading apparatus having two stirring shafts arranged side by side and a convex lens-shaped paddle incorporated by changing the phase of each stirring shaft. May be The high-viscosity reaction apparatus may be a horizontal biaxial kneading apparatus in which agitation units having a shaftless structure in which lattice-shaped blades are connected are arranged side by side.

The high-viscosity reaction device may be a horizontal biaxial kneading device in which agitation shafts in which eyeglass-shaped blades are connected are arranged side by side. The high-viscosity reaction device may be a vertical kneading device having a plate-shaped stirring blade arranged inside and a modified spiral blade arranged concentrically outside the plate-shaped stirring blade. The high-viscosity reaction device may be a vertical kneading device having an inverted conical ribbon blade.

The high-viscosity reaction device may be a vertical kneading device having an agitating blade having a shaftless structure in which twisted lattice-shaped blades are connected.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION According to the production method of the present invention, a high molecular weight polyalkylene oxide can be produced, and the high molecular weight polyalkylene oxide obtained has a number average molecular weight of 10,000 to 10,000,000. From the viewpoint of mechanical properties of the obtained high molecular weight polyalkylene oxide, its number average molecular weight is preferably 40,000 to 10,000,000, more preferably 50,000 to 7,000,000, and most preferably 60,000 to 5,000,000.

The production method of the present invention is characterized by using a reactor for high viscosity. The reaction method is not particularly limited. Specific examples of the reaction method include 1) a ring-opening polymerization method in which an aliphatic cyclic ether is subjected to ring-opening polymerization in the presence of a catalyst to obtain a high molecular weight polyalkylene oxide, 2) an aliphatic cyclic ether, or an aliphatic glycol Further, there is a chain extension method in which a low molecular weight polyalkylene oxide is reacted with a chain extender to obtain a high molecular weight polyalkylene oxide.

The ring-opening polymerization method 1) will be described in detail below. Ring-Opening Polymerization Method The ring-opening polymerization method is a method of ring-opening polymerization of an aliphatic cyclic ether in the presence of a catalyst. The aliphatic cyclic ether is not particularly limited as long as it is an aliphatic and cyclic ether. Specific examples of the aliphatic cyclic ether include ethylene oxide, propylene oxide, cyclohexene oxide, epichlorohydrin, allyl glycidyl ether, tetrahydrofuran, oxepane, 1,3-dioxolane and the like. These aliphatic cyclic ethers may be used alone or as a mixture of two or more kinds. Among them, the aliphatic cyclic ether is preferably an aliphatic cyclic ether having 2 to 6 carbon atoms because it is excellent in economic efficiency and reactivity. 2 carbon atoms
Among the aliphatic cyclic ethers of 6, at least one selected from ethylene oxide and propylene oxide is more preferable. In addition, ethylene oxide, which is particularly excellent in both economical efficiency and reactivity, is most preferable.

A part or all of ethylene oxide may be optionally substituted with other aliphatic cyclic ether. Other aliphatic cyclic ethers may be preferably substituted by 5 to 100% by weight, more preferably 5 to 50% by weight. It is preferable that the substitution amount of the other aliphatic cyclic ether is within this range, because the economical efficiency and the production efficiency can be balanced. Specific examples of other aliphatic cyclic ethers include propylene oxide, cyclohexene oxide, styrene oxide, epichlorohydrin, allyl glycidyl ether, phenyl glycidyl ether, tetrahydrofuran, oxepane, 1,3-dioxolane and the like.

An aromatic cyclic ether may be subjected to ring-opening polymerization together with an aliphatic cyclic ether. Specific examples of the aromatic cyclic ether include styrene oxide and phenylglycidyl ether. One of these or a mixture of two or more thereof may be used. Examples of the catalyst include organic metal compounds, organic metal compounds and polyhydric alcohols, organic metal compounds and water, organic metal compounds and metal oxides, and the like.

Specific examples of the organometallic compound include dimethyl zinc, diethyl zinc, dipropyl zinc, di-isopropyl zinc, dibutyl zinc, di-isobutyl zinc and di-t.
-Butyl zinc, dipentyl zinc, dihexyl zinc, diheptyl zinc, dioctyl zinc, di-2-ethylhexyl zinc, diphenyl zinc, ditolyl zinc, dicyclobutyl zinc, dicyclopentyl zinc, di-methylcyclopentyl zinc, dicyclohexyl zinc, methylphenyl zinc,
Ethylphenyl zinc, calcium amide, modified calcium amide, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triisohexyl aluminum, triphenyl aluminum, diisobutyl aluminum hydride, diethyl aluminum chloride, diisobutyl aluminum isopropoxide, aluminum methoxide, aluminum Ethoxide, aluminum-n-propoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum isobutoxide, aluminum-n-pentoxide, aluminum isopentoxide, aluminum-
2-butoxide, aluminum-t-butoxide, aluminum-t-pentoxide, aluminum hydroxide, zinc dimethoxide, zinc diethoxide, zinc diisopropoxide, zinc di-n-propoxide, zinc di-n-butoxide, zinc diisooxide Butoxide, zinc di-n-pentoxide, zinc diisopentoxide, zinc di-2-butoxide, zinc di-t-butoxide, zinc di-t-pentoxide, zinc hydroxide, calcium hydride, calcium dimethoxide, calcium di Ethoxide, calcium diisopropoxide, calcium di-n-propoxide, calcium di-n-butoxide, calcium diisobutoxide, calcium di-n-pentoxide, calcium diisopentoxide, calcium di-2-butoxide, calcium The t-but Side, calcium di-t-pentoxide, calcium hydroxide, magnesium dimethoxide, magnesium diethoxide, magnesium diisopropoxide, magnesium di-n-propoxide, magnesium, magnesium di-n-butoxide, magnesium diisobutoxide, Magnesium di-n-pentoxide, magnesium diisopentoxide, magnesium di-2-butoxide, magnesium di-t-butoxide, magnesium di-t-pentoxide, magnesium hydroxide and the like can be mentioned. These organometallic compounds may be used alone or as a mixture of two or more.

Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 2-hydroxyethoxyisopropanol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, cyclopentanediol, methylcyclopentanediol, cyclohexanediol, glycerin, resorcin, catechol, hydroquinone and the like can be mentioned. These polyhydric alcohols may be used alone or as a mixture of two or more.

Specific examples of the metal oxide include zinc oxide,
Examples thereof include aluminum oxide, calcium oxide, magnesium oxide, iron oxide, nickel oxide, molybdenum oxide, silicon oxide and zirconium oxide. These metal oxides may be used alone or as a mixture of two or more. In the above-mentioned, the mixing ratio of each component is, in terms of 0.5 to 2.0 times the polyhydric alcohol (weight) with respect to the organometallic compound,
Then, 0.5 to 2.0 times (weight) of water with respect to the organometallic compound, and 0.5 of metal oxide with respect to the organometallic compound.
~ 2.0 times the weight (weight).

The above-mentioned catalysts are raw material monomers.
0.00 with respect to the total charged amount of aliphatic cyclic ether
You may use 01-10 weight%. Preferably, 0.0
001-7% by weight, most preferably 0.001-4% by weight. When the amount of the catalyst is more than the above range, the polymerization rate becomes fast and it is difficult to remove the heat of reaction, and the molecular weight of the high molecular weight polyalkylene oxide obtained becomes small,
Manufacturing cost is high. When the amount of the catalyst is less than the above range, the polymerization rate is slow and a large amount of the raw material monomer remains,
Manufacturing efficiency decreases.

The temperature for ring-opening polymerization is not particularly limited. The temperature for ring-opening polymerization is 10 to 250 ° C, preferably 50 to 170 ° C, and most preferably 70 to 160.
° C. If it is lower than the above range, the reaction rate is lowered and the production efficiency is poor. On the other hand, when the content is higher than the above range, the reaction rate becomes too fast and the reaction goes out of control, resulting in uncontrollability and thermal deterioration of the obtained high molecular weight polyalkylene oxide.

In the ring-opening polymerization method, a high-viscosity reaction device described later is used. The pressure of the reaction vessel inside the reactor for high viscosity varies depending on the reaction temperature and other conditions, but is 50 kgf / cm ² or less as atmospheric pressure or gauge pressure (51 kgf / absolute pressure).
cm ² or less), more preferably 15 kgf / cm ² or less as atmospheric pressure or gauge pressure. Here, the pressure in the reaction vessel is the total pressure obtained by summing the partial pressures of the gases in the reaction vessel such as the inert gas such as nitrogen substituted for the gas in the reaction vessel and the vapor of the aliphatic cyclic ether.

Next, the chain extension method shown in 2) will be described in detail. Chain extension method The chain extension method is a low molecular weight polyalkylene oxide production step of obtaining a low molecular weight polyalkylene oxide from an aliphatic cyclic ether or an aliphatic glycol, and reacting the obtained low molecular weight polyalkylene oxide with a chain extender. To obtain a high molecular weight polyalkylene oxide.

The low molecular weight polyalkylene oxide can be produced in the low molecular weight polyalkylene oxide production step, and the number average molecular weight of the obtained low molecular weight polyalkylene oxide is 1,000 to 30,000.
The number average molecular weight is preferably 4,000 to 26,000.
When it is 0, the chain extension reaction is completed in a short time, which is preferable.

The low molecular weight polyalkylene oxide production process may use an aliphatic cyclic ether as a starting material or an aliphatic glycol as a starting material. The low molecular weight polyalkylene oxide production step using an aliphatic cyclic ether as a starting material is a step of producing a low molecular weight polyalkylene oxide by subjecting an aliphatic cyclic ether to a ring-opening addition reaction with a catalyst in the presence of an initiator. The aliphatic cyclic ether used here is not particularly limited, and specific examples thereof include the aliphatic cyclic ethers shown in the above ring-opening polymerization method. Also, carbon number 2
The aliphatic cyclic ethers of to 6 are preferable because they are excellent in economic efficiency and reactivity, and the same applies to the more preferable ones.

Specific examples of the initiator include water, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 2-hydroxyethoxyisopropanol, 1,4-butanediol, 1,
Examples include 5-pentanediol, 1,6-hexanediol, cyclopentanediol, methylcyclopentanediol, cyclohexanediol, glycerin, resorcin, catechol, and hydroquinone. These initiators may be used alone or as a mixture of two or more.

The above initiator may be used in an amount of 0.0001 to 10% by weight based on the total charged amount of the aliphatic cyclic ether which is a raw material monomer. Preferably 0.0001 to 7% by weight is used, most preferably 0.001 to 5% by weight. When the amount of the initiator is less than the above range, the reaction time becomes long, and moreover, the unreacted raw material monomer remains after the completion of the reaction, which lowers the production efficiency. Further, when the amount of the initiator exceeds the above range, the molecular weight of the low molecular weight polyalkylene oxide obtained becomes small, it takes a long time to increase the molecular weight, and the production efficiency is poor.

Specific examples of the catalyst used in the low molecular weight polyalkylene oxide production process include sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium-n-propoxide and sodium- n-butoxide,
Sodium isobutoxide, sodium-n-pentoxide, sodium isopentoxide, sodium-2-
Butoxide, sodium-t-butoxide, sodium-t-pentoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium-n-
Propoxide, potassium-n-butoxide, potassium isobutoxide, potassium-n-pentoxide, potassium isopentoxide, potassium-2-butoxide, potassium-t-butoxide, potassium-t-pentoxide and the like can be mentioned. These catalysts may be one kind or a mixture of two or more kinds.

This catalyst is 0.00001 with respect to the total amount of the aliphatic cyclic ether as the raw material monomer.
You may use -10 weight%. Preferably 0.000
1-5% by weight, most preferably 0.0001-2% by weight
used. When the amount of the catalyst is more than the above range, the polymerization rate becomes fast, the heat of reaction is difficult to be removed, the molecular weight of the low molecular weight polyalkylene oxide obtained becomes small, and the production cost becomes high. If the amount of the catalyst is less than the above range, the polymerization rate will be slow, a large amount of the raw material monomer will remain, and the production efficiency will decrease.

The temperature for producing the low molecular weight polyalkylene oxide from the aliphatic cyclic ether as a starting material is not particularly limited. The reaction temperature is 10 to 250 ° C, preferably 50 to 170 ° C, and most preferably 70 to
160 ° C. If it is lower than the above range, the reaction rate is lowered and the production efficiency is poor. On the other hand, when the content is higher than the above range, the reaction rate becomes too fast and the reaction goes out of control, resulting in uncontrollability and thermal deterioration of the obtained low molecular weight polyalkylene oxide.

The pressure of the reaction vessel used for producing the low molecular weight polyalkylene oxide varies depending on the reaction temperature and other conditions, but it is 50 kgf / cm ² as atmospheric pressure or gauge pressure.
Or less (absolute 51 kgf / cm ² or less in pressure), more preferably 15 kgf / cm ² or less as atmospheric or gauge pressure. Here, the pressure in the reaction vessel is the total pressure obtained by summing the partial pressures of the gases in the reaction vessel such as the inert gas such as nitrogen substituted for the gas in the reaction vessel and the vapor of the aliphatic cyclic ether.

Next, the low molecular weight polyalkylene oxide production step may be a step using an aliphatic glycol as a starting material. In that case, it is a step of producing a low molecular weight polyalkylene oxide by subjecting an aliphatic glycol to a dehydration condensation reaction. Specific examples of the aliphatic glycol include ethylene glycol, propylene glycol, tetraethylene glycol, epichlorohydrin, butanediol, pentanediol, neopentanediol and hexanediol. These aliphatic glycols may be used alone or as a mixture of two or more kinds. Among them, the aliphatic cyclic glycol is preferably an aliphatic cyclic glycol having 2 to 6 carbon atoms because it is excellent in economic efficiency and reactivity. Among the aliphatic cyclic glycols having 2 to 6 carbon atoms,
At least one selected from ethylene glycol and propylene glycol is more preferable. In addition, ethylene glycol, which is particularly excellent in both economical efficiency and reactivity, is most preferable.

When a low molecular weight polyalkylene oxide is produced by subjecting an aliphatic glycol to a dehydration condensation reaction, a catalyst may be used. Specific examples of the catalyst include sulfuric acid, hydrochloric acid, nitric acid, p-toluene acid, titanium tetraisopropoxide, and boron trifluoride. The catalyst may be used in an amount of 0.00001 to 10% by weight based on the total amount of the aliphatic glycol as a raw material monomer. Preferably 0.0001 to 5% by weight is used, most preferably 0.0001 to 2% by weight. When the amount of the catalyst is more than the above range, the polymerization rate becomes fast, the heat of reaction is difficult to be removed, the molecular weight of the low molecular weight polyalkylene oxide obtained becomes small, and the production cost becomes high. When the amount of the catalyst is less than the above range, the polymerization rate is slow,
A large amount of raw material monomer remains, resulting in a decrease in production efficiency.

There is no particular limitation on the temperature when the low molecular weight polyalkylene oxide is produced from the aliphatic glycol as a starting material. The reaction temperature is 10 to 400 ° C, preferably 50 to 350 ° C, and most preferably 80 to
250 ° C. If it is lower than the above range, the reaction rate is lowered and the production efficiency is poor. On the other hand, when the content is higher than the above range, the reaction rate becomes too fast and the reaction goes out of control, resulting in uncontrollability and thermal deterioration of the obtained low molecular weight polyalkylene oxide.

The reaction pressure for producing a low molecular weight polyalkylene oxide using an aliphatic glycol as a starting material varies depending on the reaction temperature, but is not particularly limited.
The reaction pressure is 0.0001 to 1200 mmHg, preferably,
0.005-760 mmHg, more preferably 0.01
~ 200 mmHg. If the reaction pressure is lower than the above range, a large apparatus for reducing the pressure in the reaction vessel is required. Further, if the reaction pressure is higher than the above range, the reaction does not proceed promptly and the production efficiency is low.

The chain extension step is a step of reacting the low molecular weight polyalkylene oxide obtained in any of the above steps with a chain extender to obtain a high molecular weight polyalkylene oxide. In this step, the high-viscosity reaction device described later is used. Specific examples of the chain extender include phosphoric acid ester, phosphorous acid ester, polyfunctional isocyanate, epoxy compound, polyfunctional oxazoline compound, polyfunctional aziridine compound, carbonate compound, polyfunctional ester compound, polyfunctional carboxylic acid, alkylzinc. , Alkylaluminum, and the like. These chain extenders may be used alone or as a mixture of two or more kinds.

There are no particular restrictions on the phosphoric acid ester or phosphorous acid ester, but diesters, triesters,
Any of these may be used, and examples of the ester group include methyl, ethyl, propyl, butyl, phenyl, and 2-ethylhexyl. The polyfunctional acid anhydride is not particularly limited, but it has at least 3 or more acid anhydride groups in the molecule, and examples thereof include maleic anhydride-styrene copolymer and maleic anhydride-vinyl acetate copolymer. , Maleic anhydride-vinyl chloride copolymer, maleic anhydride butadiene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer and the like.

The polyfunctional isocyanate is not particularly limited, but is one having at least two upper isocyanate groups in the molecule, and examples thereof include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate. , Isocyanate compounds such as metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate and isophorone diisocyanate; Sumidule N
Buret polyisocyanate compounds such as Sumitomo Bayer Urethane Co .; Polyisocyanate compounds having isocyanurate ring such as Desmodur IL, HL (manufactured by Bayer AG), Coronate EH (manufactured by Nippon Poe Urethane Co., Ltd.) An adduct polyisocyanate compound such as Sumidule L (Sumitomo Bayer Urethane Co., Ltd.),
Examples thereof include adduct polyisocyanate compounds such as Coronate HL (manufactured by Nippon Polyurethane Company). These may be used alone or may be a blocked isocyanate.

The epoxy compound is not particularly limited, but is one having at least two epoxy groups in the molecule, and examples thereof include (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether and polytetra. Methylene glycol diglycidyl ether, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-
Hexanediol diglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, glycerol diglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl Ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, glycerol triglycidyl ether, trimethylolpropane polyglycidyl ether and the like can be mentioned.

The carbonate compound is not particularly limited, but dimethyl carbonate, diethyl carbonate,
Examples include dipropyl carbonate and diphenyl carbonate. The polyfunctional carboxylic acid is not particularly limited, for example, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, itaconic acid, suberic acid, azelaic acid, Decanedicarboxylic acid, octadecanedicarboxylic acid, dimer acid and the like can be mentioned.

The polyfunctional ester compound is not particularly limited, and examples thereof include alkyl esters or aromatic esters of the above polyfunctional carboxylic acids. Specific examples include monomethyl ester, dimethyl ester, monoethyl ester,
Examples thereof include diethyl ester, monopropyl ester, dipropyl ester, monobutyl ester, dibutyl ester, monophenyl ester and diphenyl ester.

The polyvalent metal compound is not particularly limited and includes, for example, dimethyl zinc, diethyl zinc, dipropyl zinc, di-isopropyl zinc, dibutyl zinc, di-isobutyl zinc, di-t-butyl zinc, dipentyl zinc, dihexyl. Zinc, diheptyl zinc, dioctyl zinc, di-
2-ethylhexyl zinc, diphenyl zinc, ditolyl zinc, dicyclobutyl zinc, dicyclopentyl zinc, di-
Methyl cyclopentyl zinc, dicyclohexyl zinc, methyl phenyl zinc, ethyl phenyl zinc, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triisohexyl aluminum, triphenyl aluminum, isobutyl aluminum hydride, diethyl aluminum chloride, diisobutyl aluminum isopropoxide, aluminum methoxy , Aluminum ethoxide, aluminum-n-propoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum isobutoxide, aluminum-n-pentoxide, aluminum isopentoxide, aluminum-2-butoxide, aluminum-t-butoxide. , Aluminum-t-pentoxide, aluminum hydroxide System, zinc dimethoxide, zinc diethoxide, zinc diisopropoxide, zinc di-n-propoxide, zinc di-n-butoxide, zinc diisobutoxide, zinc di-n-pentoxide, zinc diisopentoxide, zinc di- 2-butoxide, zinc di-t-butoxide, zinc di-t-pentoxide, zinc hydroxide, calcium hydride, calcium dimethoxide, calcium diethoxide, calcium diisopropoxide, calcium di-n-propoxide, calcium Di-n-butoxide,
Calcium diisobutoxide, calcium di-n-pentoxide, calcium diisopentoxide, calcium di-2-butoxide, calcium di-t-butoxide,
Calcium di-t-pentoxide, calcium hydroxide,
Magnesium dimethoxide, magnesium diethoxide, magnesium diisopropoxide, magnesium di-
n-propoxide, magnesium, magnesium di-n
-Butoxide, magnesium diisobutoxide, magnesium di-n-pentoxide, magnesium diisopentoxide, magnesium di-2-butoxide, magnesium di-t-butoxide, magnesium di-t-pentoxide, magnesium hydroxide, titanium alkoxide ,
Examples thereof include zirconium alkoxide.

The above chain extender may be used in an amount of 0.01 to 10% by weight based on the low molecular weight polyalkylene oxide as a raw material. Preferably 0.1 to 5% by weight, most preferably 0.5 to 2.5% by weight are used. If the amount of the chain extender deviates from the above range, the balance of the charging ratio of the low molecular weight polyalkylene oxide and the chain extender will be lost, the high molecular weight reaction will not occur sufficiently, and only a low molecular weight product will be obtained. .

The temperature during the chain extension step is not particularly limited. The reaction temperature is 10 to 250 ° C., preferably 5
The temperature is 0 to 170 ° C, and most preferably 70 to 160 ° C.
If the temperature is lower than the above range, the reaction will not be completed and the molecular weight will not be sufficiently high. Further, if the temperature is higher than the above range, thermal degradation of the obtained high molecular weight polyalkylene oxide occurs.

The pressure during the chain extension step depends on the chain extender used. In the case of carrying out the condensation reaction with a chain extender, it is carried out under a low pressure in order to complete the reaction in a shorter time, preferably 0.001 to 100 mmHg. When the addition reaction is carried out with a chain extender, the reaction may be carried out under normal pressure, reduced pressure or increased pressure. High-viscosity reactor A high-viscosity reactor is used in the production method of the present invention.
It is preferable to carry out the reaction using a high-viscosity reaction device, because the production can be performed more easily and efficiently.

As a specific example of the high-viscosity reaction device, a horizontal biaxial kneading device (Irie Shokai, trade name "1 liter kneader") in which agitation shafts connecting deformation blades are arranged side by side, and two in parallel are arranged. A self-cleaning horizontal biaxial kneading device having a stirring shaft and a paddle in the shape of a convex lens that is incorporated by changing the phase on each stirring shaft, and a stirring unit having a shaftless structure in which lattice-shaped blades are connected is arranged side by side. A horizontal biaxial kneading device, a horizontal biaxial kneading device in which agitation shafts connecting eyeglass-shaped blades were arranged side by side, a plate-shaped agitation blade arranged inside, and a concentric arrangement outside the plate-shaped agitation blade Examples thereof include a vertical kneading device having a deformed spiral blade, a vertical kneading device having an inverted conical ribbon blade, and a vertical kneading device having an agitating blade having a shaftless structure in which twisted lattice-shaped blades are connected.

The reactor for high viscosity may be either continuous type or batch type. An example of a continuous high-viscosity reaction device is a horizontal biaxial kneading device (manufactured by Kurimoto Iron Works Co., Ltd., trade name “KRC Kneader”) shown in FIG. This kneading device 1
Is a kneader main body 2, a solid supply part 3 for quantitatively supplying powder or fluid to the kneader main body 2, a liquid supply part 4 for quantitatively supplying liquid or slurry liquid to the kneader main body 2, and heating the kneader main body 2. A heating / cooling device 5 for cooling is provided.

The kneader body 2 includes a drive unit 10 composed of a motor and a speed reducer, a trough 11 having two halves, and a trough 1.
It has two stirring shafts 12 (FIG. 2) which are rotatably supported by 1 and driven by a driving unit 10. As shown in FIG. 2, various stirring paddles 13 including a convex lens-shaped paddle 13 and screws (not shown) are incorporated in the stirring shaft 12 side by side in the axial direction. The paddles 13 are arranged with their phases shifted by a unit of several sheets. As a result, trough 1
Even if the two kinds of raw materials supplied in 1 have a high viscosity, they are efficiently kneaded and conveyed in a short time.

In this kneading apparatus 1, for example, the chain extender is stored in the raw material supply section 3 and the low molecular weight polyalkylene oxide is stored in the raw material supply section 4. Then, two kinds of raw materials are supplied from the supply sections 3 and 4 into the trough 11 in a predetermined amount, and the low molecular weight polyethylene oxide is heated and melted and kneaded with a chain extender under normal pressure to cause a chain extension reaction. This produces a high molecular weight polyalkylene oxide.

In addition, as a continuous high-viscosity reaction device, a biaxial horizontal kneading device with a stirring blade having an eyeglass blade (Hitachi, Ltd., trade name "Hitachi eyeglass blade polymerization machine"), a stirring blade having a grid Blades (Hitachi, Ltd., trade name "Hitachi lattice blade polymerizer"), stirring blades with petal shape, stirring blades with self-cleaning type with knitted core disk (manufactured by Mitsubishi Heavy Industries, Ltd., There is a product name "SCR"), a stirring blade having a hollow disk blade or a three-blade blade (trade name "HVR" manufactured by Mitsubishi Heavy Industries, Ltd.), and the like. In addition,
A single-screw or twin-screw extruder widely used for extrusion molding or devolatilization of plastics manufactured by Japan Steel Works under the trade name "TEX-X" may be used.

As a batch type high-viscosity reaction device, a vertical kneading device in which a stirring blade is installed on two shafts concentrically arranged, and a stirring blade having an inverted conical ribbon shape (Mitsubishi Heavy Industries Co., Ltd., trade name "VCR"), stirring blades with twisted lattice vanes (manufactured by Hitachi, Ltd.), trade name "Hitachi High Viscosity Batch Polymerizer") and the like. The high molecular weight polyalkylene oxide thus obtained can be molded and processed and effectively applied to various uses.

[0053]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In addition, the part in an example represents a weight part. The evaluation methods performed in the examples are as follows. (Molecular weight) The number average molecular weight in terms of polystyrene was measured using a gel permeation chromatograph.

-Example 1- 0.065 parts of sodium hydroxide and 15 parts of triethylene glycol were added to the autoclave, and the atmosphere was replaced with nitrogen. Next, the temperature of the autoclave was gradually raised to 150 ° C with stirring, and the pressure inside the autoclave was adjusted to 0 to 10 at the same temperature.
While maintaining at kgf / cm ² , add 570 parts of ethylene oxide to 20
Introduced continuously over time. After introducing ethylene oxide, a maturing reaction was performed at 150 ° C. for 2.0 hours and then the system was returned to room temperature to obtain a low molecular weight polyethylene oxide. The yield of this polyethylene oxide was determined to be 99%. Moreover, the number average molecular weight is 13,000 from the gel permeation chromatography measurement result.
Met.

500 parts of the obtained low molecular weight polyethylene oxide was charged into a 1-liter kneader (manufactured by Irie Shokai Co., Ltd.), heated and melted at 150 ° C., 7.4 parts of dimethyl terephthalate was added, and the pressure was reduced to 15 mmHg. A high molecular weight reaction was carried out for 4 hours. From the gel permeation chromatography measurement result, the number average molecular weight was 112,000.

Example 2-Low molecular weight polyethylene oxide and diphenyl phosphite obtained by the same method as in Example 1 were continuously charged into a high-viscosity horizontal twin-screw extruder, and the mixture was heated at 150 ° C under a reduced pressure of 20 mmHg. A molecular weight conversion reaction was performed. At this time, the retention time until the low-molecular-weight polyethylene oxide was charged into the high-viscosity horizontal twin-screw extruder and reacted with diphenyl phosphite to become a high-molecular weight product and was taken out from the outlet of the apparatus was 10 minutes. From the gel permeation chromatography measurement result, the number average molecular weight was 103,000.

-Comparative Example- A low-molecular-weight polyethylene oxide obtained in Example 1 in a 100-ml flask was used, and the number average molecular weight thereof was 13,0.
100 parts of 00 and 0.145 parts of dimethyl terephthalate were charged, and a high molecular weight reaction was carried out at 150 ° C. for 6 hours under a reduced pressure of 15 mmHg.

From the result of gel permeation chromatography measurement, the number average molecular weight was 45,000. Example 1
The high molecular weight polyalkylene oxide obtained by
The number average molecular weight is higher than that of the comparative example, and the reaction time is very short.

[0059]

EFFECTS OF THE INVENTION According to the present invention, since the reaction step is carried out by using the high-viscosity reaction apparatus, the high-molecular-weight polyalkylene oxide can be industrially efficiently produced in a short reaction time.

[Brief description of drawings]

FIG. 1 is a perspective view showing an example of a high-viscosity reaction apparatus used for carrying out the production method of the present invention.

FIG. 2 is a partial sectional view of a high-viscosity reaction device.

[Explanation of symbols]

 1 Kneading device 12 Stirring blade 13 Paddle

Claims (10)

[Claims] 1. A method for producing a high molecular weight polyalkylene oxide, which comprises using a high-viscosity reaction apparatus when producing a high molecular weight polyalkylene oxide having a number average molecular weight of 10,000 to 10,000,000. 2. The high molecular weight polyalkylene oxide according to claim 1, which is produced by ring-opening polymerization of an aliphatic cyclic ether having 2 to 6 carbon atoms in the presence of a catalyst. Production method. 3. The high molecular weight polyalkylene oxide comprises a low molecular weight polyalkylene oxide obtained from an aliphatic cyclic ether having 2 to 6 carbon atoms or an aliphatic glycol having 2 to 6 carbon atoms, and a chain extender. The method for producing a high molecular weight polyalkylene oxide according to claim 1, which is produced by reacting. 4. The high-viscosity reaction device is a horizontal biaxial kneading device in which agitation shafts connecting deformation blades are arranged side by side.
4. The method for producing a high molecular weight polyalkylene oxide according to any one of 1 to 3. 5. The self-cleaning horizontal two-axis, wherein the high-viscosity reaction device has two stirring shafts arranged side by side, and a convex lens-shaped paddle incorporated by changing the phase of each stirring shaft. The method for producing a high molecular weight polyalkylene oxide according to any one of claims 1 to 3, which is a kneading device. 6. The high molecular weight product according to claim 1, wherein the high-viscosity reaction device is a horizontal biaxial kneading device in which agitation units having a shaftless structure in which grid-shaped blades are connected are arranged side by side. Method for producing polyalkylene oxide. 7. The high-viscosity reaction device is a horizontal biaxial kneading device in which agitation shafts connecting eyeglass-shaped blades are arranged side by side.
The method for producing a high molecular weight polyalkylene oxide according to claim 1. 8. The high-viscosity reaction apparatus is a vertical kneading apparatus having a plate-shaped stirring blade arranged inside and a deformed spiral blade arranged concentrically outside the plate-shaped stirring blade. The method for producing a high molecular weight polyalkylene oxide according to any one of claims 1 to 3. 9. The method for producing a high molecular weight polyalkylene oxide according to claim 1, wherein the high-viscosity reaction device is a vertical kneading device having an inverted conical ribbon blade. 10. The high molecular weight polyalkylene according to claim 1, wherein the high-viscosity reaction device is a vertical kneading device having an agitating blade having a shaftless structure in which twisted lattice-shaped blades are connected. Method for producing oxide.