JP3776906B2 - Modified high molecular weight polyalkylene oxide, process for producing the same, and use thereof - Google Patents

Description

  The present invention relates to a modified high molecular weight polyalkylene oxide, a method for producing the same, and a use thereof.

Conventionally, a modified high molecular weight polyalkylene oxide has been used for various applications. For example, the modified high molecular weight polyalkylene oxide is formed into a sheet or a film alone or by blending various additives and used for a packaging material or the like. When a modified high molecular weight polyalkylene oxide is formed into a film, it is known that mechanical properties, which are important properties, generally depend greatly on the molecular weight. For this reason, various manufacturing methods listed below have been studied.
For example, when an aliphatic cyclic alkylene oxide such as ethylene oxide is subjected to ring-opening polymerization using a catalyst such as an organometallic complex, a high molecular weight polyalkylene oxide having a polyether structure is obtained. In this method, it is possible to obtain a polyalkylene oxide having a molecular weight of several million or more, but a method for industrially efficiently producing a polyalkylene oxide having a molecular weight of 100,000 to 1,000,000, which is considered to have good moldability, , Not yet found.

Further, ethylene oxide and / or propylene oxide is subjected to ring-opening polymerization using a base such as sodium hydroxide and / or potassium hydroxide as a catalyst to obtain a low molecular weight polyalkylene oxide, which is then reacted with various chain extenders. A method of obtaining a modified high molecular weight polyalkylene oxide by molecular weight is known.
An example in which a carboxylic acid diester is used as a chain extender is disclosed (for example, see Patent Document 1). Although the high molecular weight polyalkylene oxide obtained by this method has a molecular weight of 100,000 or more, the film is very brittle and its elongation is 100% or less. Furthermore, in this method, since the reaction proceeds by a condensation reaction, it is necessary to reduce the pressure of the reaction system in order to remove the alcohol as a by-product. Therefore, the decompression equipment and condensate recovery / treatment costs are high, and the production efficiency is low.

An example in which diisocyanate is used as a chain extender is disclosed (for example, see Patent Document 2). The modified high molecular weight polyalkylene oxide obtained by this method has good mechanical strength that can be molded, but has the problem that the diisocyanate used in the chain extension reaction is extremely toxic. . Due to the risk of diisocyanate remaining in the product, its range of use is limited to a very narrow range. In addition, since diisocyanate is highly reactive, it is difficult to control the reaction, and it is difficult to manage the process during production and the quality control of products.
Furthermore, examples using acid anhydrides as chain extenders are disclosed (see, for example, Patent Documents 3 to 5).

The method described in Patent Document 3 is a method for producing a modified high molecular weight polyalkylene oxide from dianhydropyromellitic anhydride and a low molecular weight polyalkylene oxide. In this method, since a reaction under reduced pressure is essential, branching occurs due to a crosslinking reaction by esterification of a carboxyl group and a hydroxyl group. However, the tear strength of the film is less than 80 kgf / cm ² and the elongation is less than 100%, which is very fragile.
The method described in Patent Document 4 is a method for producing a high molecular weight polyether ester copolymer using a polyether having hydroxyl groups at both terminals and trimellitic anhydride as a branching agent. In this method, the amount of relatively expensive trimellitic anhydride used is about 1.5 to 6.0 mol% per prepolymer, and the reaction is carried out under reduced pressure. Branching occurs due to a crosslinking reaction by esterification with. Further, when the polymer is produced at a high temperature of 200 ° C. or higher, the polymer is frequently thermally deteriorated in the reaction system. In order to prevent thermal degradation, expensive additives such as antioxidants are required, which is not an industrially efficient method.

The method described in Patent Document 5 is a method for producing a modified high molecular weight polyalkylene oxide using polypropylene glycol and pyromellitic dianhydride. In this method, when the molar charge ratio of the two acid anhydride groups contained in the tetracarboxylic dianhydride to the two hydroxyl groups at both ends of the prepolymer is 1.05, it is reported that the molecular weight is increased in the shortest time. Has been. However, the intrinsic viscosity is about 1.6 kg / m ³ regardless of the fact that the reaction is carried out for a long time of 66 hours at 72 ° C. using polyethylene glycol having an intrinsic viscosity of 0.8 kg / m ³ as a raw material. Only rising. Therefore, it is difficult to say that the method is industrially efficient.

When producing the modified high molecular weight polyalkylene oxides listed above, increasing the molecular weight increases the viscosity during production. If a solvent is used to lower the viscosity, a process for removing the solvent at the end of the reaction is required, which is not an industrially efficient method.
Japanese Patent Publication No. 5-68493 JP-A-6-32976 JP 58-179227 A Japanese Patent Publication No. 1-15532 Polymer, 1973, Vol. 14, October, 466-468

  In view of such circumstances, the problem to be solved by the present invention is to provide a method for easily and efficiently producing a modified high molecular weight polyalkylene oxide that can be molded and has high mechanical strength instead of molecular weight. .

The method for producing a modified high molecular weight polyalkylene oxide of the present invention comprises a step of reacting a low molecular weight polyalkylene oxide having a number average molecular weight of 1,000 to 30,000 with a polyhydric acid anhydride. In the production method, the polyhydric acid anhydride is a dihydric acid anhydride, the reaction pressure is 0.094 to 0.3 MPa , and the polyhydric acid anhydride is 1 mol of the hydroxyl group in the low molecular weight polyalkylene oxide. It is characterized by charging and reacting the acid anhydride group in the acid anhydride to 0.8 to 1.0 mol.

  The method for producing a modified high molecular weight polyalkylene oxide of the present invention comprises a step of reacting a low molecular weight polyalkylene oxide having a number average molecular weight of 1,000 to 30,000 with a polyhydric acid anhydride. In the production method, the polyhydric acid anhydride is a dihydric acid anhydride, the reaction pressure is 0.003 MPa or more, and the polyhydric acid anhydride is used with respect to 1 mol of a hydroxyl group in the low molecular weight polyalkylene oxide. It is characterized in that the acid anhydride group therein is charged to 0.8 to 1.0 mol and reacted, so that a modified high molecular weight polyalkylene oxide that can be molded and has high mechanical strength instead of molecular weight is used. It can be manufactured easily and efficiently.

Modified high molecular weight polyalkylene oxide The modified high molecular weight polyalkylene oxide contains a structural unit (1) represented by the following formula (1).

(Wherein R ¹ is a divalent organic group having 2 to 6 carbon atoms, R is a tetravalent organic group having 4 to 20 carbon atoms, and M ¹ and M ² are each a hydrogen atom, a metal atom, or an ammonium atom. And one type selected from an organic amine group and n = 25 to 700.)
R ¹ in formula (1) is not particularly limited as long as it is a divalent organic group having 2 to 6 carbon atoms. Specific examples of R _{^1, -CH 2 -CH 2 -, -} CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) -, - CH 2 -CH 2 -CH 2 -CH 2 _{-, - CH (CH 3)} -CH 2 -CH 2 -, - CH 2 -CH (CH 3) -CH 2 -, - CH 2 -CH (CH 2 CH 3) -, - CH 2 -CH 2 - _{CH 2 -CH 2 -CH 2 -,} - CH (CH 3) -CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) -CH 2 -CH 2 -, - CH 2 -CH 2 _{-CH (CH 2 CH 3) -} , - CH 2 -CH (CH 2 CH 3) -CH 2 -, - CH 2 -CH (CH 2 CH 2 CH 3) -, - CH 2 -CH 2 -CH 2 _{-CH 2 -CH 2 -CH 2 -,} - CH (CH 3) -CH 2 -CH 2 -CH 2 -C _{2 -, - CH 2 -CH (} CH 3) -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH (CH 3) -CH 2 -CH 2 -, - CH (CH 2 CH 3 _{) -CH 2 -CH 2 -CH 2 -} , - CH 2 -CH (CH 2 CH 3) -CH 2 -CH 2 -, - CH 2 -CH 2 -CH (CH 2 CH 2 CH 3) -, - _{CH 2 -CH (CH 2 CH 2} CH 3) -CH 2 -, - CH 2 -CH (CH 2 CH 2 CH 2 CH 3) -, - CH 2 -CH (CH 2 Cl) -, - CH 2 - CH ₂ —CH (CH ₂ Cl) — and the like can be mentioned. These R ¹ may be one kind or a mixture of two or more kinds as required. Among them, ^{R 1} is _{-CH 2 -CH 2 -, - CH} 2 -CH (CH 3) -, - CH 2 -CH 2 -CH 2 -CH 2 - when is at least one selected from easily available It is preferable because it is inexpensive.

  If R in Formula (1) is a C4-C20 tetravalent organic group, there will be no limitation in particular. Specific examples of R include structural units (1) containing R such as the following formulas (4) to (14). These structural units (1) containing R may be one type of modified high molecular weight polyalkylene oxide or a mixture of two or more types as required.

(In the formulas (4) to (14), R ¹ is a divalent organic group having 2 to 6 carbon atoms, and M ¹ and M ² are all selected from a hydrogen atom, a metal atom, an ammonium group, and an organic amine group. And n = 25 to 700.)
Two functional groups represented by the following formula (2) (hereinafter, the functional group represented by the following formula (2) may be referred to as “carboxyl group or the like”) are bonded to R. In addition, R is bonded to two ester groups to repeat the structural unit (1) represented by the formula (1), thereby forming the main chain of the modified high molecular weight polyalkylene oxide. Two carboxyl groups and two ester groups are bonded to R, and there is no particular limitation on the combination of these individual bond chains and carboxyl groups or ester groups.

(In the formula, M is one selected from a hydrogen atom, a metal atom, an ammonium group, and an organic amine group.)
If n in Formula (1) is 25-700, there will be no limitation in particular. n is preferably 50 to 650, more preferably 100 to 570, and most preferably 160 to 530. If n is smaller than the above-mentioned range, the proportion of R derived from an expensive polyhydric acid anhydride described later in the modified high molecular weight polyalkylene oxide becomes large, which is economically disadvantageous. On the other hand, when n is larger than the above-mentioned range, the carboxyl value described later in the modified high molecular weight polyalkylene oxide is lowered and the cohesive force is lost, so that molding becomes difficult.

In formula (1), M ¹ and M ² are each one selected from a hydrogen atom, a metal atom, an ammonium group, and an organic amine group, and M ¹ and M ² may be the same or different. Note that when M ¹ or M ² is a hydrogen atom, the aforementioned carboxyl group or the like is a carboxyl group. When M ¹ or M ² is a metal atom, the carboxyl group or the like becomes a functional group containing a metal salt of a carboxylic acid in which a hydrogen atom in the carboxyl group is replaced with a metal atom. When M ¹ or M ² is an ammonium group, the carboxyl group or the like becomes a functional group containing an ammonium salt of a carboxylic acid derived from ammonia. Further, when M ¹ or M ² is an organic amine group, the carboxyl group or the like becomes a functional group including an organic amine salt of carboxylic acid substituted with a functional group derived from the organic amine.

  The metal atom is not particularly limited as long as it forms a salt with a carboxyl group. Specific examples of metal atoms include lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, titanium, zirconium, hafnium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, Examples include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, copper, silver, zinc, cadmium, mercury, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, antimony, bismuth, scandium, etc. it can. These metal atoms may be used alone or in combination of two or more as required. Among them, when the metal atom is at least one selected from sodium, potassium, magnesium, calcium, zinc, titanium, and zirconium, it is easily available and inexpensive, and the metal is easily introduced as a carboxylate, and the resulting modified high Since the mechanical strength of molecular weight polyalkylene oxide becomes stronger, it is preferable.

  The organic amine group in the present invention has a valence of 4 as a central atom, and at least one of the substituents bonded to the nitrogen atom is an organic group, and at least one of the substituents bonded to the nitrogen atom. The species has a structure that is a hydrogen atom. The organic amine group is derived from organic amines, and is not particularly limited as long as it can form a salt from organic amines and a carboxyl group. Specific examples of such organic amines include hydrazine, trimethylamine, triethylamine, tripropylamine, pyridine, pyrrolidine, pyrrole, dimethylamine, diethylamine, dipropylamine, hexamethylenediamine, 1,4-diazabicyclo [2,2 , 2] octane, N, N-dimethylcyclohexylamine, ethylamine, aniline, toluidine, allylamine, diallylamine, triallylamine, isopropylamine, diisopropylamine, 3,3′-iminobis (propylamine), 2-ethylhexylamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (butyl Mino) propylamine, tetramethylethylenediamine, tri-n-octylamine, tert-butylamine, 2-butylamine, picoline, vinylpyridine, pipecoline, piperazine, piperidine, pyrazine, monoethanolamine, diethanolamine, triethanolamine, etc. Can do. These amines may be used alone or in combination of two or more as required. Among them, when the amine is at least one selected from triethylamine, pyridine, tripropylamine, 1,4-diazabicyclo [2,2,2] octane, tetramethylethylenediamine, the amines are easily available and inexpensive. Is preferable because it can be easily introduced as a carboxylate.

In amines having two or more valent metal atoms and two or more amino groups in the molecule, they may be cross-linked with the side chain carboxylic acid of the modified high molecular weight polyalkylene oxide. When crosslinked with the carboxylic acid in the side chain of the modified high molecular weight polyalkylene oxide, such a crosslinked structure serves to increase the molecular weight and has the effect of improving the mechanical strength. Moreover, in the high temperature range where the obtained modified high molecular weight polyalkylene oxide melts, it has fluidity due to dissociation of ionic bonds, and has ideal physical properties as a polymer material. Therefore, unlike the carbon-carbon crosslinking, no strength reduction due to gelation is observed.
The carboxyl group or the like in the modified high molecular weight polyalkylene oxide is not particularly limited as long as it is 1.0 to 3.0 moles relative to 1 mole of R in the modified high molecular weight polyalkylene oxide, preferably 1.5 to The amount is 2.8 mol, more preferably 1.7 to 2.6 mol, and most preferably 1.8 to 2.5 mol. When the number of moles of a carboxyl group or the like relative to 1 mole of R in the modified high molecular weight polyalkylene oxide (hereinafter sometimes referred to as “carboxyl value”) is within this range, the carboxyl group of the modified high molecular weight polyalkylene oxide, etc. A balance between the cohesive force and the molecular weight is obtained, so that molding is possible and high mechanical strength is achieved. When the carboxyl value is smaller than the above range, the cohesive force between the carboxyl groups and the like is insufficient, and the high mechanical strength that can be molded is not obtained. On the other hand, when the carboxyl value is larger than the above-mentioned range, it is not economical because R derived from an expensive polyhydric acid anhydride described later occupies a large amount in the modified high molecular weight polyalkylene oxide.

If the modified high molecular weight polyalkylene oxide contains only the structural unit (1), the modified high molecular weight polyalkylene oxide has no cross-linked structure and has a straight structure without branching, so that the carboxyl value is increased. Furthermore, it is preferable because the mechanical strength is improved by aggregating carboxyl groups in the side chain of the modified high molecular weight polyalkylene oxide.
The modified high molecular weight polyalkylene oxide may contain a structural unit other than the structural unit (1). As a specific example other than the structural unit (1), a carboxyl group is bonded to a polymer chain of another modified high molecular weight polyalkylene oxide via an ester bond instead of one of the carboxyl groups in the formula (1). Instead of both carboxyl groups in formula (1), both carboxyl groups are bonded to the polymer chain of another modified high molecular weight polyalkylene oxide via an ester bond. Examples include the structural unit (b) to be crosslinked. The following formula (15) represents the structural unit (a), and the following formula (16) represents the structural unit (b).

The proportion of the structural unit (a) in the modified high molecular weight polyalkylene oxide is not particularly limited as long as the carboxyl value with respect to R maintains a range of 1.0 to 3.0 mol. When the value is out of the above range, the mechanical strength is lowered. Therefore, the proportion of the structural unit (a) is preferably 20 mol% or less.
The proportion of the structural unit (b) in the modified high molecular weight polyalkylene oxide is preferably 10 mol% or less. If the structural unit (b) is included, the carboxyl value with respect to R decreases and the mechanical strength decreases significantly. Most preferably, it does not contain at all.
The number average molecular weight of the modified high molecular weight polyalkylene oxide is 40,000 to 10,000,000. Preferably it is 45,000-5,000,000, More preferably, it is 50,000-2,000,000, Most preferably, it is 55,000-1,000,000. When the number average molecular weight is smaller than the above range, the mechanical properties are low and the molding process cannot be performed. On the other hand, if it is larger than the above range, it takes a long time to produce the modified high molecular weight polyalkylene oxide, which makes it difficult to produce, and the melt viscosity at the time of molding is too high to process. When the temperature is raised, the melt viscosity is lowered, but the thermal deterioration is remarkable.

  The modified high molecular weight polyalkylene oxide is a modified high molecular weight polyalkylene oxide obtained by a production method including a step of reacting a low molecular weight polyalkylene oxide having a number average molecular weight of 1,000 to 30,000 with a polyhydric acid anhydride. The polyhydric acid anhydride is a divalent acid anhydride represented by the following formula (3), and the functional group represented by the formula (2) is 1 mol in the modified high molecular weight polyalkylene oxide. What is 1.0-3.0 mol with respect to R may be sufficient.

(In the formula, R is a tetravalent organic group having 2 to 6 carbon atoms.)
The low molecular weight polyalkylene oxide is not particularly limited as long as it has a number average molecular weight of 1,000 to 30,000. Specific examples of the low molecular weight polyalkylene oxide include aliphatic cyclic ethers having 2 to 6 carbon atoms such as polyethylene glycol, polypropylene glycol, polytetraethylene glycol, polyepichlorohydrin, and copolymers thereof, or 2 to 6 carbon atoms. And those obtained from the aliphatic glycols. These low molecular weight polyalkylene oxides may be one kind or a mixture of two or more kinds as required.

When the low molecular weight polyalkylene oxide is at least one selected from polyethylene glycol, polypropylene glycol, and polytetraethylene glycol, the resulting modified high molecular weight polyalkylene oxide has a large molecular weight and is industrially efficiently modified high molecular weight polyalkylene. Since an oxide is obtained, it is preferable.
The number average molecular weight of the low molecular weight polyalkylene oxide is 1,000 to 30,000. Preferably it is 2,000-28,000, More preferably, it is 4,000-26,000, Most preferably, it is 7,000-24,000. If the number average molecular weight is smaller than the above range, the low molecular weight polyalkylene oxide has a melting point of 40 ° C. or lower and in some cases becomes a liquid. The low molecular weight polyalkylene oxide easily absorbs moisture, and is denatured if water is not sufficiently removed. The molecular weight of the high molecular weight polyalkylene oxide cannot be increased. Moreover, when larger than the above-mentioned range, it will heat-deteriorate at the time of reaction, and the thing by which the terminal is not a hydroxyl group will be obtained.

  The polyhydric acid anhydride is not particularly limited as long as it has two or more acid anhydride groups in the molecule. Specific examples of the polyhydric acid anhydride include butane-1,2,3,4-tetracarboxylic dianhydride, dianhydropyromellitic acid, biphenyltetracarboxylic dianhydride, p-terphenyl 3, 4,3 ′, 4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid Dihydric acid anhydrides such as acid anhydrides; Rain acid-styrene copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-vinyl chloride copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride -Trivalent or more acid anhydrides, such as an ethylene copolymer, can be mentioned. These polyhydric acid anhydrides may be used alone or as a mixture of two or more if necessary.

When the polyhydric acid anhydride is a dihydric acid anhydride represented by the formula (3), the resulting modified high molecular weight polyalkylene oxide has no cross-linked structure and has a linear structure with no branching that allows aggregation of carboxyl groups and the like. Therefore, it is preferable because it can be molded and has high mechanical strength instead of molecular weight. In particular, when the dihydric acid anhydride is at least one selected from pyromellitic dianhydride and butane-1,2,3,4-tetracarboxylic dianhydride, the reactivity and production efficiency are high. Therefore, it is more preferable.
R in the formula (3) is the same as R in the above formula (1), and preferred for the same reason are the same. The carboxyl value of the modified high molecular weight polyalkylene oxide obtained by reacting a low molecular weight polyalkylene oxide having a number average molecular weight of 1,000 to 30,000 with a polyhydric acid anhydride is represented by the formula (1) described above. The same range as that of the modified high molecular weight polyalkylene oxide containing the structural unit represented by is preferable for the same reason.

The method for reacting the low molecular weight polyalkylene oxide with the dihydric acid anhydride is not particularly limited, but the production method described below is preferred.
The modified high molecular weight polyalkylene oxide containing a functional group in which M in the formula (2) is at least one selected from a metal atom, an ammonium group and an organic amine group is a low molecular weight polyalkylene oxide and a divalent acid anhydride. And a step of reacting a product (chain extension reaction step) and a step of adding at least one selected from the metal compounds containing metal atoms, ammonia, and amines corresponding to the type of M and reacting them. It is obtained by the manufacturing method described later.

The modified high molecular weight polyalkylene oxide can be used, for example, as a molding material to be described later and processed into a film, a sheet or the like.
Method for Producing Modified High Molecular Weight Polyalkylene Oxide A method for producing a modified high molecular weight polyalkylene oxide includes a step of reacting a low molecular weight polyalkylene oxide having a number average molecular weight of 1,000 to 30,000 with a polyhydric acid anhydride. A method for producing a high molecular weight polyalkylene oxide, wherein the polyhydric acid anhydride is a dihydric acid anhydride, the reaction pressure is 0.003 MPa or more, and 1 mol of hydroxyl group in the low molecular weight polyalkylene oxide, It is characterized in that the acid anhydride group in the polyhydric acid anhydride is charged and reacted so as to be 0.8 to 1.0 mol.

Hereinafter, the step of reacting the low molecular weight polyalkylene oxide and the polyhydric acid anhydride (chain extension reaction step) will be described in detail.
The low molecular weight polyalkylene oxide and the polyhydric acid anhydride are not particularly limited, but the compounds shown as specific examples above are preferred for the same reason.
The number of moles of the acid anhydride group in the polyhydric acid anhydride relative to 1 mole of the hydroxyl group in the low molecular weight polyalkylene oxide (hereinafter sometimes referred to as the molar charge ratio) is in the range of 0.8 to 1.0 mole. If there is no particular limitation. The molar charge ratio is preferably 0.85 to 1.0 mol, more preferably 0.87 to 1.0 mol, and most preferably 0.90 to 1.0 mol. When the molar charge ratio is smaller than the above range, a large amount of unreacted low molecular weight polyalkylene oxide is contained in the produced polymer, so that the mechanical strength is lowered. Moreover, when larger than the above-mentioned range, many low molecular weight polyalkylene oxides blocked with the polyhydric acid anhydride will produce | generate in a reaction system. Furthermore, since both ends of the modified polyalkylene oxide in the middle of growth are blocked with polyhydric acid anhydride, the hydroxyl group which is a growth factor in the reaction disappears from the reaction system and the reaction stops. As a result, many low molecular weight polyalkylene oxides having both ends blocked with a polyhydric acid anhydride are present in the product, and the mechanical strength is lowered.

In the method for producing a modified high molecular weight polyalkylene oxide, the polyhydric acid anhydride is a dihydric acid anhydride. The divalent acid anhydride is not particularly limited, and examples thereof include the compounds shown as specific examples above.
If the polyhydric acid anhydride is a dihydric acid anhydride, the resulting modified high molecular weight polyalkylene oxide basically has no cross-linked structure and has a linear structure with no branching, so the mechanical strength is high. Therefore, it is preferable. In particular, when the dihydric acid anhydride is at least one selected from butane-1,2,3,4-tetracarboxylic dianhydride and dianhydropyromellitic acid, the reactivity is high and the production efficiency is high. Therefore, it is preferable.

The reaction temperature in the method for producing the modified high molecular weight polyalkylene oxide is not particularly limited. The reaction temperature is preferably 70 to 250 ° C, more preferably 80 to 200 ° C, and most preferably 100 to 180 ° C. When the reaction temperature is in the above-mentioned range, the reaction can be carried out efficiently, and the modified high molecular weight polyalkylene oxide is hardly deteriorated by heat, so that an additive such as an antioxidant described later is not necessary.
The reaction pressure in the method for producing the modified high molecular weight polyalkylene oxide is not particularly limited as long as it is 0.003 MPa or more. The reaction pressure is preferably 0.030 MPa or more, more preferably 0.080 MPa or more, and most preferably 0.094 MPa or more. If the reaction pressure is too low, the reaction system will be in a reduced pressure state, and a dehydration reaction as a side reaction will be promoted between the carboxyl group in the resulting modified high molecular weight polyalkylene oxide and the hydroxyl group in the low molecular weight polyalkylene oxide. A product in which the carboxyl group as a by-product is esterified is obtained. When an esterified product is obtained, the carboxyl value of the modified high molecular weight polyalkylene oxide is decreased, the cohesive force such as carboxyl groups between the molecules of the modified high molecular weight polyalkylene oxide is lost, and the mechanical strength is significantly decreased. .

The reaction pressure is not particularly limited as long as it is 0.003 MPa or more as described above, but the reaction pressure may have an upper limit, preferably 2.0 MPa or less, more preferably 1.5 MPa or less, more preferably 1.0 MPa or less, most preferably 0.3 MPa or less. When the reaction pressure is too high, production equipment for pressurization is required, and the production efficiency may be reduced by pressurization.
In the method for producing the modified high molecular weight polyalkylene oxide, a solvent, an antioxidant, an ultraviolet absorber, a crystal nucleating agent, or the like may be used as a component other than the above-described low molecular weight polyalkylene oxide and polyhydric acid anhydride.

  In the method for producing the modified high molecular weight polyalkylene oxide, the viscosity is low in the early stage of the reaction, but a solvent may be used in order to prevent the viscosity from increasing along with the molecular weight in the late stage of the reaction and making stirring difficult. Specific examples of the reaction solvent include benzene, toluene, xylene, ethylene carbonate, propyl carbonate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, 1,4-dioxane, anisole, acetone, methyl ethyl ketone, diethyl ketone, and methyl. Examples thereof include propyl ketone, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, acetonitrile, pyridine, dimethylformamide, ethylenediamine, and propylenediamine. One of these reaction solvents or a mixture of two or more as necessary may be used.

However, when a reaction solvent is used, stirring during the reaction is facilitated. However, a step of removing the reaction solvent (devolatilization step) is required after the reaction is completed, and the modified high molecular weight polyalkylene oxide containing the reaction solvent is subjected to high vacuum. Since the reaction solvent cannot be removed completely without devolatilization below, the production efficiency may be lowered.
From such a viewpoint, in the method for producing a modified high molecular weight polyalkylene oxide, it is preferable to carry out the reaction using a high-viscosity reactor because it can be produced more easily and efficiently.
Specific examples of the high-viscosity reactor include a horizontal biaxial kneading apparatus (Irie Shokai, trade name “1 liter kneader”) in which stirring shafts with deformed blades are arranged side by side, two stirring shafts arranged side by side, Self-cleaning horizontal biaxial kneading apparatus having a convex lens-shaped paddle incorporated in each stirring shaft with a phase changed, and horizontal biaxial in which stirring portions of an axisless structure in which lattice-shaped blades are connected are arranged side by side A kneading device, a horizontal biaxial kneading device in which stirring shafts connected with glasses-like blades are arranged side by side, a plate-like stirring blade arranged on the inside, and a deformed spiral arranged concentrically on the outside of the plate-like stirring blade Examples thereof include a vertical kneading apparatus having blades, a vertical kneading apparatus having inverted conical ribbon wings, and a vertical kneading apparatus having stirring shafts having a shaftless structure in which twisted lattice blades are connected.

The high viscosity reactor may be continuous or batch.
As an example of the continuous high-viscosity reactor, there is a horizontal biaxial kneader (trade name “KRC Kneader” manufactured by Kurimoto Iron Works Co., Ltd.) shown in FIG.
The kneading apparatus 1 includes a kneader body 2, a solid supply unit 3 that supplies a powder or fluid to the kneader body 2, a liquid supply unit 4 that supplies a liquid or slurry liquid to the kneader body 2, and a kneader body. And a heating / cooling device 5 for heating / cooling 2.
The kneader body 2 includes a drive unit 10 composed of a motor and a speed reducer, a trough 11 divided into two, and two agitation shafts 12 rotatably supported by the trough 11 and driven by the drive unit 10 (FIG. 2). And have. As shown in FIG. 2, various paddles 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. Each paddle 13 is arranged with a phase shift in units of several sheets. As a result, even if the two types of raw materials supplied into the trough 11 have a high viscosity, they are efficiently kneaded and conveyed in a short time.

In the kneading apparatus 1, the polyhydric acid anhydride is stored in the raw material supply unit 3, and the low molecular weight polyalkylene oxide is stored in the raw material supply unit 4. Then, a predetermined amount of two kinds of raw materials are supplied from the supply units 3 and 4 into the trough 11, and low molecular weight polyethylene oxide is heated and melted and kneaded and reacted with a polyhydric acid anhydride under normal pressure. Thereby, a modified high molecular weight polyalkylene oxide is obtained.
Other continuous high-viscosity reactors are biaxial horizontal kneaders with stirring blades having spectacle blades (Hitachi Ltd., trade name “Hitachi Glasses blade polymerizer”), with stirring blades having lattice blades. (Hitachi, Ltd., trade name "Hitachi Lattice Blade Polymerizer"), stirring blades are petal-shaped, stirring blades are self-cleaning type with knitting core disk (Mitsubishi Heavy Industries, Ltd., trade name " SCR "), and a stirring blade having a hollow disk blade or a three-blade blade (Mitsubishi Heavy Industries, Ltd., trade name" HVR "). Moreover, you may use the uniaxial or biaxial extruder widely used for the extrusion molding or devolatilization of the brand name "TEX-X" made from Nippon Steel Works, Ltd., or a plastic.

The batch type high-viscosity reactor is a vertical kneader with two stirring shafts installed concentrically and a stirring blade with an inverted conical ribbon shape (Mitsubishi Heavy Industries, Ltd.) , Trade name “VCR”), a stirring blade having a twisted lattice blade (manufactured by Hitachi, Ltd.), a trade name “Hitachi High Viscosity Batch Polymerizer”) and the like.
The modified high molecular weight polyalkylene oxide thus obtained can be molded and applied effectively to various uses, for example, molding materials described below.
The method for producing a modified high molecular weight polyalkylene oxide may further include a step of adding and reacting at least one selected from a metal compound, ammonia, and the amines.

Adding at least one selected from a metal compound, ammonia, and the amines (hereinafter, at least one selected from a metal compound, ammonia, and the amines may be referred to as “carboxyl group modifier”) It may be at any point during the chain extension reaction, during the chain extension reaction, or after the chain extension reaction, but it is added during the chain extension reaction or during the chain extension reaction to shorten the reaction time and the production process. It is preferable to meet the simplification.
Metal compounds include oxides, carboxylates, metal alkoxides, carbonates, hydroxides, hydrides, peroxides, chlorides, nitrates, phosphates, sulfates, sulfites, carbides containing the aforementioned metal atoms. Etc. These metal compounds may be used alone or in combination of two or more as required. In particular, when the metal compound is at least one selected from oxides, carbonates, and hydroxides, the compatibility with the low molecular weight polyalkylene oxide and the modified high molecular weight polyalkylene oxide is good, so that the metal is easily introduced. It is preferable because it is safe, easy to handle during manufacture, and inexpensive.

A simple metal which is not a metal compound can be used as it is as a carboxyl group modifier. Specific examples of the simple metal include lithium, sodium, and potassium. However, when such a single metal is used, it is necessary to make every effort to ensure safety because it reacts with air and moisture and has a high risk of causing a fire.
About amines, what was illustrated above can be used as it is. In addition, the same preferable amines are the same for the same reason as described above.
The carboxyl group modifier is not particularly limited as long as it is 0.001 to 10.0 mol per mol of the polyhydric acid anhydride. The addition amount is preferably 0.1 to 5.0 mol, more preferably 0.5 to 3.0 mol. When the addition amount is larger than the above range, the carboxyl group modifier cannot be uniformly dispersed and dissolved in the modified high molecular weight polyalkylene oxide, so that the mechanical strength of the modified high molecular weight polyalkylene oxide is lowered. Moreover, when there are many carboxyl group modifiers, reaction time will become long and manufacturing efficiency will fall. When the addition amount is less than the above range, the effect of adding the carboxyl group modifier is reduced.

When the carboxyl group modifier is reacted, the reaction temperature is not particularly limited. The reaction temperature is preferably 70 to 250 ° C, more preferably 80 to 200 ° C, and most preferably 100 to 180 ° C. When the reaction temperature is in the above-mentioned range, the reaction can be carried out efficiently, and the modified high molecular weight polyalkylene oxide is hardly deteriorated by heat, so that an additive such as an antioxidant described later is not necessary.
When the carboxyl group modifier is reacted, the reaction pressure is not particularly limited. The reaction pressure is not particularly limited as long as it is 0.003 MPa or more, as in the above-described chain extension reaction step. The reaction pressure is preferably 0.030 MPa or more, more preferably 0.080 MPa or more, and most preferably 0.094 MPa or more.

Furthermore, as the reaction apparatus used when reacting the carboxyl group modifier, the high-viscosity reaction apparatus used in the above-described chain extension reaction step is preferably used.
Use of modified high molecular weight polyalkylene oxide (molding material)
The molding material contains the aforementioned modified high molecular weight polyalkylene oxide.
The molding material is heated as necessary, and the melt viscosity at that time is preferably 10,000 to 100,000,000 cP, more preferably 20,000 to 80,000,000 cP, most preferably 50, 000-70,000,000 cP. If the melt viscosity of the molding material is too high, the molding process cannot be performed. Conversely, if the melt viscosity of the molding material is too low, the fluidity is too high to perform the molding process. The temperature of the molding material at the time of melt viscosity measurement is not particularly limited. However, if it is 70 to 200 ° C., which is a normal molding temperature, the melting point of the modified high molecular weight polyalkylene oxide is exceeded, and thermal deterioration occurs during molding. It is preferable because it is difficult.

The molding material may contain a modified high molecular weight polyalkylene oxide as an essential component and may contain other material components. Specific examples of components other than the modified high molecular weight polyalkylene oxide include inorganic fillers, ultraviolet absorbers, and pigments.
The molding method of the molding material is not particularly limited. Specific examples of the molding method of the molding material include injection molding, compression molding, T-die method, inflation method, calendar method and the like.
The molding material can be processed into various molded products by the above-described molding method, and specifically can be molded into a film, a sheet, or the like.
〔the film〕
All films contain the aforementioned modified high molecular weight polyalkylene oxide. Among them, the film (1) has a tensile strength of 80 kgf / cm ² or more, and the film (2) has an elongation percentage of 100% or more. In addition, any film may have a tensile strength of 80 kgf / cm ² or more and an elongation of 100% or more.

The modified high molecular weight polyalkylene oxide in the film is not particularly limited as long as it has a number average molecular weight of 40,000 to 10,000,000. The number average molecular weight is preferably 45,000 to 2,000,000, more preferably 50,000 to 1,000,000. When the number average molecular weight is smaller than the above range, the mechanical properties (tensile strength and elongation) are low, and the film cannot be formed. On the other hand, if the number average molecular weight is larger than the above range, the melt viscosity at the time of forming into a film is too high to form.
The tensile strength of the film (1) is not particularly limited as long as it is 80 kgf / cm ² or more. Tensile strength is preferably 85 kgf / cm ² or more, more preferably 90 kgf / cm ² or more, most preferably 100 kgf / cm ² or more. When the tensile strength is outside the above range, the tensile strength is low, and the film may burst due to its own weight when used as a packaging material or the like, and the content may not be wrapped.

If the elongation rate of a film (2) is 100% or more, there will be no limitation in particular. The elongation is preferably 200%, more preferably 500% or more, and most preferably 700%. If the tensile strength is outside the above range, the elongation is low, the elasticity of the film is low, and the film is broken. The elasticity of the film acts as a cushion when a force is applied to the film, and functions to prevent the film from breaking.
There is no particular limitation on the thickness of the film. The thickness of the film is preferably 2 to 700 μm, more preferably 5 to 500 μm, and most preferably 10 to 300 μm. It is preferable that the thickness of the film is in the above-mentioned range since a flexible and tough film can be obtained. However, when the film can be multilayered and the strength can be ensured by the base material to be overlapped, there may be no problem even if it is thinner than 10 μm.

  There is no restriction | limiting in particular in the manufacturing method of the film containing a modified | denatured high molecular weight polyalkylene oxide, The manufacturing method of a conventionally well-known film can be applied. Specific examples of the film production method include a T-die method, an inflation method, and a calendar method. In the T-die method, the inflation method, and the calendar method, the modified high molecular weight polyalkylene oxide can be molded into a film by extruding at a molding machine outlet temperature of 50 to 250 ° C, preferably 100 to 180 ° C. When the exit temperature of the molding machine is higher than this temperature range, the melt viscosity of the modified high molecular weight polyalkylene oxide becomes very low, so that the inflation cannot be supported by the inflation method, making it difficult to continuously remove the film. Further, in the T-die method, the width of the molten film after extrusion becomes narrow due to surface tension, and problems such as perforation and tearing occur. Furthermore, it is not preferable to store the modified high molecular weight polyalkylene oxide at 250 ° C. or higher for a long time because it causes thermal deterioration and the quality of the resulting film is lowered. When the molding machine outlet temperature is lower than this temperature range, the melt state of the modified high molecular weight polyalkylene oxide becomes non-uniform, making it difficult to obtain a homogeneous film, and the production efficiency of the film is remarkably high because the melt viscosity is high. May decrease.

The melted film thus extruded has good surface smoothness, transparency, uniformity and mechanical properties by cooling to 0 to 45 ° C. with a cooling time of 5 seconds to 3 minutes. A film can be obtained with high production efficiency.
In the method for producing a film, a molding material containing the above-described modified high molecular weight polyalkylene oxide may be molded.
The obtained film may be further stretched in the length and / or width direction.
The film may contain material components other than the modified high molecular weight polyalkylene oxide. Examples of such material components include stabilizers, crystal nucleating agents, extenders, pigments, colorants, ultraviolet absorbers, surface brighteners, inorganic fillers, antioxidants, plasticizers, lubricants, and the like. . These material components may be added to the modified high molecular weight polyalkylene oxide before production of the film, or may be added to the film after production. When the blending amount of the material component is 0.0001 to 30% by weight based on the modified high molecular weight polyalkylene oxide, the effect of adding the material component can be obtained.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the examples, “part” represents “part by weight”.
-Example A1-
A 100 ml flask was charged with 10 parts of polyethylene glycol having a number average molecular weight of 10,000 and 0.207 parts of pyromellitic dianhydride and subjected to a high molecular weight reaction for 3 hours under the reaction conditions of 0.099 MPa and 150 ° C. The resulting modified high molecular weight polyalkylene oxide (A1) had a number average molecular weight of 84,000 and a melt viscosity of 102,000 cP. The measurement result of the acid value by neutralization titration was 9.92 mgKOH / g, and the carboxyl value was 1.99 mol.

Using a modified high molecular weight polyalkylene oxide (A1) as a molding material, using a compression molding machine under a molding temperature of 150 ° C., a molding pressure of 100 kgf / cm ² , and a molding time of 2 minutes, a 200 micron thick film (A1 )was gotten. The film (A1) was subjected to a tensile test and had a tensile strength of 95 kgf / cm ² and an elongation of 912%.
These results are summarized in Table 1.
The elemental analysis, infrared absorption spectrum, and ¹ H-NMR measurement results of the modified high molecular weight polyalkylene oxide (A1) are as follows.
Elemental analysis measurement Measured value H: 9.08% (theoretical value H: 9.00%)
C: 54.34% (theoretical value C: 54.50%)
Infrared absorption spectrum 2954.2 cm ⁻¹ (C—H, stretching vibration)
1731.6 cm ⁻¹ (C═O, stretching vibration, carboxyl group, ester group)
1160.1 cm ⁻¹ (C—O, stretching vibration)
¹ H-NMR (δ value, CDCl ₃ )
_{3.44-3.36 (-OCH 2 CH 2 O-,} m)
4.44-3.51 (-OH, m)
8.03 (-COOH meeting, s)
8.08 (Aromatic proton derived from dianhydropyromellitic anhydride, 2H, s)
8.12 (-COOH meeting, s)
The number average molecular weight, carboxyl number, melt viscosity, tensile strength, and elongation were measured by the following methods.
(Number average molecular weight)
The number average molecular weight in terms of polystyrene was measured using a gel permeation chromatograph.
(Carboxyl value)
The definition of the carboxyl value is described above, and the amount of R in the modified high molecular weight polyalkylene oxide is 1 mole of R in the modified high molecular weight polyalkylene oxide (1 mole of polyhydric acid anhydride charged in the reaction). The number of moles of the carboxyl group or the like was defined as the carboxyl value. Specifically, the obtained modified high molecular weight polyalkylene oxide was dissolved in pure water, and the carboxyl value was determined from the acid value measured according to JIS K0070 and the number average molecular weight measured by the above method. Further, in the modified high molecular weight polyalkylene oxide in which M is at least one selected from a metal atom, an ammonium group and an organic amine group, this is dissolved in pure water, an acid such as hydrochloric acid is added, and the metal atom, ammonium group is added. After completely releasing an organic amine group and the like to completely release a weakly acidic carboxyl group, the carboxyl value of the released carboxyl group can be determined in the same manner as described above.
(Melt viscosity)
Measurement was performed using a Shimadzu flow tester (model: CFT-500C). The measurement conditions are 150 ° C., constant temperature method, and cylinder pressure 30 kgf / cm ² . The die used was L (length): 1.00 mm and D (hole diameter): 0.50 mm.
(Tensile strength and elongation)
In accordance with JIS K7113 , a tensile test was performed at a test speed of 20 mm / min, and the tensile strength and elongation at the time of fracture were measured.

-Examples A2-A5-
Except having changed the molecular weight of polyethyleneglycol into what was shown in Table 1, it reacted like Example A1, and modified high molecular weight polyalkylene oxide (A2)-(A5) was obtained. Further, films (A2) to (A5) were obtained in the same manner as in Example A1. These results are summarized in Table 1.
-Examples A6 to A8-
Example A1 except that the molecular weight of polyethylene glycol was changed to that shown in Table 1, and further changed to 3,4,9,10-perylenetetracarboxylic dianhydride as the polyhydric acid anhydride. Reaction was performed in the same manner to obtain modified high molecular weight polyalkylene oxides (A6) to (A8). Further, films (A6) to (A8) were obtained in the same manner as in Example A1. These results are summarized in Table 1.

-Example A9-
A modification containing a calcium salt of a carboxylic acid in which the hydrogen atom of the carboxyl group was replaced with calcium was carried out in the same manner as in Example A1, except that 0.108 part of calcium carbonate was further added to the preparation of Example A1. A high molecular weight polyalkylene oxide (A9) was obtained. Further, a film (A9) was obtained in the same manner as in Example A1. These results are summarized in Table 1.
-Example A10-
A high molecular weight reaction was carried out in the same manner as in Example A1, except that 0.231 parts of 1,4-diazabicyclo [2,2,2] octane was further added to the preparation of Example A1, and the hydrogen atom of the carboxyl group was organic. A modified high molecular weight polyalkylene oxide (A10) containing an organic amine salt of a carboxylic acid substituted with an amine group was obtained. Further, a film (A10) was obtained in the same manner as in Example A1. These results are summarized in Table 1.

-Example A11-
0.051 part of calcium carbonate was added to the modified high molecular weight polyalkylene oxide (A8) obtained in Example A8 and in the molten state immediately after the reaction, and heated and stirred for 1 hour under the same reaction conditions as in Example A8. . A modified high molecular weight polyalkylene oxide (A11) containing a calcium salt of a carboxylic acid in which the hydrogen atom of the carboxyl group was substituted with calcium was obtained. Further, a film (A11) was obtained in the same manner as in Example A1. These results are summarized in Table 1.
-Example A12-
Example A1 except that 0.111 part of 1,4-diazabicyclo [2,2,2] octane was added to the modified high molecular weight polyalkylene oxide (A8) obtained in Example A8 and in the molten state immediately after the reaction. In the same manner as above, a high molecular weight reaction was carried out to obtain a modified high molecular weight polyalkylene oxide (A12) containing an organic amine salt of a carboxylic acid in which the hydrogen atom of the carboxyl group was substituted with an organic amine group. Further, a film (A12) was obtained in the same manner as in Example A1. These results are summarized in Table 1.

-Comparative examples A1-A3-
The molecular weight of polyethylene glycol was changed to that shown in Table 2, and the reaction was conducted in the same manner as in Example A1 except that the charge ratio of pyromellitic dianhydride to polyethylene glycol was changed. The alkylene oxides (A1) to (A3) were obtained. Further, a film (A2) and a film (A3) were obtained in the same manner as in Example A1, but a film (A1) was not obtained. These results are summarized in Table 2.

The melt viscosity of the modified high molecular weight polyalkylene oxide shown in the above examples is in a viscosity range suitable for molding and can be molded into a film or the like. Further, the films shown in the above examples are superior to the mechanical strength of the comparative film.
-Example B1-
A 100 ml flask is charged with 10 parts of polyethylene glycol having a number average molecular weight of 20,000 and 0.106 part of dianhydropyromellitic acid (note that the hydroxyl group in polyethylene glycol and the acid anhydride group in dianhydropyromellitic acid The molar ratio [acid anhydride group / hydroxyl group] was 0.97), and the high molecular weight reaction was carried out for 4 hours under the reaction conditions of 0.100 MPa and 150 ° C. The number average molecular weight of the obtained modified high molecular weight polyalkylene oxide (B1) was 146,000.

Using a modified high molecular weight polyalkylene oxide (B1) as a molding material, using a compression molding machine under the conditions of a molding temperature of 150 ° C., a molding pressure of 100 kgf / cm ² , and a molding time of 2 minutes, a film (B1 )was gotten. The film (B1) was subjected to a tensile test and had a tensile strength of 187 kgf / cm ² and an elongation of 2001%.
These results are summarized in Table 3.
-Examples B2-B6-
The molecular weight of polyethylene glycol and the molar ratio of the hydroxyl group in polyethylene glycol to the acid anhydride group in pyromellitic dianhydride (molar charge ratio, acid anhydride group / hydroxyl group) were changed to those shown in Table 3. Otherwise, the reaction was carried out in the same manner as in Example B1, to obtain modified high molecular weight polyalkylene oxides (B2) to (B6). Further, films (B2) to (B6) were obtained in the same manner as in Example B1. These results are summarized in Table 3.

-Examples B7 to B8-
Example B1 except that pyromellitic dianhydride was replaced with 3,4,9,10-perylenetetracarboxylic dianhydride in Example B1 and the others were changed to those shown in Table 3. Reaction was performed in the same manner to obtain modified high molecular weight polyalkylene oxides (B7) to (B8). Further, films (B7) to (B8) were obtained in the same manner as in Example B1. These results are summarized in Table 3.
-Example B9-
A modification containing a calcium salt of a carboxylic acid in which the hydrogen atom of the carboxyl group was replaced with calcium was carried out in the same manner as in Example A1, except that 0.058 part of calcium carbonate was further added to the preparation of Example B1. A high molecular weight polyalkylene oxide (B9) was obtained. Further, a film (B9) was obtained in the same manner as in Example A1. These results are summarized in Table 3.

-Example B10-
A high molecular weight reaction was carried out in the same manner as in Example A1 except that 0.119 part of 1,4-diazabicyclo [2,2,2] octane was further added to the preparation of Example B1, and the hydrogen atom of the carboxyl group was organic. A modified high molecular weight polyalkylene oxide (B10) containing an organic amine salt of a carboxylic acid substituted with an amine group was obtained. Further, a film (B10) was obtained in the same manner as in Example A1. These results are summarized in Table 3.
-Example B11-
0.055 parts of calcium carbonate was added to the modified high molecular weight polyalkylene oxide (B8) obtained in Example B8 and in the molten state immediately after the reaction, and the mixture was heated and stirred for 1 hour under the same reaction conditions as in Example B8. . A modified high molecular weight polyalkylene oxide (B11) containing a calcium salt of a carboxylic acid in which the hydrogen atom of the carboxyl group was substituted with calcium was obtained. Further, a film (B11) was obtained in the same manner as in Example A1. These results are summarized in Table 3.

-Example B12-
Example A1 except that 0.120 part of 1,4-diazabicyclo [2,2,2] octane was added to the modified high molecular weight polyalkylene oxide (B8) obtained in Example B8 and in the molten state immediately after the reaction. In the same manner as above, a high molecular weight reaction was carried out to obtain a modified high molecular weight polyalkylene oxide (B12) containing an organic amine salt of a carboxylic acid in which the hydrogen atom of the carboxyl group was substituted with an organic amine group. Further, a film (B12) was obtained in the same manner as in Example A1. These results are summarized in Table 3.

-Comparative examples B1-B4-
The reaction was conducted in the same manner as in Example B1 except that the molecular weight of polyethylene glycol, the molar charge ratio of pyromellitic dianhydride, and the reaction temperature were changed to those shown in Table 4, and comparatively modified high molecular weight polyalkylene oxide ( B1) to (B4) were obtained. Furthermore, the film (B1) and the film (B4) were obtained in the same manner as in Example B1, and films (B2) to (B3) were not obtained. These results are summarized in Table 4.

The high molecular weight polyalkylene oxides shown in the above examples have a number average molecular weight larger than that of the comparative example, and the film has excellent mechanical strength.
-Example C1-
To the autoclave, 0.065 parts of sodium hydroxide and 15 parts of triethylene glycol were added, and nitrogen substitution was performed. Next, the temperature of the autoclave was gradually raised to 150 ° C. with stirring, and 570 parts of ethylene oxide was continuously introduced over 20 hours while maintaining the pressure in the autoclave at 0 to 10 kgf / cm ² at the same temperature. After introducing ethylene oxide, a aging reaction was performed at 150 ° C. for 2.0 hours, and then the reaction system was returned to room temperature to obtain low molecular weight polyethylene oxide. The yield of polyethylene oxide was 99%. Moreover, the number average molecular weight was 13,000 from the gel permeation chromatograph measurement result.

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., 7.8 parts of pyromellitic dianhydride was added, and the reaction pressure was 0.100 MPa. The high molecular weight reaction was performed for 30 minutes.
From the results of gel permeation chromatography, the number average molecular weight of the obtained modified high molecular weight polyalkylene oxide was 112,000.
-Example C2-
Low molecular weight polyethylene oxide and pyromellitic dianhydride obtained in the same manner as in Example C1 are continuously charged into a horizontal biaxial extruder for high viscosity and subjected to a high molecular weight reaction at 150 ° C. and a reaction pressure of 0.100 MPa. It was. At this time, the residence time until the low molecular weight polyethylene oxide was charged in the horizontal biaxial extruder for high viscosity, reacted with pyromellitic dianhydride to increase the molecular weight, and was taken out from the apparatus outlet was 10 minutes.

From the results of gel permeation chromatography, the number average molecular weight of the obtained modified high molecular weight polyalkylene oxide was 103,000.
-Comparative Example C1-
A 100 ml flask was charged with 10 parts of the low molecular weight polyethylene oxide number average molecular weight 13,000 obtained in Example C1 and 0.1 part of pyromellitic dianhydride at 150 ° C. and a reaction pressure of 0.100 MPa for 6 hours. The reaction was carried out.
From the results of gel permeation chromatography, the number average molecular weight was 45,000.

  The high molecular weight polyalkylene oxide obtained in Examples C1 and C2 has a large number average molecular weight and a very short reaction time compared to Comparative Example C1.

The perspective view which shows an example of the reactor for high viscosity used for implementation of the manufacturing method of this invention. FIG.

Explanation of symbols

1 Kneading device 12 Stirring blade 13 Paddle

Claims (1)

A method for producing a modified high molecular weight polyalkylene oxide comprising a step of reacting a low molecular weight polyalkylene oxide having a number average molecular weight of 1,000 to 30,000 with a polyhydric acid anhydride,
The polyhydric acid anhydride is a dihydric acid anhydride, the reaction pressure is 0.094 to 0.3 MPa , and the acid in the polyhydric acid anhydride is 1 mol of hydroxyl group in the low molecular weight polyalkylene oxide. A method for producing a modified high molecular weight polyalkylene oxide, characterized in that an anhydride group is charged and reacted so as to be 0.8 to 1.0 mol.

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