JPH0948847A - Modified high molecular weight polyalkylene oxide, its production and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject moldable polymer having specific structure units, having a high mechanical strength in comparison with the molecular weight, capable of being easily and efficiently produced, and giving films high in mechanical strengths. SOLUTION: A modified high mol.wt. polyalkylene oxide has structural units of the formula (R<1> is a 2-6C divalent organic groups; R is a 4-20C tetravalent organic groups; M<1> , M<2> are each H, a metal atom, etc.; n is 25-700), contains one to three functional groups of formula: -COOM (M is M<1> ) per mole of R, and has a number-average mol.wt. of 40000-10000000. The objective polymer is obtained by charging a polyalkylene oxide having a number-average mol.wt. of 1000-30000 and a divalent acid anhydride in a reactor so that the acid anhydride group content of the divalent acid anhydride is 0.8-1 mole per mole of the hydroxyl group of the polyalkylene oxide, reacting the compounds with each other at >=0.003MPa, and further reacting the reaction product with a compound corresponding to the M, such as a metal compound or an amine compound. The divalent acid anhydride is preferably pyromellitic acid dianhydride.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, a modified high molecular weight polyalkylene oxide has been used for various purposes. For example, it has been used alone or by blending various additives to form a sheet or film, and used as a packaging material. There is. It is known that when a modified high molecular weight polyalkylene oxide is formed into a film, its mechanical properties, which are important properties, generally depend largely on its molecular weight. Therefore, various manufacturing methods listed below have been investigated.

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 can be obtained. With 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 said to have good moldability, is , Currently not found.

Further, ethylene oxide and / or propylene oxide are 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, and then various chain extenders are added. A method is known in which a modified high molecular weight polyalkylene oxide is obtained by reacting to obtain a high molecular weight. An example of using a carboxylic acid diester as a chain extender is disclosed in JP-B-5-684.
No. 93 publication. The high molecular weight polyalkylene oxide obtained by this method has a molecular weight of 100,000 or more, but its film is very fragile and its elongation is 100% or less. Further, in this method, since the reaction proceeds by the condensation reaction, it is necessary to bring the reaction system into a reduced pressure state in order to remove the by-product alcohol. Therefore, the decompression equipment and the cost for collecting and treating the condensate are high, and the production efficiency is low.

An example of using diisocyanate as a chain extender is disclosed in JP-A-6-32976.
The modified high molecular weight polyalkylene oxide obtained by this method has good mechanical strength capable of being molded and processed, but has a problem that the toxicity of diisocyanate used in the chain extension reaction is extremely high. . Due to the risk of diisocyanate remaining in the product, its use is limited to a very narrow range. Further, since diisocyanate has high reactivity, it is difficult to control the reaction, and it is difficult to control the process during production and the quality control of the product.

Further, examples of using an acid anhydride as a chain extender are disclosed in JP-A-58-179227, JP-B-1-15532 and Polymer, 197.
3, Vol. 14, October, 466-468. The method described above is a method for producing a modified high molecular weight polyalkylene oxide from pyromellitic dianhydride and a low molecular weight polyalkylene oxide. In this method, since the 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 100
%, Which is very vulnerable.

The method described above is a method for producing a high molecular weight polyether ester copolymer by using a polyether having hydroxyl groups at both ends as trimellitic anhydride as a branching agent. In this method, the amount of relatively expensive trimellitic anhydride used is about 1.5 per prepolymer.
Since the reaction is performed in a very large amount of up to 6.0 mol% and under reduced pressure, branching occurs due to a crosslinking reaction by esterification of a carboxyl group and a hydroxyl group. Furthermore, 200 ℃
When produced at the above high temperature, thermal degradation of the polymer frequently occurs in the reaction system. In order to prevent thermal deterioration, expensive additives such as antioxidants are required, which is not an industrially efficient method.

The method described above is based on polypro
Highly modified with pyrene glycol and pyromellitic dianhydride
A method for producing a molecular weight polyalkylene oxide.
You. In this method, two hydroxyl groups at both ends of the prepolymer are used.
Two included in tetracarboxylic acid dianhydride for the group
If the molar charge ratio of the acid anhydride group is 1.05, the shortest
It has been reported that the molecular weight increases with time. But firm
Viscosity 0.8kg / m ^ThreeOf polyethylene glycol
As a raw material, the reaction was performed at 72 ° C for a long time of 66 hours.
Inherent viscosity of 1.6kg
/ M^ThreeThe molecular weight has risen only to a certain degree. Accordingly
It is hard to say that it is an industrially efficient method.

When the above-mentioned modified high molecular weight polyalkylene oxide is produced, the viscosity at the time of production is increased by increasing the molecular weight. If a solvent is used to reduce the viscosity, a step of removing the solvent is required at the end of the reaction,
Not an industrially efficient method.

[0010]

In view of such circumstances, an object of the present invention is to provide a modified high molecular weight polyalkylene oxide which is moldable and has high mechanical strength in view of its molecular weight. is there. Another problem to be solved by the present invention is to provide a film having high mechanical strength.

Still another object to be solved by the present invention is to provide a method for easily and efficiently producing a modified high molecular weight polyalkylene oxide which is moldable and has high mechanical strength in view of its molecular weight.

[0012]

The modified high molecular weight polyalkylene oxide of the present invention is a modified high molecular weight polyalkylene oxide containing a structural unit represented by the following formula (1) and is represented by the following formula (2). The functional group is 1.0 to 3.0 mol with respect to 1 mol of R in the modified high molecular weight polyalkylene oxide, and the number average molecular weight is 40,000.
It is about 10,000,000.

[0013]

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(In the formula, 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 each of M ¹ and M ² is a hydrogen atom or a metal. Atom, an ammonium group, and an organic amine group, and n = 2
5 to 700. )

[0015]

[Chemical 6]

(In the formula, M is one selected from a hydrogen atom, a metal atom, an ammonium group and an organic amine group.) Another modified high molecular weight polyalkylene oxide of the present invention has a number average molecular weight of 1,000 to 1,000. A modified high-molecular-weight polyalkylene oxide obtained by a production method comprising a step of reacting 30,000 low-molecular-weight polyalkylene oxide with a polyvalent acid anhydride, wherein the polyvalent acid anhydride is represented by the following formula (3): The functional group represented by the following formula (2) is 1.0 to 3.0 mol with respect to 1 mol of R in the modified high molecular weight polyalkylene oxide.

[0017]

[Chemical 7]

(In the formula, M is one selected from a hydrogen atom, a metal atom, an ammonium group and an organic amine group.)

[0019]

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(In the formula, R is a tetravalent organic group having 4 to 20 carbon atoms.) The film of the present invention contains the modified high molecular weight polyalkylene oxide and has a tensile strength of 80 kgf / cm ^2.
That is all. Another film of the present invention contains the modified high molecular weight polyalkylene oxide and has an elongation of 100% or more.

The method for producing a modified high molecular weight polyalkylene oxide of the present invention has a number average molecular weight of 1,000 to 30,
000 of a low molecular weight polyalkylene oxide and a polyhydric acid anhydride are reacted, wherein the polyhydric acid anhydride is a dihydric acid anhydride and the reaction pressure is 0. It is 0.003 MPa or more, and the acid anhydride group in the polyvalent acid anhydride is charged and reacted in an amount of 0.8 to 1.0 mol with respect to 1 mol of the hydroxyl group in the low molecular weight polyalkylene oxide. It is characterized by

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Modified high molecular weight polyalkylene oxide The modified high molecular weight polyalkylene oxide contains a structural unit (1) represented by the following formula (1).

[0023]

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(In the formula, R¹Is a divalent organic having 2 to 6 carbon atoms
Group, R is a tetravalent organic group having 4 to 20 carbon atoms, and M¹Oh
And M²Are all hydrogen atoms, metal atoms, ammonium
Group and an organic amine group, n = 2
5 to 700. ) R in formula (1)¹Is a divalent organic group having 2 to 6 carbon atoms.
If there is no particular limitation. R¹As a specific example of,₂-
CH₂-, -CH₂-CH₂-CH₂-, -CH₂-CH (C
H_Three)-, -CH₂-CH₂-CH₂-CH₂-, -CH (C
H_Three) -CH₂-CH₂-, -CH₂-CH (CH_Three)-
CH₂-, -CH₂-CH (CH₂CH _Three)-, -CH
₂-CH₂-CH₂-CH₂-CH₂-, -CH (CH_Three) -C
H₂-CH ₂-CH₂-, -CH₂-CH (CH_Three) -CH₂-
CH₂-, -CH₂-CH₂-CH (CH₂CH_Three)-,-
CH₂-CH (CH₂ CH_Three) -CH₂-, -CH₂-C
H (CH₂CH₂ CH_Three)-, -CH₂-CH₂-CH₂-C
H₂-CH₂-CH₂-, -CH (CH_Three) -CH₂-CH₂-
CH₂-CH₂-, -CH₂-CH (CH_Three) -CH₂-CH
₂-CH₂-, -CH₂-CH₂-CH (CH_Three) -CH₂-C
H₂-, -CH (CH₂CH_Three) -CH₂-CH₂-CH₂
-, -CH₂-CH (CH₂CH_Three) -CH₂-CH₂−,
-CH₂-CH₂-CH (CH₂CH₂CH_Three)-, -CH
₂-CH (CH ₂CH₂CH_Three) -CH₂ -, -CH₂−
CH (CH₂CH₂CH₂CH_Three)-, -CH₂-CH
(CH₂Cl)-, -CH₂-CH₂-CH (CH₂C
l)-and the like. These R¹Is one
Alternatively, a mixture of two or more kinds may be used if necessary. During ~
But R¹Is -CH₂-CH₂-, -CH₂-CH (C
H_Three)-, -CH₂-CH₂-CH₂-CH₂Selected from
At least one type is easily available and inexpensive.
preferable.

R in the formula (1) is not particularly limited as long as it is a tetravalent organic group having 4 to 20 carbon atoms. Specific examples of R include structural units (1) containing R of the formulas (4) to (14) shown below. The structural unit (1) containing R may be one type of modified high molecular weight polyalkylene oxide or a mixture of two or more types thereof as necessary.

[0026]

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[0027]

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[0028]

[Chemical 12]

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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(In the formulas (4) to (14), R ¹ has 2 carbon atoms.
To 6 are divalent organic groups, each of M ¹ and M ² is one 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 etc.”) are bound to R. Further, R repeats the structural unit (1) represented by the formula (1) through a bond with two ester groups to form a main chain of the modified high molecular weight polyalkylene oxide. Two carboxyl groups and the like and two ester groups are bound to R, and there is no particular limitation on the combination of these individual binding chains and the carboxyl group or the ester group.

[0038]

[Chemical 21]

(In the formula, M is one selected from a hydrogen atom, a metal atom, an ammonium group and an organic amine group.) In the formula (1), n is not particularly limited as long as it is 25 to 700. n is preferably 50 to 650, more preferably 1
00 to 570, and most preferably 160 to 530.
When n is smaller than the above range, R derived from an expensive polyhydric acid anhydride described later accounts for a large proportion in the modified high molecular weight polyalkylene oxide, which is economically disadvantageous. On the other hand, when n is larger than the above range, the carboxyl value, which will be described later, in the modified high molecular weight polyalkylene oxide is reduced and the cohesive force is lost, which makes molding difficult.

Each of M ¹ and M ² in the formula (1) is one kind 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. good. When M ¹ or M ² is a hydrogen atom, the above-mentioned carboxyl group and the like are carboxyl groups. When M ¹ or M ² is a metal atom, a 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. M ¹
Alternatively, when 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. When M ¹ or M ² is an organic amine group, a carboxyl group or the like becomes a functional group containing an organic amine salt of carboxylic acid replaced with a functional group derived from an organic amine.

The metal atom is not particularly limited as long as it forms a salt with a carboxyl group. Specific examples of the metal atom, lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, titanium, zirconium, hafnium, vanadium, niobium,
Chromium, molybdenum, tungsten, manganese, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, copper, silver, zinc, cadmium, mercury, aluminum, gallium, indium, thallium, silicon,
Examples thereof include germanium, tin, lead, antimony, bismuth, scandium and the like. These metal atoms may be used alone or in combination of two or more if necessary. 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, resulting in a high degree of modification. The molecular weight polyalkylene oxide is preferable because the mechanical strength becomes more tough.

In the present invention, the organic amine group has a valence of 4 as the central nitrogen atom, at least one of the substituents bonded to the nitrogen atom is an organic group, and a substituent bonded to the nitrogen atom. At least one of the above has a structure which is a hydrogen atom. The organic amine group is derived from organic amines and is not particularly limited as long as it has a structure capable of forming 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- (butylamino) propylamine, tetra Methylethylenediamine, tri-n-octylamine, tert-butylamine, 2-butylamine, picoline, vinylpyridine, pipecoline, piperazine, piperidine, pyrazine,
Mention may be made of monoethanolamine, diethanolamine, triethanolamine and the like. These amines may be used alone or in combination of two or more as required. Among them, when the amines are at least one selected from triethylamine, pyridine, tripropylamine, 1,4-diazabicyclo [2,2,2] octane, and tetramethylethylenediamine, they are easily available and inexpensive, and the amines Is preferable because it can be easily introduced as a carboxylate.

Amines having a divalent or higher valent metal atom and two or more amino groups in the molecule may be crosslinked with a carboxylic acid on the side chain of the modified high molecular weight polyalkylene oxide. When crosslinked with the carboxylic acid of the side chain of the modified high molecular weight polyalkylene oxide, such a crosslinked structure has the function of increasing the molecular weight and has the effect of improving the mechanical strength. In addition, in the high temperature range where the obtained modified high molecular weight polyalkylene oxide melts, it has fluidity due to dissociation of ionic bond, and has ideal physical properties as a polymer material. Therefore, unlike carbon-carbon cross-linking, strength reduction due to gelation is not observed.

The carboxyl group and the like in the modified high molecular weight polyalkylene oxide are not particularly limited as long as they are 1.0 to 3.0 mol with respect to 1 mol of R in the modified high molecular weight polyalkylene oxide, and preferably 1 The amount is 0.5 to 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 with respect 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. The cohesive force and the molecular weight are well balanced between them, resulting in moldability and high mechanical strength. When the carboxyl value is smaller than the above range, the cohesive force between the carboxyl groups and the like is insufficient, and moldable high mechanical strength cannot be obtained. When the carboxyl value is larger than the above range, R derived from an expensive polyhydric acid anhydride, which will be described later, becomes large in the modified high molecular weight polyalkylene oxide, which is not economical.

When the modified high molecular weight polyalkylene oxide contains only the structural unit (1), the modified high molecular weight polyalkylene oxide has no cross-linking structure and has a linear structure without branching, so that the carboxyl value increases. Furthermore, by aggregating a carboxyl group or the like in the side chain of the modified high molecular weight polyalkylene oxide,
It is preferable because the mechanical strength is improved.

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), instead of one carboxyl group or the like in the formula (1), a carboxyl group is bonded to a polymer chain of another modified high molecular weight polyalkylene oxide through an ester bond. A structural unit (a) which is crosslinked by; instead of both carboxyl groups or the like in the formula (1), both carboxyl groups are bonded to the polymer chain of another modified high molecular weight polyalkylene oxide through an ester bond. The structural unit (b) which bridge | crosslinks etc. can be mentioned. The following formula (15) is a structural unit (a)
The following formula (16) represents the structural unit (b).

[0047]

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[0048]

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The ratio of the structural unit (a) in the modified high molecular weight polyalkylene oxide is not particularly limited as long as the ratio of the carboxyl value to R is in the range of 1.0 to 3.0 mol. When the carboxyl value for R is out of the above range, the mechanical strength decreases, so that 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. When the structural unit (b) is contained, the carboxyl value with respect to R is lowered and the mechanical strength is remarkably increased. Since it decreases, it is most preferable not to include it at all. The number average molecular weight of the modified high molecular weight polyalkylene oxide is 40,000 to
It is 10,000,000. Preferably 45,000
~ 5,000,000, more preferably 50,000
~ 2,000,000, most preferably 55,000 ~
It is 1,000,000. When the number average molecular weight is smaller than the above range, mechanical properties are low and molding 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 make it difficult to process. It should be noted that when the temperature is raised, the melt viscosity is lowered, but thermal deterioration remarkably occurs.

The modified high molecular weight polyalkylene oxide is also a modified high molecular weight 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 polyvalent acid anhydride. In the polyalkylene oxide, the polyhydric acid anhydride is a divalent acid anhydride represented by the following formula (3), and the functional group represented by the above formula (2) is contained in the modified high molecular weight polyalkylene oxide. 1.0 to 3.0 with respect to 1 mol of R
It may be molar.

[0052]

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(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 C 2-6 aliphatic cyclic ethers such as polyethylene glycol, polypropylene glycol, polytetraethylene glycol, polyepichlorohydrin, and copolymers thereof, or C 2-6. Examples thereof include those obtained from the aliphatic glycols. These low molecular weight polyalkylene oxides may be used alone or as a mixture of two or more kinds as necessary.

The low molecular weight polyalkylene oxide is at least 1 selected from polyethylene glycol, polypropylene glycol and polytetraethylene glycol.
The seeds are preferable because the resulting modified high molecular weight polyalkylene oxide has a large molecular weight and the modified high molecular weight polyalkylene oxide can be industrially efficiently obtained.

The number average molecular weight of the low molecular weight polyalkylene oxide is 1,000 to 30,000. Preferably 2,000 to 28,000, more preferably 4,
000-26,000, most preferably 7,000-2
It is 4,000. When the number average molecular weight is smaller than the above range, the melting point of the low molecular weight polyalkylene oxide is 4
At 0 ° C. or less, it becomes liquid in some cases, and the low molecular weight polyalkylene oxide easily absorbs water, and unless the water is sufficiently removed, the molecular weight of the modified high molecular weight polyalkylene oxide cannot increase. On the other hand, if it is larger than the above range, thermal deterioration occurs during the reaction, and a product having a terminal not having a hydroxyl group is 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 acid dianhydride, pyromellitic dianhydride, biphenyltetracarboxylic acid dianhydride, p-terphenyl 3, 4,3 ′, 4′-tetracarboxylic dianhydride,
3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid Dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,
3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-
Divalent acid anhydrides such as 2,3,5,6-tetracarboxylic acid dianhydride; maleic anhydride-styrene copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-vinyl chloride copolymer Coalesce, maleic anhydride-butadiene copolymer, maleic anhydride-methyl vinyl ether copolymer,
An acid anhydride having a valence of 3 or more, such as maleic anhydride-ethylene copolymer, may be mentioned. These polyhydric acid anhydrides are 1
It may be a species or a mixture of two or more species as required.

When the polyhydric acid anhydride is the dihydric acid anhydride represented by the formula (3), the resulting modified high molecular weight polyalkylene oxide has no cross-linking structure and no branching capable of aggregating carboxyl groups and the like. Since it has a linear structure, it is preferable because it can be molded and has high mechanical strength in terms of molecular weight. Particularly, when the divalent acid anhydride is at least one selected from pyromellitic dianhydride and butane-1,2,3,4-tetracarboxylic acid dianhydride, the reactivity and the production efficiency are high. Therefore, it is more preferable.

R in the formula (3) is R in the above formula (1).
The same is used, and the same is preferable for the same reason. Further, the number average molecular weight of 1,000 to 30,
000 of the modified high molecular weight polyalkylene oxide obtained by reacting a low molecular weight polyalkylene oxide with a polyhydric acid anhydride has a carboxyl value of the modified high molecular weight polyalkylene oxide containing the structural unit represented by the formula (1) described above. The same range as the alkylene oxide is preferable for the same reason.

The reaction method of the low molecular weight polyalkylene oxide and the divalent acid anhydride is not particularly limited, but the production method described below is preferable. The modified high molecular weight polyalkylene oxide having 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. A step of reacting with a substance (chain extension reaction step), and a step of adding and reacting at least one selected from a metal compound containing a metal atom, ammonia, and amines corresponding to the type of M It is obtained by the manufacturing method described below.

The modified high molecular weight polyalkylene oxide can be used, for example, as a molding material described later and processed into a film, a sheet and the like. Method for producing modified high molecular weight polyalkylene oxide The method for producing modified high molecular weight polyalkylene oxide,
A method for producing a modified high molecular weight polyalkylene oxide, comprising the step of reacting a low molecular weight polyalkylene oxide having a number average molecular weight of 1,000 to 30,000 with a polyvalent acid anhydride, wherein the polyvalent acid anhydride is 2 A polyhydric acid anhydride having a reaction pressure of 0.003 MPa or more, and 0.8 to 1.0 of the acid anhydride group in the polyhydric acid anhydride with respect to 1 mol of the hydroxyl group in the low molecular weight polyalkylene oxide. It is characterized in that it is charged so that it becomes a mole and reacted.

Hereinafter, a step of reacting a low molecular weight polyalkylene oxide with a 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 preferable for the same reason. The number of moles of the acid anhydride group in the polyvalent acid anhydride (hereinafter, sometimes referred to as a molar charging ratio) relative to 1 mole of the hydroxyl group in the low molecular weight polyalkylene oxide 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 0.8.
It is 7 to 1.0 mol, most preferably 0.90 to 1.0 mol. When the molar charging ratio is smaller than the above range, unreacted low molecular weight polyalkylene oxide is contained in the produced polymer in a large amount, so that the mechanical strength is lowered. On the other hand, when it is larger than the above range, a large amount of low molecular weight polyalkylene oxide blocked with a polyhydric acid anhydride is produced in the reaction system. Further, 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 is stopped. As a result,
A large number of low molecular weight polyalkylene oxides having both ends blocked with a polyhydric acid anhydride are present in the product, resulting in a decrease in mechanical strength.

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

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 2
The temperature is 00 ° C, most preferably 100 to 180 ° C. When the reaction temperature is within the above range, the reaction can be carried out efficiently, and deterioration of the modified high molecular weight polyalkylene oxide due to heat hardly occurs. Therefore, additives such as an antioxidant described later are 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,
Most preferably, it is 0.094 MPa or more. If the reaction pressure is too low, the reaction system becomes a reduced pressure state, between the carboxyl group in the resulting modified high molecular weight polyalkylene oxide and the hydroxyl group in the low molecular weight polyalkylene oxide, the dehydration reaction which is a side reaction is promoted. A product in which the carboxyl group, which is a by-product, is esterified is obtained.
When the esterified product is obtained, the carboxyl value of the modified high molecular weight polyalkylene oxide is reduced, the cohesive force of the carboxyl groups between molecules of the modified high molecular weight polyalkylene oxide is lost, and the mechanical strength is significantly reduced. .

The reaction pressure is 0.003 MPa as described above.
There is no particular limitation as long as it is 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. It is the following. If the reaction pressure is too high, manufacturing equipment for pressurization is required, and the pressurization may reduce the manufacturing efficiency.

In the method for producing a modified high molecular weight polyalkylene oxide, a solvent, an antioxidant, an ultraviolet absorber, a crystal nucleating agent, etc. are used as a component other than the above-mentioned low molecular weight polyalkylene oxide and polyhydric acid anhydride. Good. In the method for producing a modified high molecular weight polyalkylene oxide,
Although it has a low viscosity in the initial stage of the reaction, a solvent may be used in order to prevent the viscosity from increasing with the molecular weight in the latter 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,
Examples thereof include diethyl ketone, methylpropyl ketone, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, acetonitrile, pyridine, dimethylformamide, ethylenediamine, propylenediamine and the like. One of these reaction solvents or a mixture of two or more thereof may be used if necessary.

However, when a reaction solvent is used, stirring at the time of reaction becomes easy, but on the other hand, a step (devolatilization step) of removing the reaction solvent after completion of the reaction is required, and a modified high molecular weight polyalkylene oxide containing the reaction solvent is required. Since the reaction solvent cannot be completely removed without devolatilization under high vacuum, the production efficiency may decrease. 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 reaction device, because the reaction can be more easily and efficiently produced.

As a concrete 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 high viscosity reactor may be continuous or batch type. As an example of a continuous high-viscosity reactor, FIG.
There is a horizontal twin-screw kneading device (trade name “KRC kneader” manufactured by Kurimoto Iron Works Co., Ltd.) shown in FIG. This kneading device 1 includes a kneader body 2, a solid supply unit 3 that supplies a fixed amount of powder or a fluid to the kneader body 2, a liquid supply unit 4 that supplies a fixed amount of a liquid or a slurry liquid to the kneader body 2, and a kneader body. A heating / cooling device 5 for heating / cooling 2 is provided.

The kneader body 2 includes a drive unit 10 composed of a motor and a speed reducer, a trough 11 divided into two, 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, the polyhydric acid anhydride 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 into the trough 11 from the supply units 3 and 4 in a predetermined amount, and the low-molecular-weight polyethylene oxide is melted by heating and kneaded with the polyhydric acid anhydride under normal pressure to react. Thereby, a modified high molecular weight polyalkylene oxide is obtained.

As other continuous high-viscosity reaction apparatus, a biaxial horizontal type kneading apparatus having a stirring blade with an eyeglass blade (Hitachi, Ltd., trade name "Hitachi eyeglass blade polymerization machine"), a stirring blade with 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.

Further, as a batch type high-viscosity reaction apparatus, a vertical kneading apparatus in which the stirring blades are installed on two shafts arranged concentrically, and the stirring blades 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 modified high-molecular-weight polyalkylene oxide thus obtained can be molded and processed, and can be effectively applied to various applications such as a molding material shown below.

The method for producing the modified high molecular weight polyalkylene oxide may further include the step of adding and reacting at least one selected from a metal compound, ammonia and the amines. At least one selected from metal compounds, ammonia, and the amines (hereinafter,
At least one selected from metal compounds, ammonia, and the above amines may be referred to as a “carboxyl group modifier”. ) May be added at any time during the chain extension reaction, during the chain extension reaction, and after the chain extension reaction.However, it is recommended to add)) during the chain extension reaction or during the chain extension reaction. It is preferable because the reaction time can be shortened and the manufacturing process can be simplified.

The metal compound includes oxides, carboxylates, metal alkoxides, carbonates, hydroxides, hydrides, peroxides, chlorides, nitrates, phosphates containing the above-mentioned metal atoms.
Examples thereof include sulfates, sulfites, and carbides. These metal compounds may be used alone or in combination of two or more if necessary. Among them, when the metal compound is at least one selected from oxides, carbonates and hydroxides, compatibility with low molecular weight polyalkylene oxides and modified high molecular weight polyalkylene oxides is good, and therefore a metal is easily introduced. It is preferable because it can be manufactured, has high safety, is easy to handle during manufacturing, and is 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, potassium and the like. However, in the case of using such a metal simple substance, it is necessary to ensure the safety because there is a high risk of causing a fire by reacting with air or moisture. As the amines, those exemplified above can be used as they are. Further, the same is preferable as amines for the same reason as described above.

The carboxyl group modifier is a polyhydric acid anhydride.
There is no particular limitation as long as it is 0.001 to 10.0 mol per mol. The addition amount is preferably 0.1 to 5.0 mol, more preferably 0.5 to 3.0 mol. When the addition amount is more than the above range, the carboxyl group modifier is uniformly dispersed in the modified high molecular weight polyalkylene oxide,
Since it becomes impossible to dissolve, the mechanical strength of the modified high molecular weight polyalkylene oxide decreases. Further, when the amount of the carboxyl group modifier is large, the reaction time becomes long and the production efficiency is lowered. If the addition amount is less than the above range, the addition effect of the carboxyl group modifier becomes small.

The reaction temperature for reacting the carboxyl group-modifying agent 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 within the above range, the reaction can be carried out efficiently, and deterioration of the modified high molecular weight polyalkylene oxide due to heat hardly occurs. Therefore, additives such as an antioxidant described later are not necessary.

When reacting the carboxyl group modifier,
There is no particular limitation on the reaction pressure of. The reaction pressure is
Similar to the chain extension reaction step described above, at 0.003 MPa or more
If there is no particular limitation. The reaction pressure is preferably 0.03
0 MPa or more, more preferably 0.080 MPa or less
Above all, it is most preferably 0.094 MPa or more. Further
Used when reacting a carboxyl group modifier
The reactor is also used in the chain extension reaction process described above.
A high-viscosity reactor is preferably used. Applications of modified high molecular weight polyalkylene oxide [Molding material] The molding material is the above-mentioned modified high molecular weight polyalkyl
Contains ren oxide.

The molding material is heated, if necessary, so that the melt viscosity at that time is 10,000 to 100,000.
It is preferably 0 cP, more preferably 20,000.
0-80,000,000 cP, most preferably 50,
It is 000 to 70,000,000 cP. If the melt viscosity of the molding material is too high, molding cannot be performed. On the contrary, if the melt viscosity of the molding material is too low, the fluidity is too large to perform molding. The temperature of the molding material at the time of measuring the melt viscosity is not particularly limited, but when it is a normal molding temperature of 70 to 200 ° C., the melting point of the modified high molecular weight polyalkylene oxide becomes the melting point or more, and heat deterioration occurs during molding. It is difficult and preferable.

The molding material contains a modified high molecular weight polyalkylene oxide as an essential component, and may contain other material components. Specific examples of the component other than the modified high molecular weight polyalkylene oxide include an inorganic filler, an ultraviolet absorber and a pigment. 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, calender method and the like.

The molding material can be processed into various molded articles by the above-mentioned molding method, and specifically, it can be molded into a film, a sheet or the like. [Film] Each of the films contains the modified high molecular weight polyalkylene oxide described above. Among them, the film (1) has a tensile strength of 80 kgf / cm ² or more, and the film (2) has a film elongation of 100% or more. Further, any of the films 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 has a number average molecular weight of 40,000 to 10,000.
If it is 10,000, there is no particular limitation. 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. Further, if the number average molecular weight is larger than the above range, the melt viscosity at the time of molding into a film is too high to form the film.

The tensile strength of the film (1) is 80 kg.
There is no particular limitation as long as it is f / cm ² or more. Tensile strength is preferably 85 kgf / cm ² or more, more preferably 90 kgf / cm ² or more, most preferably 100k
gf / cm ² or more. When the tensile strength is out of the above range, the tensile strength is low, and when used as a packaging material or the like, the film may rupture due to the self-weight of the content, and the content may not be wrapped.

The elongation of the film (2) is not particularly limited as long as it is 100% or more. The elongation is preferably 200
%, More preferably 500% or more, most preferably 7
It is 00%. When the tensile strength is out of the above range, the elongation is low, the elasticity of the film is low, and the film breaks. The elasticity of the film acts as a cushion when a force is applied to the film and prevents the film from breaking.

The thickness of the film is also not particularly limited. The thickness of the film is preferably 2-700 μm, more preferably 5-500 μm, most preferably 10-μm.
It is 300 μm. When the film thickness is in the above range, a flexible and tough film can be obtained, which is preferable. However, in the case where the film is multi-layered and the strength can be secured by the base material to be laminated, there may be no problem even if it is thinner than 10 μm.

The method for producing a film containing a modified high molecular weight polyalkylene oxide is not particularly limited, and a conventionally known method for producing a film can be applied. Specific examples of the method for producing the film include a T-die method, an inflation method, a calendar method and the like. In the T-die method, inflation method, and calendar method,
The modified high molecular weight polyalkylene oxide can be formed into a film by extruding at a machine outlet temperature of 50 to 250 ° C, preferably 100 to 180 ° C. When the temperature at the outlet of the molding machine is higher than this temperature range, the melt viscosity of the modified high molecular weight polyalkylene oxide becomes extremely low, and therefore the inflation method cannot support the weight of the film, and continuous withdrawal of the film becomes difficult. Further, in the T-die method, the width of the melted film after extrusion is narrowed due to surface tension, which causes problems such as perforation and stiffening. Further, if the modified high molecular weight polyalkylene oxide is stored at 250 ° C. or higher for a long time, thermal deterioration occurs and the quality of the obtained film deteriorates, which is not preferable. If the molding machine outlet temperature is lower than this temperature range, the molten state of the modified high molecular weight polyalkylene oxide becomes non-uniform, and it becomes difficult to obtain a homogeneous film, and the melt viscosity is high, so the production efficiency of the film is remarkably high. It may decrease.

The extruded film in the molten state was cooled to 0 to 45 ° C. in a cooling time of 5 seconds to 3 minutes to obtain good surface smoothness, transparency, uniformity and mechanical properties. A film having physical properties can be obtained with high production efficiency. In the method for producing a film, the molding material containing the 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 include a material component other than the modified high molecular weight polyalkylene oxide. As such material components,
Stabilizer, crystal nucleating agent, extender, pigment, colorant, UV absorber, surface brightener, inorganic filler, antioxidant, plasticizer,
Lubricants and the like can be mentioned. These material components may be added to the modified high molecular weight polyalkylene oxide before manufacturing the film, or may be added to the film after manufacturing. When the content of the material components is 0.0001 to 30% by weight with respect to the modified high molecular weight polyalkylene oxide, the addition effect of the material components can be obtained.

[0090]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, "part" in an example represents "part by weight". Example A1-100 ml flask, number average molecular weight 10,0
10 parts of polyethylene glycol and 0.207 parts of pyromellitic dianhydride were charged, and 0.099 MPa,
The high molecular weight reaction was carried out for 3 hours under the reaction condition of 150 ° C.
The resulting modified high molecular weight polyalkylene oxide (A
The number average molecular weight of 1) is 84,000, and the melt viscosity is 10.
It was 20,000 cP. The acid value measured by neutralization titration is
It is 9.92 mgKOH / g, and the carboxyl value is 1.
It was 99 mol.

Using the modified high molecular weight polyalkylene oxide (A1) as a molding material, a compression molding machine was used under conditions of a molding temperature of 150 ° C., a molding pressure of 100 kgf / cm ² and a molding time of 2 minutes. Film (A1)
was gotten. The film (A1) was subjected to a tensile test and found to have a tensile strength of 95 kgf / cm ² and an elongation of 912%. The results are summarized in Table 1.

Elemental analysis, infrared absorption spectrum and modified high molecular weight polyalkylene oxide (A1)
The measurement results of ¹ H-NMR 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 (CO, 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 association, s) 8.08 (aromatic derived from pyromellitic dianhydride Group proton, 2H, s) 8.12 (-COOH association, s) The above number average molecular weight, carboxyl value, 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 as described above, and 1 mol of R in the modified high molecular weight polyalkylene oxide (1 mol of polyvalent acid anhydride charged in the reaction).
On the other hand, the number of moles of the carboxyl group and the like in the modified high molecular weight polyalkylene oxide 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, M is at least 1 selected from a metal atom, an ammonium group and an organic amine group.
In the modified high molecular weight polyalkylene oxide that is a seed,
Dissolve this in pure water, add acid such as hydrochloric acid,
Completely liberate ammonium groups, organic amine groups, etc.,
After completely releasing the weakly acidic carboxyl group,
The carboxyl value of the liberated carboxyl group can be determined by the same method as described above. (Melt viscosity) Shimadzu flow tester (Model: CF
T-500C). The measurement condition is 15
0 ° C., constant temperature method, cylinder pressure 30 kgf / cm ² . The die has L (length): 1.00 mm and D (hole diameter):
0.50 mm was used. (Tensile Strength and Elongation) A tensile test was performed at a test speed of 20 mm / min in accordance with JIS K7121 to measure the tensile strength and elongation at the time of breaking.

Examples A2 to A5-The reaction was carried out in the same manner as in Example A1 except that the molecular weights of polyethylene glycol were changed to those shown in Table 1.
Modified high molecular weight polyalkylene oxide (A2) to (A
5) was obtained. Further, films (A2) to (A5) were obtained in the same manner as in Example A1. The results are summarized in Table 1.

-Examples A6 to A8- The molecular weight of polyethylene glycol was changed to that shown in Table 1, and polyhydric acid anhydrides of 3, 4, 9, 1 were used.
The reaction was performed in the same manner as in Example A1 except that 0-perylenetetracarboxylic dianhydride was used to obtain modified high molecular weight polyalkylene oxides (A6) to (A8). Further, in the same manner as in Example A1, films (A6)-
(A8) was obtained. The results are summarized in Table 1.

-Example A9-In addition to the charge of Example A1, calcium carbonate 0.10 was added.
A high molecular weight reaction was carried out in the same manner as in Example A1 except that 8 parts were added to obtain a modified high molecular weight polyalkylene oxide (A9) containing a calcium salt of a carboxylic acid in which a hydrogen atom of a carboxyl group was replaced with calcium. Further, a film (A9) was obtained in the same manner as in Example A1. The results are summarized in Table 1.

-Example A10-A high molecular weight reaction was performed in the same manner as in Example A1 except that 0.231 parts of 1,4-diazabicyclo [2,2,2] octane was added to the charge of Example A1. Thus, a modified high molecular weight polyalkylene oxide (A10) containing an organic amine salt of a carboxylic acid in which a hydrogen atom of a carboxyl group is substituted with an organic amine group was obtained. Further, a film (A10) was obtained in the same manner as in Example A1. The results are summarized in Table 1.

-Example A11- To the modified high molecular weight polyalkylene oxide (A8) obtained in Example A8 and in a molten state immediately after the reaction, 0.051 part of calcium carbonate was added, and the same reaction conditions as in Example A8 were used. The mixture was heated and stirred for 1 hour. Modified high molecular weight polyalkylene oxide containing calcium salt of carboxylic acid in which hydrogen atom of carboxyl group is replaced by calcium (A11)
I got Further, in the same manner as in Example A1, a film (A1
1) was obtained. The results are summarized in Table 1.

-Example A12- To the modified high molecular weight polyalkylene oxide (A8) obtained in Example A8 and in a molten state immediately after the reaction, 1,4-
Polymerization reaction was carried out in the same manner as in Example A1 except that 0.111 parts of diazabicyclo [2,2,2] octane was added to give an organic amine salt of a carboxylic acid in which a hydrogen atom of a carboxyl group was replaced with an organic amine group. A modified high molecular weight polyalkylene oxide (A12) containing was obtained. Further Example A
A film (A12) was obtained in the same manner as in 1. The results are summarized in Table 1.

[0099]

[Table 1]

Comparative Examples A1 to A3 The same as Example A1 except that the molecular weight of polyethylene glycol was changed to that shown in Table 2 and the charging ratio of pyromellitic dianhydride to polyethylene glycol was changed. The reaction was performed to obtain comparative modified high molecular weight polyalkylene oxides (A1) to (A3). Further, an attempt was made to form a film in the same manner as in Example A1,
The film (A2) and the film (A3) were obtained, but the film (A1) was not obtained. The results are summarized in Table 2.

[0101]

[Table 2]

The modified high molecular weight polyalkylene oxides shown in the above examples have a melt viscosity within a viscosity range suitable for molding and can be molded into a film or the like. Furthermore, the films shown in the above examples are superior to the mechanical strength of the comparative films. Example B1-A 100 ml flask was charged with a number average molecular weight of 20,0.
100 parts of polyethylene glycol of 00 and 0.106 parts of pyromellitic dianhydride were charged (the molar ratio of the hydroxyl group in polyethylene glycol to the acid anhydride group in pyromellitic dianhydride [acid anhydride group / hydroxyl group]). Is 0.97
Met. ), 0.100 MPa, and 150 ° C. for 4 hours. The number average molecular weight of the obtained modified high molecular weight polyalkylene oxide (B1) was 146,000.

Using the modified high molecular weight polyalkylene oxide (B1) as a molding material, a compression molding machine was used 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. Film (B1)
was gotten. The film (B1) was subjected to a tensile test and found to have a tensile strength of 187 kgf / cm ² and an elongation of 2001%.

The results are summarized in Table 3. —Examples B2 to B6— Table 3 shows the molecular weight of polyethylene glycol and the molar ratio of the hydroxyl group in polyethylene glycol and the acid anhydride group in pyromellitic dianhydride (molar charging ratio, acid anhydride group / hydroxyl group). The modified high-molecular-weight polyalkylene oxides (B2) to (B6) were obtained by carrying out the reaction in the same manner as in Example B1 except that the modification was carried out in the same manner as in Example B1. Further, films (B2) to (B6) were obtained in the same manner as in Example B1. The results are summarized in Table 3.

-Examples B7 to B8-In Example B1, pyromellitic dianhydride was added to 3,4,9,10.
-Modified high molecular weight polyalkylene oxide (B7) to the reaction was carried out in the same manner as in Example B1 except that perylene tetracarboxylic acid dianhydride was replaced with those shown in Table 3 in addition to the above. (B8) was obtained. Further, films (B7) to (B8) were obtained in the same manner as in Example B1. The results are summarized in Table 3.

-Example B9-In addition to the charge of Example B1, 0.05% of calcium carbonate was added.
A high molecular weight reaction was carried out in the same manner as in Example A1 except that 8 parts were added to obtain a modified high molecular weight polyalkylene oxide (B9) containing a calcium salt of a carboxylic acid in which the hydrogen atom of the carboxyl group was replaced with calcium. Further, a film (B9) was obtained in the same manner as in Example A1. The results are summarized in Table 3.

Example B10-A high molecular weight reaction was performed in the same manner as in Example A1 except that 0.119 parts of 1,4-diazabicyclo [2,2,2] octane was added to the charge of Example B1. A modified high molecular weight polyalkylene oxide (B10) containing an organic amine salt of a carboxylic acid in which a hydrogen atom of a carboxyl group is substituted with an organic amine group was obtained. Further, a film (B10) was obtained in the same manner as in Example A1. The 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 same reaction conditions as in Example B8 were added. The mixture was heated and stirred for 1 hour. Modified high molecular weight polyalkylene oxide containing calcium salt of carboxylic acid in which hydrogen atom of carboxyl group is replaced by calcium (B11)
I got Further, in the same manner as in Example A1, a film (B1
1) was obtained. The results are summarized in Table 3.

-Example B12- To the modified high molecular weight polyalkylene oxide (B8) obtained in Example B8 and in a molten state immediately after the reaction, 1,4-
Polymerization reaction was performed in the same manner as in Example A1 except that 0.120 parts of diazabicyclo [2,2,2] octane was added to give an organic amine salt of a carboxylic acid in which a hydrogen atom of a carboxyl group was replaced with an organic amine group. A modified high molecular weight polyalkylene oxide (B12) containing was obtained. Further Example A
A film (B12) was obtained in the same manner as in 1. The results are summarized in Table 3.

[0110]

[Table 3]

Comparative Examples B1 to B4-A reaction was carried out 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. Comparative modified high molecular weight polyalkylene oxide (B
1)-(B4) were obtained. Further, an attempt was made to form a film in the same manner as in Example B1, and film (B1) and film (B4) were obtained, but films (B2) to (B2)-
(B3) was not obtained. The results are summarized in Table 4.

[0112]

[Table 4]

The high molecular weight polyalkylene oxides shown in the above examples have a large number average molecular weight as compared with the comparative examples, and the mechanical strength of the film is excellent. -Example C1-0.065 parts of sodium hydroxide and 15 parts of triethylene glycol were added to the autoclave, and nitrogen substitution was performed. 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 carried out at 150 ° C. for 2.0 hours and then the reaction system was returned to room temperature to obtain a 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 chromatography measurement result.

500 parts of the obtained low molecular weight polyethylene oxide was charged into 1 liter kneader (manufactured by Irie Shokai Co., Ltd.) and melted by heating at 150 ° C., 7.8 parts of pyromellitic dianhydride was added, and the reaction pressure was 0. Polymerization reaction was performed at 100 MPa for 30 minutes. From the gel permeation chromatography measurement results, 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 by the same method as in Example C1 were continuously charged into a high-viscosity horizontal twin-screw extruder at 150 ° C. and a reaction pressure of 0.
The high molecular weight reaction was carried out at 100 MPa. At this time, the residence time until the low-molecular-weight polyethylene oxide was charged into the high-viscosity horizontal twin-screw extruder, reacted with pyromellitic dianhydride to have a high molecular weight, 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 of the obtained modified high molecular weight polyalkylene oxide was 103,000.

Comparative Example C1-Low-molecular-weight polyethylene oxide number-average molecular weight 13, obtained in Example C1 above, in a 100 ml flask.
10 parts of 000 and 0.1 part of pyromellitic dianhydride were charged, and a high molecular weight reaction was performed at 150 ° C. and a reaction pressure of 0.100 MPa for 6 hours. From the gel permeation chromatography measurement result, the number average molecular weight was 45,000.

The high molecular weight polyalkylene oxides obtained in Examples C1 to C2 have a higher number average molecular weight and a shorter reaction time than Comparative Example C1.

[0118]

The modified high molecular weight polyalkylene oxide of the present invention is a modified high molecular weight polyalkylene oxide containing the structural unit represented by the above formula (1), and the functional group represented by the above formula (2) is 1.0 to 3.0 with respect to 1 mol of R in modified high molecular weight polyalkylene oxide
The number average molecular weight is 40,000 to 10,000
Since it is 10,000, it can be molded and has high mechanical strength in spite of its molecular weight.

Another modified high molecular weight polyalkylene oxide of the present invention has a number average molecular weight of 1,000 to 30,000.
Which is a modified high molecular weight polyalkylene oxide obtained by a production method including a step of reacting a low molecular weight polyalkylene oxide with a polyhydric acid anhydride, wherein the polyhydric acid anhydride is represented by the above formula (3). It is a valent acid anhydride, and the functional group represented by the above formula (2) is 1.0 to 3. with respect to 1 mol of R in the modified high molecular weight polyalkylene oxide.
Since it is 0 mol, it can be molded and has high mechanical strength in view of its molecular weight.

The film of the present invention contains the modified high molecular weight polyalkylene oxide and has a tensile strength of 80 k.
Since it is gf / cm ² or more, the mechanical strength of the film is high. Another film of the present invention contains the modified high molecular weight polyalkylene oxide and has an elongation percentage of 100% or more, and thus the film has high mechanical strength. The method for producing a modified high molecular weight polyalkylene oxide according to 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 polyvalent acid anhydride is a divalent acid anhydride, the reaction pressure is 0.003 MPa or more, and the polyvalent acid anhydride is based on 1 mol of the hydroxyl group in the low molecular weight polyalkylene oxide. It is characterized in that the acid anhydride group therein is charged so as to be 0.8 to 1.0 mol and reacted, so that a modified high molecular weight polyalkylene oxide which is moldable and has high mechanical strength in view of molecular weight is used. It can be easily and efficiently manufactured.

[Brief description of drawings]

FIG. 1 is a perspective view showing an example of a high-viscosity reaction apparatus used for carrying out a 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 (5)

[Claims] 1. A modified high molecular weight polyalkylene oxide containing a structural unit represented by the following formula (1), wherein the functional group represented by the following formula (2) is 1 mol of the modified high molecular weight polyalkylene oxide. 1.0 to 3.0 for R
The number average molecular weight is 40,000 to 10,000
A modified high molecular weight polyalkylene oxide that is 10,000. Embedded image (In the formula, 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 ammonium. Group and an organic amine group, and n = 25 to 700.) (In the formula, M is one selected from a hydrogen atom, a metal atom, an ammonium group and an organic amine group.) 2. A modified high molecular weight polyalkylene oxide obtained by a production method 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, wherein: The polyvalent acid anhydride is a divalent acid anhydride represented by the following formula (3), and the functional group represented by the following formula (2) is 1 with respect to 1 mol of R in the modified high molecular weight polyalkylene oxide. Modified high molecular weight polyalkylene oxide having a content of 0.0 to 3.0 mol. Embedded image (In the formula, M is one selected from a hydrogen atom, a metal atom, an ammonium group and an organic amine group.) (In the formula, R is a tetravalent organic group having 4 to 20 carbon atoms.) 3. A film containing the modified high molecular weight polyalkylene oxide according to claim 1 and having a tensile strength of 80 kgf / cm ² or more. 4. The modified high molecular weight polyalkylene oxide according to claim 1, which has an elongation of 100%.
That's it, the film. 5. A method for producing a modified high molecular weight polyalkylene oxide, which comprises the step of reacting a low molecular weight polyalkylene oxide having a number average molecular weight of 1,000 to 30,000 with a polyvalent acid anhydride, wherein Acid anhydride is divalent acid anhydride, reaction pressure is 0.003
The pressure is not less than MPa, and the acid anhydride group in the polyvalent acid anhydride is charged to 0.8 mol to 1.0 mol with respect to 1 mol of the hydroxyl group in the low molecular weight polyalkylene oxide and reacted. A method for producing a modified high molecular weight polyalkylene oxide, comprising: