WO2021182342A1

WO2021182342A1 - Block copolymer

Info

Publication number: WO2021182342A1
Application number: PCT/JP2021/008782
Authority: WO
Inventors: 伊藤　和幸; 健典前川
Original assignee: 住友化学株式会社
Priority date: 2020-03-09
Filing date: 2021-03-05
Publication date: 2021-09-16

Abstract

The present invention relates to a block copolymer containing an aromatic polysulfone block (A) and a polyoxyalkylene block (B), wherein the ratio of [the number average molecular weight of the polyoxyalkylene block (B)] / [the number average molecular weight of the aromatic polysulfone block (A)], as calculated using ¹H-NMR, is 0.010-0.030.

Description

Block copolymer

The present invention relates to block copolymers.
The present application claims priority based on Japanese Patent Application No. 2020-040190 filed in Japan on March 9, 2020, the contents of which are incorporated herein by reference.

Aromatic polysulfone is used for various purposes as a material for molded products because it has excellent heat resistance and chemical resistance. Hydrophilized aromatic polysulfone may be required depending on the application.

Conventionally, block copolymers having aromatic polysulfone as a polymer chain have been produced. Block copolymers containing an aromatic polysulfone block (A) and a polyoxyalkylene block (B) tend to have excellent hydrophilicity.
Patent Document 1 discloses a method for producing a polyaryl ether sulfone-polyalkylene oxide-block copolymer.

Special Table 2016-516875A

However, in the above-mentioned hydrophilized block copolymer, improvement of thermal properties and mechanical properties may be required.

The present invention has been made to solve the above-mentioned problems, and is a block copolymer containing an aromatic polysulfone block (A) and a polyoxyalkylene block (B), which has thermal properties and mechanical properties. It is an object of the present invention to provide a block copolymer having excellent properties.

The present inventors have, to solve the above problems, a result of intensive studies, calculated by ^{1 H-NMR,} the number average of the number average molecular weight of the polyoxyalkylene block (B) / the aromatic polysulfone block (A) We have found that it is possible to improve thermal properties and mechanical properties by setting the ratio represented by the molecular weight within a specific range, and have completed the present invention.
That is, the present invention has the following aspects.

<1> A block copolymer containing an aromatic polysulfone block (A) and a polyoxyalkylene block (B).
^{1 The} ratio represented by the number average molecular weight of the polyoxyalkylene block (B) / the number average molecular weight of the aromatic polysulfone block (A) calculated by 1 H-NMR is 0.005 to 0.030. , Block copolymer.
<2> ¹ The block copolymer according to <1>, wherein the number average molecular weight of the polyoxyalkylene block (B) calculated by 1 H-NMR is 900 or less.
<3> The block copolymer according to <1> or <2>, wherein the block copolymer has a weight average molecular weight of 20,000 to 70,000, which is obtained as an absolute molecular weight by gel permeation chromatography.
<4> A linear triblock copolymer having the above three blocks and the polyoxy in the order of the polyoxyalkylene block (B), the aromatic polysulfone block (A), and the polyoxyalkylene block (B). A linear diblock copolymer having the above two blocks of an alkylene block (B) and the aromatic polysulfone block (A),
The block copolymer according to any one of <1> to <3>, which comprises at least one of.
<5> The block copolymer according to any one of <1> to <4>, wherein the aromatic polysulfone block (A) is composed of a polymer chain having a structural unit represented by the following formula (1). ..

[In equation (1),
R ¹ and R ² independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom.
n1 and n2 are independently integers of 0 to 4, respectively.
When n1 or n2 is 2 or more, plural R ¹ and R ² may be the same or different from each other. ]
<6> The above-described one of <1> to <5>, wherein the polyoxyalkylene block (B) is composed of a polymer chain having a structural unit represented by the following formula (2-1). Block copolymer.

<7> The block copolymer according to any one of <1> to <6>, wherein the glass transition point of the block copolymer is 200 ° C. or higher.
<8> The block copolymer according to any one of <1> to <7>, wherein the 1% mass reduction temperature of the block copolymer is 370 ° C. or higher.
<9> The block according to any one of <1> to <8>, wherein the tensile strength of the molded product obtained by molding the block copolymer, which is obtained by the following measuring method, is 100 MPa or more. Copolymer.
(Measuring method)
As the molded body, a JIS K6251 dumbbell-shaped No. 3 test piece having a thickness of 30 μm was used, and in accordance with JIS K7127, an autograph was used to pull the product at a grip interval of 50 mm and a tensile speed of 5 mm / min at 23 ° C. The tensile strength when the test piece is cut (broken) in an atmosphere of 50% relative humidity is determined.

According to the present invention, it is possible to provide a block copolymer containing an aromatic polysulfone block (A) and a polyoxyalkylene block (B), which is excellent in thermal properties and mechanical properties.

Hereinafter, embodiments of the block copolymer of the present invention will be described.

≪Block Copolymer≫
The block copolymer of the embodiment is a block copolymer containing an aromatic polysulfone block (A) and a polyoxyalkylene block (B), and the number average of the polyoxyalkylene block (B) calculated by ^{1 H-NMR.} The ratio represented by the molecular weight / the number average molecular weight of the aromatic polysulfone block (A) is 0.005 to 0.030.

The aromatic polysulfone block (A) has a _{structural unit containing at least a structure in which a sulfonyl group (-SO 2-} ), an arylene group (-Ar-), and an ether bond (-O-) are bonded in this order. Examples thereof include those composed of polymer chains.

The aromatic polysulfone block (A) preferably has a structural unit represented by the following general formula (1) from the viewpoint of heat resistance and chemical resistance.

[In equation (1),
R ¹ and R ² independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom.
n1 and n2 are independently integers of 0 to 4, respectively.
When n1 or n2 is 2 or more, plural R ¹ and R ² may be the same or different from each other. ]

Examples of the alkyl group having 1 to 10 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. Examples thereof include a group, an n-hexyl group, a 2-ethylhexyl group, an n-octyl group, an n-decyl group and the like.
Examples of the aryl group having 6 to 20 carbon atoms in R ¹ and R ² include a phenyl group, an o-trill group, an m-trill group, a p-trill group, a 1-naphthyl group, a 2-naphthyl group and the like. Be done.
Examples of the halogen atom in R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
n1 and n2 are independently integers of 0 to 4, preferably 0 to 2, and more preferably 0 to 1.

For example, the structural unit represented by the general formula (1) is contained in an amount of 80 mol% or more and 100 mol% or less with respect to a total amount of 100 mol% of all the structural units constituting the aromatic polysulfone block (A). It may be contained in an amount of 90 mol% or more and 100 mol% or less, or may be contained in a content of 98 mol% or more and 100 mol% or less.

Examples of the polyoxyalkylene block (B) include those composed of a polymer chain having an oxyalkylene group as a structural unit. The polyoxyalkylene block (B) preferably has a structural unit represented by the following formula (2).

[In the formula (2), R ³ represents an alkylene group having 2 to 6 carbon atoms. ]

Examples of the alkylene group having 2 to 6 carbon atoms in R ³ _{include an ethylene group, a trimethylene group, -CH (CH 3} ) CH _2- , tetramethylene group, -CH ₂ CH ₂ CH (CH ₃ )-, and hexamethylene. The basis etc. can be mentioned.

Of the above examples, the polyoxyalkylene block (B) preferably has a structural unit represented by the following formula (2-1).

For example, the structural unit represented by the above general formula (2-1) is 80 mol% or more and 100 mol% or less with respect to the total amount of 100 mol% of all the structural units constituting the polyoxyalkylene block (B). It may be contained, may be contained in 90 mol% or more and 100 mol% or less, and may be contained in 98 mol% or more and 100 mol% or less.

The block copolymers of the embodiment are a linear triblock copolymer having the above three blocks in the order of polyoxyalkylene block (B), aromatic polysulfone block (A), and polyoxyalkylene block (B), and polyoxy. It may contain at least one of a linear diblock copolymer having the above two blocks of an alkylene block (B) and an aromatic polysulfone block (A).

The block copolymers of the embodiment are a linear triblock copolymer having the above three blocks in the order of polyoxyalkylene block (B), aromatic polysulfone block (A), and polyoxyalkylene block (B), and polyoxy. It may contain at least one block copolymer selected from the group consisting of a linear diblock copolymer having the above two blocks of an alkylene block (B) and an aromatic polysulfone block (A).

The linearity referred to here may mean that the block copolymer does not have a branched structure (branched chain). As the linear triblock copolymer, for example, the end of the main chain of the polymer chain of the aromatic polysulfone block (A) and the end of the main chain of the polymer chain of the polyoxyalkylene block (B) are directly linked to each other. Examples include combined ones.

As an example of a linear triblock copolymer having the above three blocks in the order of polyoxyalkylene block (B), aromatic polysulfone block (A), and polyoxyalkylene block (B), the following general formula (I) is used. What is represented can be exemplified.

[In formula (I),
R ¹ , R ² , R ³ , n1 and n2 have the same meanings as those in the above equations (1) and (2).
n is an integer of 0 or more, m is an integer of 1 or more, R ³ existing in plural numbers may be the same or different from each other, the m there are a plurality, it may be the same or different from each other. ]

n is the number of repetitions of the structural unit of the aromatic polysulfone block (A) in the formula (I).
m is the number of repetitions of the structural unit of the polyoxyalkylene block (B) in the formula (I).

The ratio of the aromatic polysulfone block (A) and the polyoxyalkylene block (B) to the whole block copolymer of the embodiment may be 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% or more. It may be 98% by mass or less, and may be 98% by mass or more and 100% by mass or less.

In the block copolymer of the embodiment, the ratio represented by the number average molecular weight of the polyoxyalkylene block (B) and the number average molecular weight of the aromatic polysulfone block (A) calculated by ^{1 H-NMR is 0.005.} It is ~ 0.030, preferably 0.010 to 0.025, and more preferably 0.015 to 0.020.
When the value of the above ratio is not more than the above lower limit value, the hydrophilicity of the block copolymer becomes good, which is preferable. When the value of the above ratio is not more than the above upper limit value, the thermal properties and mechanical properties of the block copolymer are improved, which is preferable. Improvements in the thermal and mechanical properties of block copolymers are confirmed by comparison with block copolymers containing aromatic polysulfone blocks (A) and polyoxyalkylene blocks (B), where the above ratio values exceed the above upper limits. can.

The number average molecular weight of the aromatic polysulfone block (A) (Mn of the block (A)) may be, for example, 20,000 to 60,000, 25,000 to 50,000, or 27,000 to 40,000. It may be 30,000 to 36,000.

The number average molecular weight of the polyoxyalkylene block (B) (Mn of the block (B)) is, for example, preferably 900 or less, preferably 300 to 900, more preferably 400 to 700, further preferably 450 to 600, and further preferably 500 to 600. 550 is particularly preferable.

The block copolymers of the embodiments are among those exemplified above.
The number average molecular weight of the aromatic polysulfone block (A) may be 20000 to 60,000, the number average molecular weight of the polyoxyalkylene block (B) may be 300 to 900, and the number average molecular weight of the aromatic polysulfone block (A). 25,000 to 50,000, the number average molecular weight of the polyoxyalkylene block (B) may be 400 to 700, the number average molecular weight of the aromatic polysulfone block (A) is 27,000 to 40,000, and the polyoxyalkylene block. The number average molecular weight of (B) may be 450 to 600, the number average molecular weight of the aromatic polysulfone block (A) is 30,000 to 36,000, and the number average molecular weight of the polyoxyalkylene block (B) is 500 to 550. May be. By setting the number average molecular weights of the aromatic polysulfone block (A) and the polyoxyalkylene block (B) within the above numerical range, the balance between hydrophilicity, thermal properties and mechanical properties is excellent. Block copolymers are easily obtained.

The number average molecular weight of the polyoxyalkylene block (B) (Mn of the block) and the number average molecular weight of the aromatic polysulfone block (A) (Mn of the block) can be specified by the NMR method and obtained by 1 H-NMR measurement of ^{solution 1.} The NMR-converted number average molecular weight calculated based on the obtained spectrum can be adopted.

The Mn of the polyoxyalkylene block (B) ^{corresponds to the peak intensity I PAO-Main} corresponding to the main chain of the polyoxyalkylene and the binding site of the polyoxyalkylene bound to the aromatic polysulfone _{as the NMR-equivalent molecular weight M n} ^PAO. The number of repeating units of polyoxyalkylene calculated from the ratio of peak intensity I ^PAO-Link ^{(I PAO-Main} / I ^PAO-Link ^{) n PAO} can be calculated from the value obtained by multiplying the molecular weight per repeating unit of polyoxyalkylene. ..

The Mn of the aromatic polysulfone block (A) corresponds to the peak intensity I ^PES-Main corresponding to the main chain of the aromatic polysulfone and the binding site of the aromatic polysulfone bonded to polyoxyalkylene _{as the NMR-equivalent molecular weight M n} ^PES. The number of repeating units of aromatic polysulfone calculated from the ratio of peak intensity I ^PES-Link ^(IPES-Main / I ^PES-Link ^{) n PES} can be calculated from the value obtained by multiplying the molecular weight per repeating unit of aromatic polysulfone. ..

As an example, the weight average molecular weight (Mw) of the block copolymer of the embodiment may be 20000 to 70000, 30000 to 65000, 40500 to 60000, 43000 to 55000, and 44000. It may be ~ 54000.

The block copolymer of the embodiment contains a polymer that does not contain the aromatic polysulfone block (A) and the polyoxyalkylene block (B) due to unintended decomposition or residual unreacted raw materials. It is also assumed that a very small amount is mixed. In such a case, the weight average molecular weight (Mw) of the block copolymer may be the weight average molecular weight (Mw) of the resin composition containing the block copolymer of the embodiment. The resin composition contains 95% by mass or more and 100% by mass or less of a block copolymer containing the aromatic polysulfone block (A) and the polyoxyalkylene block (B) with respect to the total mass of the resin composition. It may be contained in an amount of 98% by mass or more and 100% by mass or less.

In the present specification, the weight average molecular weight (Mw) is the weight average absolute molecular weight measured by gel permeation chromatography (GPC).

The block copolymer of the embodiment has moderate hydrophilicity and is excellent in thermal properties and mechanical properties.
As an index of the hydrophilicity of the block copolymer, for example, the value of the contact angle of the film obtained by molding the block copolymer with water can be adopted.
The following glass transition temperature (Tg) and 1% mass loss temperature values can be used as indicators of the thermal properties of block copolymers.
The following values of tensile strength and tensile elongation of the molded product can be adopted as an index of the mechanical properties of the block copolymer.

The glass transition temperature (Tg) of the block copolymer of the embodiment is preferably 200 ° C. or higher, more preferably 210 ° C. or higher, still more preferably 215 ° C. or higher.
The upper limit of the glass transition temperature is not particularly limited, and for example, it may be 250 ° C. or lower, 240 ° C. or lower, or 230 ° C. or lower.
The upper limit value and the lower limit value of the glass transition temperature can be arbitrarily combined, and the glass transition temperature (Tg) of the block copolymer of the embodiment may be, for example, 200 ° C. or higher and 250 ° C. or lower, and 210 ° C. or higher and 240 ° C. or higher. The temperature may be 215 ° C or higher and 230 ° C or lower.

The glass transition temperature can be measured by a method according to JIS-K7121 (differential scanning calorimetry (DSC)), and the glass transition temperature when the temperature is raised to 400 ° C. at 10 ° C./min is measured.

The block copolymer of the embodiment in which the glass transition temperature (Tg) is at least the above lower limit value is preferable because it is more excellent in heat resistance. The block copolymer of the embodiment in which the glass transition temperature (Tg) is not more than the above upper limit value is preferable because it facilitates molding.

The 1% mass reduction temperature of the block copolymer of the embodiment is preferably 370 ° C. or higher, more preferably 400 ° C. or higher, still more preferably 430 ° C. or higher.
The upper limit of the 1% mass reduction temperature is not particularly limited, and for example, it may be 500 ° C. or lower, 480 ° C. or lower, or 450 ° C. or lower.
The upper limit value and the lower limit value of the above 1% mass reduction temperature can be arbitrarily combined, and the 1% mass reduction temperature of the block copolymer of the embodiment may be, for example, 370 ° C. or higher and 500 ° C. or lower, and 400 ° C. or higher. It may be 480 ° C. or lower, and may be 430 ° C. or higher and 450 ° C. or lower.

The 1% mass reduction temperature indicates the temperature at which the temperature is raised to 800 ° C. at a heating rate of 10 ° C./min and the mass is reduced by 1% based on the mass of the sample at 200 ° C.

The block copolymer of the embodiment in which the 1% mass reduction temperature is at least the above lower limit value is more excellent in heat resistance.

(Molded body)
The molded article of the embodiment contains the block copolymer of the embodiment. The molded product of the embodiment is molded from the block copolymer of the embodiment.
The molded product of the embodiment can be made by using the block copolymer of the embodiment as a molding material.

The content ratio of the block copolymer of the embodiment with respect to the total mass of the molded product of the embodiment may be, for example, 50 to 100% by mass, 80 to 99.5% by mass, or 90 to 99% by mass. It may be there.

Examples of the method for producing a molded product include a method having a step of molding the block copolymer of the embodiment into a desired shape.

As the molding method, a method of molding the material containing the block copolymer of the embodiment by a solution casting method, extrusion molding, T-die molding, blow molding, injection molding or the like can be exemplified. The block copolymer of the embodiment can be molded into various shapes by selecting a molding method according to the desired shape of the molded product and the like.

As an example of the molded product of the embodiment, a film containing the block copolymer of the embodiment can be exemplified.
The thickness of the film of the embodiment is not particularly limited, but may be, for example, 5 to 200 μm, 7 to 100 μm, or 10 to 50 μm.

Since the molded product of the embodiment contains the block copolymer of the embodiment, it can have appropriate hydrophilicity and is excellent in thermal properties and mechanical properties.

The tensile strength of the molded product obtained by molding the block copolymer of the embodiment is preferably 100 MPa or more, more preferably 101 MPa or more, still more preferably 103 MPa or more.
The upper limit of the tensile strength is not particularly limited, and for example, it may be 150 MPa or less, 130 MPa or less, or 120 MPa or less.
The upper limit value and the lower limit value of the tensile strength can be arbitrarily combined, and the tensile strength of the molded product obtained by molding the block copolymer of the embodiment may be, for example, 100 MPa or more and 150 MPa or less, and 101 MPa. It may be 130 MPa or more, and may be 103 MPa or more and 120 MPa or less.

The above tensile strength can be obtained by the method described in Examples.

The molded product of the block copolymer of the embodiment in which the tensile strength is equal to or higher than the lower limit value is further excellent in mechanical properties.

The tensile elongation of the molded product obtained by molding the block copolymer of the embodiment is preferably 6% or more, more preferably 7% or more, still more preferably 8% or more.
The upper limit of the tensile elongation is not particularly limited, and for example, it may be 30% or less, 20% or less, or 15% or less.
The upper limit value and the lower limit value of the tensile elongation can be arbitrarily combined, and the tensile elongation of the molded product obtained by molding the block copolymer of the embodiment may be, for example, 6% or more and 30% or less. It may be% or more and 20% or less, and may be 8% or more and 15% or less.

The tensile elongation can be obtained by the method described in Examples.
(Measurement of tensile properties of film)
Tensile strength and tensile elongation at break are measured according to JIS K7127. Using a JIS K6251 dumbbell-shaped No. 3 test piece obtained by punching a film with a thickness of 30 μm, the test piece was pulled by an autograph at a grip interval of 50 mm and a tensile speed of 5 mm / min, at 23 ° C. and a relative humidity of 50%. When the test piece is cut (broken) in an atmosphere, the tensile strength (the value obtained by dividing the tensile load value by the cross-sectional area of the test piece) and the tensile elongation (%) are measured.
The tensile elongation was calculated by the following formula. The larger the tensile elongation, the larger the film elongation.
Tensile elongation (%) = (L-Lo) / Lo × 100
Lo: Gripping interval before test (50 mm), L: Gripping interval at break (mm)

The molded product of the block copolymer of the embodiment in which the tensile elongation is equal to or higher than the above lower limit value is further excellent in mechanical properties.

The block copolymer of the embodiment has moderate hydrophilicity and is excellent in thermal properties and mechanical properties.
The block copolymer of the embodiment has appropriate hydrophilicity by containing the polyoxyalkylene block (B).
Block copolymers of embodiments ¹ calculated by ^H-NMR, the ratio represented by the number-average molecular weight of the number average molecular weight of the polyoxyalkylene block (B) / the aromatic polysulfone block (A) is, the specific When it is within the numerical range of, the thermal characteristics and the mechanical characteristics are excellent.

≪Manufacturing method of block copolymer≫
The method for producing the block copolymer of the embodiment is not particularly limited, but as one embodiment, the following method for producing the block copolymer can be exemplified.

The method for producing a block copolymer of the embodiment is a step of reacting an aromatic polysulfone (a) having at least one Cl atom at the end with a polyoxyalkylene compound (b) having at least one hydroxy group at the end ( It may include a block copolymer manufacturing process).

The method for producing a block copolymer of the embodiment is intended to react a prepolymerized aromatic polysulfone (a) with a polyoxyalkylene compound (b), and a step of preparing the aromatic polysulfone (a) in advance is performed. It may also be included.

The method for producing the block copolymer of the embodiment includes a step of preparing an aromatic polysulfone (a) having at least one Cl atom at the terminal in advance and a step of preparing the aromatic polysulfone (a) in advance.
It may include a step (block copolymer manufacturing step) of reacting the aromatic polysulfone (a) with a polyoxyalkylene compound (b) having at least one hydroxy group at the terminal.

The step of preparing the aromatic polysulfone (a) in advance includes obtaining the aromatic polysulfone (a) and simply preparing a commercially available aromatic polysulfone (a).
Alternatively, the method for producing the block copolymer of the embodiment may further include a step of producing the aromatic polysulfone (a) (aromatic polysulfone production step).

The method for producing a block copolymer of the embodiment includes a step of obtaining an aromatic polysulfone (a) having at least one Cl atom at the terminal by a polycondensation reaction.
It may include a step (block copolymer manufacturing step) of reacting the aromatic polysulfone (a) with a polyoxyalkylene compound (b) having at least one hydroxy group at the terminal.

As an example of the aromatic polysulfone (a), for example, by a polycondensation reaction between a compound represented by the following general formula (a1) and a compound represented by the following general formula (a2), the following general formula (a-1) ) Can be obtained.

Wherein ^(a1), R ^1, R 2, n1 and n2 represent the same meaning as in the formula (1). ]

Wherein ^(a2), R ^1, R 2, n1 and n2 represent the same meaning as in the formula (1). ]

Examples of the aromatic polysulfone (a) obtained by the above polycondensation reaction include compounds represented by the following general formula (a-1).

Wherein ^{^{(a-1), R 1}} , R 2, n1, n2 and n represent the same meaning as in the formula (I).
-X ¹ and -X ² are independently -OH or -Cl, and at least one of ^{-X 1} and -X ^{2 is -Cl.} ]

N is the number of repetitions of the structural unit of the aromatic polysulfone (a-1).

In the reaction between the aromatic polysulfone (a) and the polyoxyalkylene compound (b), examples of the aromatic polysulfone (a) include those described above.

The value of the weight average molecular weight of the aromatic polysulfone (a) used as a raw material may be appropriately determined according to the weight average molecular weight of the produced block copolymer.
From the viewpoint of improving the molecular weight of the produced block copolymer, the weight average molecular weight of the above aromatic polysulfone (a) used as a raw material may be 30,000 or more, 30,000 or more and 70,000 or less. It may be 40,000 or more and 65,000 or less.

Examples of the polyoxyalkylene compound (b) include compounds represented by the following general formula (b-1).

Wherein (b-1), ^{R 3} and m represent the same meaning as in the formula (I).
-Y is an alkyl group having 1 to 3 carbon atoms. ]

Examples of the alkyl group having 1 to 3 carbon atoms of —Y include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like, and a methyl group is preferable.

As an example of the reaction between the aromatic polysulfone (a) and the polyoxyalkylene compound (b), a compound represented by the general formula (a-1) and a compound represented by the general formula (b-1) The reaction of, can be exemplified. The reaction can be represented by the following reaction formula. By this reaction, as an example, a block copolymer represented by the general formula (I-1) is obtained.

[In the formula, R ¹ , R ² , R ³ , n1, n2, n, m, X ¹ , X ² and Y are in the above formula (a-1), formula (b-1) and formula (I). Represents the same meaning as. ]

Aromatic polysulfone (a) may be used alone or in combination of two or more.

As the polyoxyalkylene compound (b), one type may be used alone, or two or more types may be used in combination.

The amount of the polyoxyalkylene compound (b) having at least one hydroxy group at the terminal is 0.4 to 2.0 with respect to 1 mol of the aromatic polysulfone (a) having at least one Cl atom at the end. It is preferably mol, more preferably 0.4 to 1.5 mol, even more preferably 0.5 to 1.2 mol, and particularly preferably 0.5 to 0.9 mol. When the amount is within the above range, the Mw measured by GPC of the obtained block copolymer can be further improved, which is preferable.
Here, as the aromatic polysulfone (a) having at least one Cl atom at the terminal, the compound represented by the general formula (a-1) is preferable. As the polyoxyalkylene compound (b) having at least one hydroxy group at the terminal, the compound represented by the general formula (b-1) is preferable.

The reaction between the aromatic polysulfone (a) and the polyoxyalkylene compound (b) is preferably carried out using an alkali metal carbonate and / or an alkali metal bicarbonate as the base of the catalyst. Further, the reaction is preferably carried out in an organic solvent as a solvent, and more preferably carried out in an organic solvent using an alkali metal salt of carbonic acid as a base.

The alkali metal salt of carbonic acid may be an alkali carbonate (alkali metal carbonate) which is a positive salt, or a bicarbonate alkali (hydrogen carbonate alkali, alkali metal hydrogen carbonate) which is an acidic salt. It may be a mixture of these (alkali carbonate and alkali bicarbonate). Examples of preferable alkali carbonate include sodium carbonate, potassium carbonate and the like. Examples of preferable alkali bicarbonate include sodium bicarbonate (sodium hydrogen carbonate), potassium bicarbonate (potassium hydrogen carbonate) and the like.

The blending ratio of the alkali metal salt of carbonic acid is preferably 0.90 mol or more and 1.30 mol or less as the alkali metal with respect to 1 mol of the polyoxyalkylene compound (b), and 0.95 mol or more and 1 mol. More preferably, it is 20 mol or less.

Examples of the organic solvent include an aprotic polar solvent, and the boiling point of the aprotic polar solvent under 1 atm is preferably 250 ° C. or lower. By using an aprotic polar solvent having a boiling point of 250 ° C. or lower, the reaction can proceed while refluxing the aprotic polar solvent at a relatively low temperature to remove by-products.

The boiling point of the aprotic polar solvent is preferably 250 ° C. or lower, and may be 230 ° C. or lower, or 210 ° C. or lower. The boiling point of the aprotic polar solvent may be 120 ° C. or higher, 140 ° C. or higher, or 150 ° C. or higher.
As an example of the numerical range of the boiling point of the above-mentioned aprotic polar solvent, it may be 120 ° C. or higher and 230 ° C. or lower, 140 ° C. or higher and 210 ° C. or lower, or 150 ° C. or higher and 210 ° C. or lower. May be good.

Examples of the aprotonic polar solvent having a boiling point of 250 ° C. or lower include sulfonic solvents such as dimethylsulfone and diethylsulfone, N, N-dimethylacetamide, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, N-methylcaprolactam, N, Amide solvents such as N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N-methylpropionamide, dimethylimidazolidinone, lactone solvents such as γ-butyllactone and β-butyllactone, Examples thereof include sulfoxide-based solvents such as methyl sulfoxide and methylphenyl sulfoxide, cellosolve-based solvents such as tetramethylphosphoric amide and hexamethylphosphoric amide, and cellosolve-based solvents such as ethyl cellosolve acetate and methyl cellosolve acetate.

In the reaction of the aromatic polysulfone (a) and the polyoxyalkylene compound (b), water may be produced as a by-product, and for the purpose of removing this water, a solvent "a solvent that forms an azeotropic mixture with water" is used. May be added.

However, in the production method of the present embodiment, in the reaction of the aromatic polysulfone (a) and the polyoxyalkylene compound (b), an azeotropic mixture with water is formed with respect to the total amount of the solvent used in the reaction. The proportion of the solvent to be used is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, further preferably 0 to 3% by mass, and the solvent used for the reaction is water. It is particularly preferred that it contains substantially no solvent to form an azeotropic mixture with.
By reducing the amount of solvent used to form an azeotropic mixture with water in the reaction of aromatic polysulfone (a) and polyoxyalkylene compound (b), the molecular weight of the block copolymer produced can be increased. be.

The boiling point of the solvent forming the azeotropic mixture with water is preferably 250 ° C. or lower, and may be 230 ° C. or lower, or 210 ° C. or lower. The boiling point of the solvent forming the azeotropic mixture with water may be 40 ° C. or higher, 80 ° C. or higher, or 100 ° C. or higher.
As an example of the numerical range of the boiling point of the solvent forming the azeotropic mixture with water, it may be 40 ° C. or higher and 250 ° C. or lower, 80 ° C. or higher and 230 ° C. or lower, and 100 ° C. or higher and 210 ° C. It may be as follows.

Examples of the solvent for forming an azeotropic mixture with water having a boiling point of 250 ° C. or lower include benzene, chlorobenzene, toluene, xylene, ethylbenzene, methyl isobutyl ketone, hexane, cyclohexane and the like.

The reaction between the aromatic polysulfone (a) and the polyoxyalkylene compound (b) is preferably carried out at 250 ° C. or lower. By carrying out the reaction at a relatively low temperature of 250 ° C. or lower, the energy load can be kept low. The reaction temperature is preferably 250 ° C. or lower, may be 230 ° C. or lower, or may be 210 ° C. or lower. The lower limit of the reaction temperature is not limited, but may be 100 ° C. or higher, 120 ° C. or higher, or 140 ° C. or higher.
As an example of the numerical range of the reaction temperature between the aromatic polysulfone (a) and the polyoxyalkylene compound (b), the temperature may be 100 ° C. or higher and 250 ° C. or lower, or 120 ° C. or higher and 230 ° C. or lower. It may be 140 ° C. or higher and 210 ° C. or lower.

Next, from the reaction mixture obtained by the reaction of the aromatic polysulfone (a) and the polyoxyalkylene compound (b), unreacted bases and by-products (halogen when an alkali metal salt is used as the base). Alkali chemicals) and organic solvents can be removed by filtration, extraction, centrifugation, etc. to separate the block copolymer from the reaction mixture.

The organic solvent may be removed by distilling off the organic solvent directly from the solution, or the solution may be mixed with a poor solvent of the block copolymer to precipitate the block copolymer, which may be filtered or centrifuged. It may be done by separating. A predetermined amount of the organic solvent may remain.

Examples of poor solvents for block copolymers include methanol, ethanol, 2-propanol, acetone, hexane, heptane and water, with preference given to water and methanol due to their low cost.
In the present embodiment, one type of poor solvent for the block copolymer may be used alone, or two or more types may be used in combination.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

<Measurement of Mn and Mw and calculation of Mw / Mn in block copolymers, etc.>
The weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw / Mn) of each polymer (each block copolymer and raw material polyethylene glycol monomethyl ether) were determined by GPC measurement. Both Mn and Mw were measured twice, and the average value thereof was calculated as Mn and Mw, respectively, and the average value of Mw / Mn was obtained.
[Measurement condition]
Sample: 0.002 g of aromatic polysulfone is mixed with 1 mL of N, N-dimethylformamide solution containing 10 mM lithium bromide Sample injection amount: 100 μL
Column (stationary phase): Two "TSKgel GMHHR-H" (7.8 mmφ x 300 mm) manufactured by Tosoh Corporation are connected in series. Column temperature: 40 ° C.
Eluent (mobile phase): N, N-dimethylformamide containing 10 mM lithium bromide Eluent flow rate: 0.8 mL / min Detector: Differential refractive index meter (RI) + light scattering photometric meter (LS)
Standard reagent: Polystyrene Molecular weight calculation method: Absolute molecular weight is calculated from the measurement results of a light scattering photometer (LS).

< ^{Measurement of solution 1 1} H-NMR>
^{Solution 1} for calculating NMR-equivalent molecular weight For 1 H-NMR measurement, a sample dissolved in deuterated dimethylsulfoxide was used so that the concentration of the block copolymer to be measured was 50 mg / ml. The measurement conditions are as follows.

Measuring device: PS400WB (manufactured by Varian)
Static magnetic field strength: 9.4 Tesla (resonance frequency: 400 MHz ( ¹ H))
Spinning: 16Hz
Repeat time: 1.5s
Number of integrations: 128 times Temperature: 40 ° C
Chemical shift reference material: Tetramethylsilane

<Calculation of NMR-equivalent molecular weight of PES block and PAO block>
The NMR equivalent number average molecular weight (Mn of the block) of the polyether sulfone (PES) block and the polyoxyalkylene (PAO) block contained in the block copolymer to be measured is calculated based on the spectrum obtained by the ^{solution 1 H-NMR measurement.} bottom.

The Mn of the PAO block contained in the block copolymer has ^{a peak intensity I PAO-Main} corresponding to the main chain of PAO and a peak intensity I corresponding to the binding site of PAO bound to PES _{as an NMR equivalent number average molecular weight M n} ^PAO. It was calculated from the value obtained by multiplying the number of repeating units of ^PAO n PAO calculated from the ratio of ^PAO-Link ^{(I PAO-Main} / I ^PAO-Link ) by the molecular weight per repeating unit of PAO. In this example, n ^PAO was calculated by the following formula.
(I ^PAO-Main / I ^PAO-Link ) = (4 × n ^PAO ) / 4

The Mn of the PES block contained in the block copolymer has ^{a peak intensity I PES-Main} corresponding to the main chain of ^{PES and a peak intensity I PES-} corresponding to the binding site of PES bound to PAO _{as an NMR-equivalent molecular weight M n} ^PES. ^It was calculated from the value obtained by multiplying the number of repeating units of ^PES n PES calculated from the ratio of ^{Link (IPES-Main} / I ^PES-Link ) by the molecular weight per repeating unit of PES. In the block copolymer according to this example, which contains a PEG block as a PAO block, n ^PES was calculated by the following formula.
(I ^PES-Main / I ^PES-Link ) = [{(4 × n ^PES ) + 4} -4] / 4

The Mn / PES block Mn ratio of the PAO block contained in the block copolymer was calculated by dividing _{M n} ^PAO by M _n ^PES.

<Measurement of glass transition temperature (Tg) of block copolymers, etc.>
The glass transition temperature was measured by a method according to JIS-K7121 (differential scanning calorific value measurement (DSC)), and the glass transition temperature when the temperature was raised to 400 ° C. at 10 ° C./min was measured.

<Measurement of 1% mass reduction temperature of block copolymers, etc.>
The 1% mass reduction temperature indicates the temperature at which the temperature was raised to 800 ° C. at a heating rate of 10 ° C./min and the mass was reduced by 1% based on the mass of the sample at 200 ° C.

<Measurement of film contact angle>
A film was attached to a smooth glass plate, and 2 μL of pure water was dropped onto the film. The contact angle was measured 10 seconds after the droplet was applied.
Measuring device: DM-501 (manufactured by Kyowa Interface Science)
Temperature: 23 ° C
Measurement method: θ / 2 method

<Measurement of film tensile properties>
Tensile strength and tensile elongation at break were measured according to JIS K7127. Using a JIS K6251 dumbbell-shaped No. 3 test piece obtained by punching a film with a thickness of 30 μm, the test piece was pulled by an autograph at a grip interval of 50 mm and a tensile speed of 5 mm / min, at 23 ° C. and a relative humidity of 50%. The tensile strength (the value obtained by dividing the tensile load value by the cross-sectional area of the test piece) and the tensile elongation (%) when the test piece was cut (broken) in an atmosphere were measured.
The tensile elongation was calculated by the following formula. The larger the tensile elongation, the larger the film elongation.
Tensile elongation (%) = (L-Lo) / Lo × 100
Lo: Gripping interval before test (50 mm), L: Gripping interval at break (mm)

<Manufacturing of block copolymers>
[Experimental Example 1]
In a polymerization tank equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a condenser with a receiver at the tip, 1.5 g of polyethylene glycol monomethyl ether (manufactured by Tokyo Kasei, weight average molecular weight 570), 0.46 g of potassium carbonate, and 150 g of N-methyl-2-pyrrolidone (NMP) is mixed, the temperature is raised to 100 ° C., and then the absolute weight measured with a DMF solvent by polyether sulfone (manufactured by Sumitomo Chemical Co., Ltd., Sumika Excel PES 5900P, gel permeation chromatography). (Average molecular weight of 30,000 or more) 100 g was added. After the polyether sulfone was dissolved, it was heated at 200 ° C. and reacted for 14 hours. The resulting reaction mixture was then diluted with NMP and cooled to room temperature to precipitate unreacted potassium carbonate and by-product potassium chloride. The above solution was added dropwise to water to precipitate aromatic polysulfone, and unnecessary NMP was removed by filtration to obtain a precipitate.
The obtained precipitate was carefully washed repeatedly with methanol and water and dried by heating at 150 ° C. to obtain an aromatic polysulfone block copolymer having polyethylene glycol at the end.

[Experimental Examples 2-4]
Experimental Example 1 above, except that the molecular weight and compounding amount of the polyethylene glycol monomethyl ether used above were changed as shown in Table 1 (Tokyo Kasei, weight average molecular weight 1000, Tokyo Kasei, weight average molecular weight 4600). In the same manner as above, an aromatic polysulfone block copolymer having polyethylene glycol at the end was obtained.

[Experimental Example 5]
The above-mentioned polyether sulfone (Sumika Excel PES 5900P, manufactured by Sumitomo Chemical Co., Ltd.) was used as a sample of Experimental Example 5.

Experimental Examples 1 and 2 above correspond to Examples to which the present invention is applied.

For the aromatic polysulfone block copolymers of Experimental Examples 1 to 4 and the aromatic polysulfone of Experimental Example 5, weight average absolute molecular weight (Mw), polydispersity (Mw / Mn), Mn of PES block, Mn of PEG block, PEG. The values of Mn, Tg and 1% mass reduction temperature of the Mn / PES block of the block were measured.

<Making cast film>
In a heating container, 18 parts by mass of the aromatic polysulfone block copolymer of Experimental Examples 1 to 4 or 18 parts by mass of aromatic polysulfone and 82 parts by mass of NMP of Experimental Example 5 are mixed and stirred at 80 ° C. for 2 hours to obtain a pale yellow color. Solution was obtained. This was applied to one surface of a glass plate having a thickness of 3 mm using a film applicator, and then dried at 60 ° C. using a high-temperature hot air dryer to form a coating film. This coating film was heat-treated at 250 ° C. while flowing nitrogen to form a film having a thickness of 30 μm on a glass plate. A film was obtained by peeling this film from a glass plate.
For the obtained film, the contact angle with water, the tensile strength and the tensile elongation were measured.

The above measurement results are shown in Tables 2 and 3.

From the results shown in Table 2, the films obtained from the aromatic polysulfone block copolymers of Experimental Examples 1 and 2 have smaller contact angle values and are hydrophilic than the films obtained from the aromatic polysulfone of Experimental Example 5. Was shown to be improving.

From the results shown in Table 3, the aromatic polysulfone block copolymers of Experimental Examples 1 and 2 in which the values of PEG block Mn / PES block Mn satisfy 0.005 to 0.030 do not satisfy the values in Experimental Example 3. It was shown that the values of Tg and 1% mass reduction temperature were higher than those of the aromatic polysulfone block copolymers of -4, and the thermal properties were excellent.

From the results shown in Table 3, the aromatic polysulfone block copolymers of Experimental Examples 1 and 2 in which the values of PEG block Mn / PES block Mn satisfy 0.005 to 0.030 do not satisfy the values in Experimental Example 3. It was shown that the values of tensile strength and tensile elongation were higher and the mechanical properties were superior to those of the aromatic polysulfone block copolymers of ~ 4.

Each configuration in each embodiment and a combination thereof are examples, and the configuration can be added, omitted, replaced, and other changes are possible without departing from the spirit of the present invention. Moreover, the present invention is not limited to each embodiment, but is limited only to the scope of claims.

Claims

A block copolymer containing an aromatic polysulfone block (A) and a polyoxyalkylene block (B).
1 The ratio represented by the number average molecular weight of the polyoxyalkylene block (B) / the number average molecular weight of the aromatic polysulfone block (A) calculated by 1 H-NMR is 0.005 to 0.030. , Block copolymer.
1 The block copolymer according to claim 1, wherein the number average molecular weight of the polyoxyalkylene block (B) calculated by 1 H-NMR is 900 or less.
The block copolymer according to claim 1 or 2, wherein the block copolymer has a weight average molecular weight of 20,000 to 70,000, which is obtained as an absolute molecular weight by gel permeation chromatography.
A linear triblock copolymer having the above three blocks, and the polyoxyalkylene block (B) in the order of the polyoxyalkylene block (B), the aromatic polysulfone block (A), and the polyoxyalkylene block (B). A linear diblock copolymer having the above two blocks of B) and the aromatic polysulfone block (A),
The block copolymer according to any one of claims 1 to 3, which comprises at least one of the above.
The block copolymer according to any one of claims 1 to 4, wherein the aromatic polysulfone block (A) comprises a polymer chain having a structural unit represented by the following formula (1).

[In equation (1),
R 1 and R 2 independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom.
n1 and n2 are independently integers of 0 to 4, respectively.
When n1 or n2 is 2 or more, plural R 1 and R 2 may be the same or different from each other. ]
The block copolymer according to any one of claims 1 to 5, wherein the polyoxyalkylene block (B) is composed of a polymer chain having a structural unit represented by the following formula (2-1).
The block copolymer according to any one of claims 1 to 6, wherein the glass transition point of the block copolymer is 200 ° C. or higher.
The block copolymer according to any one of claims 1 to 7, wherein the 1% mass reduction temperature of the block copolymer is 370 ° C. or higher.
The block copolymer according to any one of claims 1 to 8, wherein the tensile strength of the molded product obtained by molding the block copolymer, which is obtained by the following measuring method, is 100 MPa or more.
(Measuring method)
As the molded body, a JIS K6251 dumbbell-shaped No. 3 test piece having a thickness of 30 μm was used, and in accordance with JIS K7127, an autograph was used to pull the product at a grip interval of 50 mm and a tensile speed of 5 mm / min at 23 ° C. The tensile strength when the test piece is cut (broken) in an atmosphere of 50% relative humidity is determined.