阅读说明：本技术 聚联苯醚砜树脂及成型品 (Polybiphenyl ether sulfone resin and molded article ) 是由 伊藤和幸 于 2019-09-20 设计创作，主要内容包括：本发明涉及聚联苯醚砜树脂等,所述聚联苯醚砜树脂实质上由下述式(1)的重复结构构成,所述聚联苯醚砜树脂的聚苯乙烯基准的质均分子量Mw以及温度为350℃条件下的熔融粘度μ满足式(6)和式(7)。[式(1)中,n表示1以上的整数。]60000≤Mw≤90000(6)；0.0906×Mw－4930≤μ≤3500(7),(The present invention relates to a polybiphenyl ether sulfone resin and the like, wherein the polybiphenyl ether sulfone resin is substantially composed of a repeating structure of the following formula (1), and the polystyrene-based mass average molecular weight Mw and the melt viscosity μ at a temperature of 350 ℃ of the polybiphenyl ether sulfone resin satisfy the formulae (6) and (7). [ in the formula (1), n represents an integer of 1 or more.]60000≤Mw≤90000(6)；0.0906×Mw－4930≤μ≤3500(7)，)

1. A polybiphenyl ether sulfone resin, which is substantially composed of a repeating structure of the following formula (1), wherein the mass average molecular weight Mw based on polystyrene and the melt viscosity mu at a temperature of 350 ℃ satisfy the following formulae (6) and (7), and the unit of the melt viscosity mu is Pa s,

wherein n represents an integer of 1 or more,

60000≤Mw≤90000 (6)；

0.0906×Mw－4930≤μ≤3500 (7)。

2. the polybiphenyl ether sulfone resin of claim 1, wherein the mass average molecular weight Mw satisfies the following formula (6-1),

65000≤Mw≤75000 (6-1)。

3. the polybiphenyl ether sulfone resin of claim 1 or 2, wherein the mass average molecular weight Mw and the melt viscosity μ satisfy the following formula (7-1),

0.0906×Mw－4930≤μ≤2000 (7-1)。

4. a melt-molded article comprising the polybiphenyl ether sulfone resin according to any one of claims 1 to 3.

Technical Field

The present invention relates to a polybiphenyl ether sulfone resin and a molded article comprising the same.

The present application is based on the Japanese patent application No. 2018-180561, filed in Japan on 26.9.2018, the contents of which are incorporated herein by reference, and claims priority thereto.

Background

A molded article of a polybiphenyl ether sulfone resin having a repeating unit represented by the following formula (1-1) is excellent in heat resistance, impact resistance, solvent resistance and the like. It is also known that, in general, the higher the molecular weight of the polybiphenyl ether sulfone resin is, the higher the heat resistance and impact resistance of the resulting molded article is,

as a method for producing a polybiphenyl ether sulfone resin, for example, patent documents 1 to 3 and the like report a method of polymerizing 4, 4 '-dihydroxybiphenyl and 4, 4' -dihalodiphenylsulfone compounds in an aprotic polar solvent in the presence of potassium carbonate.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2004-107606;

patent document 2: japanese patent laid-open publication No. 2004-263154;

patent document 3: japanese Kohyo publication No. 2002-525406.

Disclosure of Invention

Problems to be solved by the invention

Molded articles of a polybiphenyl ether sulfone resin excellent in heat resistance, impact resistance, solvent resistance and the like are expected to be applied to applications in which they are used under high-temperature environments. However, it is known that a compressed tablet obtained by compression molding a conventional polybiphenyl ether sulfone resin shrinks at a high temperature of 200 ℃ and then returns to normal temperature, and dimensional changes (hereinafter, sometimes referred to as "post shrinkage") occur due to the shrinkage compared to the original dimensions.

The purpose of the present invention is to provide a polybiphenyl ether sulfone resin which can provide a molded article that, even when returned to room temperature after thermal annealing, has little change from its original dimensions, i.e., has little post-shrinkage, and to provide a molded article that has little post-shrinkage.

Means for solving the problems

In order to solve the above problem, the present invention adopts the following configuration.

[1] A polybiphenyl ether sulfone resin which is substantially composed of a repeating structure represented by the following formula (1) and satisfies the following formulae (6) and (7) in terms of a polystyrene-based mass average molecular weight Mw and a melt viscosity [ mu ] Pa s ] at a temperature of 350 ℃.

[ in the formula, n represents an integer of 1 or more. ]

60000≤Mw≤90000 (6)

0.0906×Mw－4930≤μ≤3500 (7)

[2] The polybiphenyl ether sulfone resin of [1], wherein the mass average molecular weight Mw satisfies the following formula (6-1),

65000≤Mw≤75000 (6-1)。

[3] the polybiphenyl ether sulfone resin of [1] or [2], wherein the mass average molecular weight Mw and the melt viscosity μ satisfy the following formula (7-1),

0.0906×Mw－4930≤μ≤2000 (7-1)。

[4] a melt-molded article comprising the polybiphenyl ether sulfone resin according to any one of [1] to [3 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The molded article obtained from the polybiphenyl ether sulfone resin of the present invention shows little change from the original dimensions, i.e., little post-shrinkage, even when returned to room temperature after thermal annealing.

Drawings

FIG. 1 is a graph showing the relationship between melt viscosity. mu. and mass average molecular weight Mw.

Detailed Description

The present invention will be described in detail below.

Poly (biphenyl ether sulfone) resin

The polybiphenyl ether sulfone resin of the present invention is substantially composed of a repeating structure of the following formula (1).

[ in the formula, n represents an integer of 1 or more. ]

The polybiphenyl ether sulfone resin of the present invention can be represented by, for example, the following formula (1-2), formula (1-3) or formula (1-4). The polybiphenyl ether sulfone resin (1-2) represented by the following formula (1-2) having a halogen atom at the terminal has a higher thermal decomposition temperature, is less likely to be colored, and has excellent thermal stability, as compared with the polybiphenyl ether sulfone resin (1-3) represented by the following formula (1-3) having a phenolic hydroxyl group at the terminal and the polybiphenyl ether sulfone resin (1-4) represented by the following formula (1-4) having a methoxy group at the terminal.

[ in the formula, X¹And X²Each independently represents a halogen atom, and n represents an integer of 1 or more.]

In the present specification, the phrase "the poly (biphenyl ether sulfone) resin substantially consists of the repeating structure of the formula (1)" means that the mass of the repeating structure of the formula (1) is 90 mass% or more, more preferably 95 mass% or more, more specifically, may be 90 mass% or more and 100 mass% or less, more preferably 95 mass% or more and 100 mass% or less, with respect to the total mass of the poly (biphenyl ether sulfone) resin.

n represents an integer of 1 or more, and the polybiphenyl ether sulfone resin of the present invention may be a mixture containing a compound in which n is an integer of 1 or 2 or more. n may be an integer of 10000 or less.

The poly biphenyl ether sulfone resin of the invention has a polystyrene-based mass average molecular weight Mw and a melt viscosity [ mu [ Pa.s ] at a temperature of 350 ℃ satisfying the following formulas (6) and (7).

60000≤Mw≤90000 (6)

0.0906×Mw－4930≤μ≤3500 (7)

In the present specification, the melt viscosity μ [ Pa · s ] can be measured by the method described in the measurement of the melt viscosity of the polybiphenyl ether sulfone resin described later.

FIG. 1 is a graph showing the relationship between melt viscosity. mu. and mass average molecular weight Mw. FIG. 1 is a graph showing that the mass average molecular weight (Mw) and the melt viscosity [ mu ] Pa · s of the polybiphenyl ether sulfone resin of the example of the present invention satisfy the formula (6) and the formula (7).

To the left of equation (7), the value of "0.0906" representing the slope is based on the finding: when the mass average molecular weight Mw is plotted on the horizontal axis and the melt viscosity μ is plotted on the vertical axis, it is found from the data of examples and comparative examples described later that the relationship between the mass average molecular weight (Mw) of the polybiphenyl ether sulfone resin and the melt viscosity μ [ Pa · s ] at a temperature of 350 ℃ is approximately aligned on a straight line having a slope of "0.0906".

The polybiphenyl ether sulfone resin of the present invention has a relationship between the polystyrene-based mass average molecular weight (Mw) and the melt viscosity [ mu ] Pa.s ] at a temperature of 350 ℃ in accordance with the formula [ 0.0906X Mw-4930. ltoreq. mu ]. When the formula [0.0906 XMw-4930. ltoreq. mu ] is satisfied, a molded article obtained from the polybiphenyl ether sulfone resin undergoes a small change from the original size, that is, a small post-shrinkage even when returned to room temperature after thermal annealing.

Further, the data of examples and comparative examples described later show that: the formula [ μ ═ 0.0906 × Mw-4930] is a boundary line between a molded article with less after-shrinkage and a molded article with large after-shrinkage in a molded article containing a polybiphenyl ether sulfone resin substantially composed of the repeating structure of the formula (1).

The polybiphenyl ether sulfone resin of the present invention is particularly preferably a resin having a polystyrene-based mass average molecular weight Mw and a melt viscosity μ [ Pa · s ] at a temperature of 350 ℃ satisfying the following formula (7-1),

0.0906×Mw－4930≤μ≤2000 (7-1)。

the polybiphenyl ether sulfone resin of the present invention may have a relationship between the polystyrene-based mass average molecular weight (Mw) and the melt viscosity [ mu ] Pa.s at a temperature of 350 ℃ in the formula [ mu ] 0.0906X Mw-3430], the formula [ mu ] 0.0906X Mw-3930], and the formula [ mu ] 0.0906X Mw-4430 ].

The polydispersity (Mw/Mn) of the polybiphenyl ether sulfone resin of the present invention can be 1.5 to 8.0, can be 2.0 to 7.0, can be 3.0 to 6.0, and can be 4.5 to 4.8. By setting the polydispersity (Mw/Mn) to an upper limit or less, the impact resistance can be further improved.

The polybiphenyl ether sulfone resin of the present invention has a polystyrene-based mass average molecular weight (Mw) of 60000 to 90000, may be 63000 to 80000, may be 65000 to 75000, and may be 68500 to 75000, and can have impact resistance more excellent by setting the mass average molecular weight Mw to a lower limit or more, and processability more excellent by setting the mass average molecular weight Mw to an upper limit or less.

In one aspect of the present invention, there is provided a polybiphenyl ether sulfone resin having a polystyrene-based mass average molecular weight (Mw) of 68500 to 75000 and a polydispersity (Mw/Mn) of 4.5 to 4.8.

The melt viscosity μ of the polybiphenyl ether sulfone resin of the present invention at a temperature of 350 ℃ is 3500Pa · s or less, preferably 3000Pa · s or less, more preferably 2500Pa · s or less, and particularly preferably 2000Pa · s. By setting the melt viscosity μ to be not more than the upper limit value, the moldability can be further improved.

The melt viscosity μ of the polybiphenyl ether sulfone resin of the present invention at a temperature of 350 ℃ may be 500Pa · s or more, and may be 1300Pa · s or more.

That is, the melt viscosity μ is preferably 500Pa · s or more and 3500Pa · s or less, 500Pa · s or more and 3000Pa · s or less, 500Pa · s or more and 2500Pa · s or less, 500Pa · s or more and 2000Pa · s or less, 1300Pa · s or more and 2500Pa · s or less, or 1300Pa or more and 2000Pa · s or less.

The mass average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw/Mn) of the polybiphenyl ether sulfone resin were measured by Gel Permeation Chromatography (GPC) using a column based on styrene-divinylbenzene and in accordance with standard polystyrene standards.

Method for producing polybiphenyl ether sulfone resin

A polybiphenyl ether sulfone resin can be produced by a polycondensation reaction of a 4, 4 '-dihalodiphenylsulfone compound and 4, 4' -dihydroxybiphenyl in an aprotic polar solvent.

The 4, 4' -dihalodiphenylsulfone compound used in the method for producing a polybiphenyl ether sulfone resin is a compound represented by the following formula (2).

[ in the formula, X¹And X²Each independently represents a halogen atom.]

In the formula (2), as represented by X¹And X²Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the 4, 4 '-dihalodiphenylsulfone compound include 4, 4' -difluorodiphenylsulfone, 4 '-dichlorodiphenylsulfone and 4, 4' -dibromodiphenylsulfone.

The 4, 4' -dihydroxybiphenyl used in the present invention is a compound represented by formula (3).

In one aspect of the present invention, the method for producing the polybiphenyl ether sulfone resin represented by the following formula (1-2) can be represented by the following reaction formula (4) when an alkali metal carbonate is used, for example.

[ in the formula, X¹And X²The same meanings as above, M represents an alkali metal, and n represents an integer of 1 or more.]

In the method for producing a polybiphenyl ether sulfone resin, the polycondensation reaction is preferably performed under the condition that the mass a of the polybiphenyl ether sulfone resin obtained by the polycondensation reaction and the mass B of the aprotic polar solvent satisfy the following formula (5).

35≤A×100÷(A+B)≤44 (5)

When the charged mole number of the 4, 4 ' -dihalodiphenylsulfone compound (2) is not less than the charged mole number of the 4, 4 ' -dihydroxybiphenyl (3) (for example, relative to the 4, 4 ' -dihydroxybiphenyl)(3)1 mol, and preferably 1.02 to 1.05 mol of 4, 4 '-dihalodiphenylsulfone compound (2), the mass A of the polybiphenyl ether sulfone resin (1-2) represented by the formula (1-2) obtained by the polycondensation reaction can be obtained by subtracting the hydrogen Halide (HX) equivalent to 2 times the charged mass of 4, 4' -dihydroxybiphenyl (3) from the sum of the charged mass of the 4, 4 '-dihalodiphenylsulfone compound (2) and the charged mass of the 4, 4' -dihydroxybiphenyl (3) in the reaction formula (4)¹、HX²) The mass of (b) is obtained as a quantity. Here, when the halogen atom X¹And X²Mutually different, the mass to be subtracted being the equivalent molar number of hydrogen Halide (HX) to the charged mass of 4, 4' -dihydroxybiphenyl (3)¹) The mass of (3) and the molar number of the hydrogen Halide (HX) equivalent to the equivalent molar number of the charged mass of 4, 4' -dihydroxybiphenyl (3)²) The sum of the masses of (a) and (b).

When the charged mole number of the 4, 4 '-dihalodiphenylsulfone compound (2) is less than the charged mole number of the 4, 4' -dihydroxybiphenyl (3) (for example, when 0.90 to 1 mole, preferably 0.95 to 0.98 mole of the 4, 4 '-dihalodiphenylsulfone compound (2) is used relative to 1 mole of the 4, 4' -dihydroxybiphenyl (3)), the same polycondensation reaction as in the reaction formula (4) is carried out to obtain the polybiphenyl ether sulfone resin (1-3) represented by the formula (1-3). Further, a halogenated methyl group is reacted with the polybiphenyl ether sulfone resin (1-3) to obtain the polybiphenyl ether sulfone resin (1-4) represented by the formula (1-4). The calculated mass A of the polybiphenyl ether sulfone resin (1-3) represented by the formula (1-3) and the polybiphenyl ether sulfone resin (1-4) represented by the formula (1-4) obtained by the polycondensation reaction can be obtained by subtracting a hydrogen Halide (HX) in an amount of 2 times by mol as much as the charged mass of the 4, 4 ' -dihalodiphenylsulfone compound (2) from the sum of the charged mass of the 4, 4 ' -dihalodiphenylsulfone compound (2) and the charged mass of the 4, 4 ' -dihydroxybiphenyl (3)¹、HX²) The mass of (b) is obtained as a quantity. Here, when the halogen atom X¹And X²The mass to be subtracted is equivalent to the equivalent molar number of the charged mass of the 4, 4' -dihalodiphenylsulfone compound (2) and the hydrogen Halide (HX)¹) Quality and ofEquivalent mole number of hydrogen Halide (HX) to equivalent mole number of charge mass of 4, 4' -dihalodiphenylsulfone compound (2)²) The sum of the masses of (a) and (b).

In the method for producing a polybiphenyl ether sulfone resin, the polymerization concentration defined by [ a × 100 ÷ (a + B) ] is preferably 35% or more and 44% or less. The polybiphenyl ether sulfone resin manufactured under the condition satisfying the condition of formula (5) can satisfy the formula (7). The polymerization concentration is preferably 43% or less, more preferably 42% or less. When the polymerization concentration is not more than the upper limit, the formula (7) can be satisfied, and a molded article which is less changed in size from the original size even when returned to normal temperature after thermal annealing, that is, which is, less post-shrinkage can be provided. The polymerization concentration is preferably 37% or more, more preferably 39% or more, and particularly preferably 41% or more. When the polymerization concentration is not less than the lower limit, the polycondensation reaction can be efficiently performed in a short time.

That is, the polymerization concentration may be, for example, 35% or more and 44% or less, 37% or more and 44% or less, 39% or more and 43% or less, 41% or more and 44% or less, 39% or more and 42% or less, 41% or more and 43% or less, or 41% or more and 42% or less.

Although the polycondensation reaction is carried out in an aprotic polar solvent, the reaction is not a reaction of a homogeneous system but a reaction in a slurry state. Therefore, it is considered that, when the polymer intermolecular structure of the polybiphenyl ether sulfone resin of the reaction product is different in polymerization concentration defined by [ a × 100 ÷ (a + B) ], the polymer molecules are entangled with each other even if the mass average molecular weight Mw and the polydispersity Mw/Mn are the same. Further, it is considered that when the polymerization concentration is not more than the upper limit, the formula (7) can be satisfied, and a molded article which is less in dimensional change from the original size even when it is returned to normal temperature after use in a high-temperature environment, that is, which is, less in post-shrinkage can be provided.

The amount of the 4, 4 '-dihalodiphenylsulfone compound (2) to be used is not limited as long as it is adjusted to satisfy the above formula (6), but is usually 0.90 to 1.10 mol or 0.95 to 1.05 mol, preferably 0.95 to 0.98 mol or 0.96 to 0.98 mol, or 1.02 to 1.05 mol or 1.02 to 1.04 mol based on 1 mol of 4, 4' -dihydroxybiphenyl (3). It is preferably 0.95 to 1.05 mol because the molecular weight of the resulting polybiphenyl ether sulfone resin tends to be high.

In the method for producing a polybiphenyl ether sulfone resin, an alkali metal carbonate and/or an alkali metal bicarbonate can be used as an alkali catalyst. For example, the alkali metal carbonate includes potassium carbonate and sodium carbonate, the alkali metal bicarbonate includes potassium bicarbonate and sodium bicarbonate, and potassium carbonate is generally used.

In addition, as the alkali catalyst, it is preferable to use a powder of an alkali metal carbonate and/or an alkali metal bicarbonate.

The amount of the alkali metal carbonate and/or alkali metal bicarbonate to be used is usually 1 mol or more and 1.2 mol or less, may be 1.01 mol or more and 1.15 mol or less, and may be 1.02 mol or more and 1.15 mol or less based on 1 mol of 4, 4' -dihydroxybiphenyl (3).

Examples of the aprotic polar solvent used in the present invention include sulfone-based solvents, amide-based solvents, lactone-based solvents, sulfoxide-based solvents, organophosphorus-based solvents, and cellosolve-based solvents. Examples of the sulfone solvent include diphenyl sulfone, dimethyl sulfone, diethyl sulfone, and sulfolane. Examples of the amide solvent include N, N-dimethylacetamide, N-methyl-pyrrolidone, N-methylcaprolactam, N-dimethylformamide, N-diethylformamide, N-diethylacetamide, N-methylpropionamide, and dimethylimidazolidinone. Examples of the lactone-based solvent include γ -butyl lactone and β -butyl lactone. Examples of the sulfoxide solvent include dimethyl sulfoxide and methylphenyl sulfoxide. Examples of the organophosphorus solvent include tetramethylphosphoramide and hexamethylphosphoramide. Examples of the cellosolve solvent include ethyl cellosolve acetate and methyl cellosolve acetate.

The aprotic polar solvent used in the present invention is preferably a sulfone solvent, and more preferably diphenyl sulfone.

The temperature of the polycondensation reaction is preferably 180 ℃ to 300 ℃, more preferably 240 ℃ to 300 ℃. At 240 ℃ or higher, the reaction rate of polymerization tends to be increased, and therefore, it is preferable, and at 300 ℃ or lower, the molecular weight dispersion of the obtained polybiphenyl ether sulfone resin tends to be reduced, that is, the molecular weight distribution tends to be more uniform. The time required for the polycondensation reaction is usually about 3 to 20 hours.

The polycondensation reaction is carried out in this manner, but in order to obtain the polybiphenyl ether sulfone resin from the reaction mixture after the reaction, for example, the reaction mixture after the reaction is solidified to be a powder, and then washed with a solvent. The reaction mixture after the reaction may be solidified by cooling, and can be solidified by cooling to about room temperature. In order to make the solidified reaction mixture into powder, the reaction mixture may be pulverized. As the solvent used for washing, a solvent which is insoluble in the poly (biphenyl ether sulfone) resin and can dissolve the alkali metal salt such as the alkali metal halide produced by polymerization and the aprotic polar solvent is used, and for example, water; aliphatic ketones such as acetone and methyl ethyl ketone; and aliphatic alcohols such as methanol, ethanol, and isopropanol, and mixed solvents thereof.

Melt-molded article

The melt-molded article of the present invention contains the above-mentioned polybiphenyl ether sulfone resin of the present invention. The melt-molded article of the present invention may be in the form of powder, granule, film, sheet, extruded long-length molded article, or injection molded article. The polybiphenyl ether sulfone resin can be obtained in the form of a film or a sheet by hot pressing, in the form of a long molded article by extrusion molding, in the form of a film by T-die molding, in the form of a hollow product such as various containers, building materials, sporting goods and the like by blow molding, and in the form of an injection molded article by injection molding, for example. The injection-molded article can be produced by injection-molding the polybiphenyl ether sulfone resin using a general injection molding machine under conditions of a mold temperature of 120 to 180 ℃ and a resin melting temperature of 330 to 380 ℃. In one aspect, the melt-molded article of the present invention is a molded article which is less susceptible to dimensional change than the original dimensions even when the temperature is returned to room temperature after thermal annealing, because the above-described polybiphenyl ether sulfone resin of the present invention is used. In another aspect, the melt-molded article of the present invention is a molded article which is excellent in impact resistance and is less likely to change in impact resistance before and after thermal annealing, that is, is less likely to thermally deteriorate, because the polybiphenyl ether sulfone resin of the present invention is used.

The melt-molded article of the present invention can have an impact resistance represented by an Izod impact resistance of 200 to 2000J/m, 400 to 1500J/m, 500 to 1000J/m, and 600 to 800J/m.

An Izod impact resistance [ J/m ] of a melt-molded article was measured in accordance with ASTM D256 on a test piece having a length of 70mm, a width of 10mm, and a thickness of 1.9mm, and having a notch (notch) at the center portion with a tip radius of 0.25mm and a depth of 5mm, which was manufactured by a method described in an impact resistance test described later.

The test piece may be produced using a powder obtained by freeze-pulverizing a melt-molded product by a freeze-pulverizer described later, instead of the "polybiphenyl ether sulfone resin" described in the impact resistance test described later. For the freeze-pulverization, a sample can be filled in a stainless steel container and carried out, for example, under the following conditions.

A freezing and crushing machine: freezer Mill 6770 manufactured by SPEX corporation

Temperature: temperature of liquid nitrogen

And (3) crushing time: 3 minutes

The heat aging property of the melt-molded article of the present invention can be evaluated by the Izod impact resistance after heat annealing after placing the article in an oven at 180 ℃ for 24 hours. The melt-molded article of the present invention can have an Izod impact resistance after thermal annealing substantially unchanged from that before thermal annealing, and the Izod impact resistance before and after thermal annealing can be set to 200 to 2000J/m, 400 to 1500J/m, 500 to 1000J/m, and 600 to 800J/m, respectively.

In one aspect of the melt-molded article of the present invention, the change in the Izod impact resistance after the thermal annealing is in the range of-50% to + 50%, preferably-30% to + 30%, more preferably-10% to + 30%, more preferably-7% to + 30%, and still more preferably-7% to + 10% relative to the Izod impact resistance before the thermal annealing.

As one aspect of the polybiphenyl ether sulfone resin of the present invention, the following properties are exhibited: when the post shrinkage of a measurement sample (5 mm. times.20 mm, thickness of about 0.2mm) prepared by the method described in the preparation of a compressed tablet and the measurement of the post shrinkage described later is measured by the same method, the post shrinkage is 17.0 μm or less, preferably 15.0 μm or less, more preferably 13.5 μm or less, and still more preferably 13.0 μm or less. The smaller the amount of the after-shrinkage, the more preferable it is, the more preferable it may be 0 μm, but it may usually be 5.0 μm or more.

The polybiphenyl ether sulfone resin of the present invention has characteristics that the melt-molded article can be produced.

As another aspect of the polybiphenyl ether sulfone resin of the present invention, the following properties are provided: a test piece having a length of 70mm, a width of 10mm, a thickness of 1.9mm, a notch having a tip radius of 0.25mm at the center and a depth of 5mm was prepared by the method described in the impact resistance test described later, and when the Izod impact resistance [ J/m ] was measured according to ASTM D256, the Izod impact resistance was 200 to 2000J/m, preferably 400 to 1500J/m, more preferably 500 to 1000J/m, and further preferably 600 to 800J/m.

As another aspect of the polybiphenyl ether sulfone resin of the present invention, the following properties are provided: further, when the test piece is placed in an oven at 180 ℃ and the Izod impact resistance after thermal annealing is measured after 24 hours of storage, the Izod impact resistance before and after thermal annealing is 200 to 2000J/m, preferably 400 to 1500J/m, more preferably 500 to 1000J/m, and still more preferably 600 to 800J/m, respectively.

As still another aspect of the polybiphenyl ether sulfone resin of the present invention, the following properties are provided: the Izod impact resistance of the test piece after the thermal annealing was changed to a range of-50% to + 50%, preferably-30% to + 30%, more preferably-10% to + 30%, more preferably-7% to + 30%, and still more preferably-7% to + 10% relative to the Izod impact resistance of the test piece before the thermal annealing.

Examples

The present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

< measurement of Mn and Mw of Polybiphenyl Ether sulfone resin, calculation of Mw/Mn >

The mass average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw/Mn) of the polybiphenyl ether sulfone resin based on polystyrene were determined by GPC measurement under the following measurement conditions.

[ measurement conditions ]

Sample preparation: 0.025g of a polybiphenyl ether sulfone resin to be measured was added to 10mL of a 10mM lithium bromide-containing N, N-dimethylformamide solution

Sample injection amount: 10 μ L

Chromatography column (stationary phase): "TSKgel SuperHZM-M (substrate: styrene-divinylbenzene)" made by Tosoh corporation (DONG ソー Co., Ltd.) "2 in series

Temperature of the column: 40 deg.C

Eluent (mobile phase): n, N-dimethylformamide with 10mM lithium bromide

Eluent flow rate: 0.35mL/min

A detector: UV detector

Detection wavelength: 300nm

Molecular weight standard: polystyrene

< measurement of melt viscosity of Polybiphenyl Ether sulfone resin >

Using a thermal flow evaluation device ("flow tester CFT500 type" manufactured by Shimadzu corporation), a load of 50kgf/cm was applied²Under the conditions (1 mm in inner diameter and 10mm in length) of a combination die, and a melt viscosity [ mu ] Pa s of a polybiphenyl ether sulfone resin heated at 350 ℃ for 5 minutes was extruded from the combination die]。

< preparation of compressed tablet >

An appropriate amount of a poly (biphenyl ether sulfone) resin was placed in a gap portion of an aluminum spacer (spacer) having a thickness of about 0.2mm, and the spacer was sandwiched between a pair of aluminum flat plates. The whole was sandwiched between a pair of steel plates, preheated at 305 ℃ for 13 minutes by a hot press, and then fused with a poly (biphenyl ether sulfone) resin, and heated and compressed under a pressure sufficient to make the thickness of the resin the same as that of the aluminum separator for 2 minutes. Then, the molded article was produced as a compressed tablet having a thickness of about 0.2mm by cooling the molded article with a cold press set at 25 ℃.

< measurement of after shrinkage >

A 5mm × 20mm sample for measurement was cut out from the pressed sheet, and the temperature was raised from 30 ℃ to 200 ℃ at a rate of 5 ℃/min in a stretching mode under an air atmosphere using a thermomechanical analyzer ("TMA-8310" manufactured by japan society of science and society, ltd. リガク) (step 1), and then cooled from 200 ℃ to 30 ℃ at a rate of 20 ℃/min (step 2). The post-shrinkage was measured by subtracting the length of the sample at 50 ℃ in step 1 from the length of the sample at 50 ℃ in step 2.

< impact resistance test >

A polybiphenyl ether sulfone resin as a measurement object was disposed in a gap portion of an SUS spacer having a thickness of 2mm, and sandwiched between a pair of aluminum flat plates. The whole was sandwiched between a pair of steel plates, preheated at 305 ℃ for 13 minutes by a hot press, and then fused together with a poly (biphenyl ether sulfone) resin, and heated and compressed under a pressure sufficient to make the thickness of the resin the same as that of the SUS spacer for 2 minutes. Then, cooling was performed by a cold press set to 25 ℃ to obtain a sheet having a thickness of 1.9 mm. The molded plate thus obtained was cut into a test piece having a length of 70mm, a width of 10mm and a thickness of 1.9mm, and a notch having a tip radius of 0.25mm and a depth of 5mm at the center, and the Izod impact resistance [ J/m ] was measured in accordance with ASTM D256.

< Heat aging test >

After molding, the test piece was placed in an oven at 180 ℃ for 24 hours, and the test piece was used for the impact resistance test as a thermally annealed test piece. Impact resistance testing was performed according to ASTM D256.

Production of Polybiphenyl Ether sulfone resin

[ example 1]

In a polymerization vessel equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser equipped with a receiver at the tip, 100.0 parts by mass (1 molar ratio) of 4, 4 '-dihydroxybiphenyl, 159.0 parts by mass (1.031 molar ratio) of 4, 4' -dichlorodiphenyl sulfone and 308.9 parts by mass of diphenyl sulfone were mixed, and the temperature was raised to 180 ℃ while flowing nitrogen gas in the system, 76.1 parts by mass (1.025 molar ratio) of potassium carbonate was added to the resulting mixed solution, and then the temperature was gradually raised to 290 ℃ to further react at 290 ℃ for 4 hours. Next, the obtained reaction mixture solution was cooled to room temperature to solidify it, and after being finely pulverized, it was washed several times by decantation and filtration using warm water and a mixed solvent of acetone and methanol. The obtained solid was dried by heating at 150 ℃ to obtain a polybiphenyl ether sulfone resin of example 1. Table 1 shows the results of measurement of polymerization concentration, mass average molecular weight Mw, polydispersity Mw/Mn, melt viscosity, and after shrinkage. Table 2 shows the evaluation results of the impact resistance test and the heat aging test.

In addition, when the polymerization concentration was determined in example 1, the mass a of the polybiphenyl ether sulfone resin obtained by the polycondensation reaction was determined as an amount (219.8 parts by mass) obtained by subtracting the mass (2 × 36.46 × 0.537) of hydrogen halide corresponding to 2 times the mole number of the charged mass of 4, 4 ' -dihydroxybiphenyl from the sum (259.0 parts by mass) of the charged mass (159.0 parts by mass) of the 4, 4 ' -dihalodiphenylsulfone compound and the charged mass (100.0 parts by mass) of the 4, 4 ' -dihydroxybiphenyl. The polymerization concentration was calculated from 219.8X 100 ÷ (219.8+ 308.9).

The mass average molecular weight Mw based on polystyrene of the polybiphenyl ether sulfone resin of example 1 and the melt viscosity μ [ Pa · s ] at a temperature of 350 ℃ satisfy the formulae (6) and (7), and a compressed sheet obtained from the polybiphenyl ether sulfone resin is less changed from the original size, that is, less post-shrinkage, even when it is returned to room temperature after thermal annealing. Further, a melt-molded article obtained from the polybiphenyl ether sulfone resin is excellent in impact resistance, and the change in impact resistance is small before and after thermal annealing, that is, it is difficult to thermally age.

[ example 2]

A polybiphenyl ether sulfone resin of example 2 was obtained under the same conditions as example 1 except that the reaction time at 290 ℃ was 6 hours. Table 1 shows the results of measurement of polymerization concentration, mass average molecular weight Mw, polydispersity Mw/Mn, melt viscosity, and after shrinkage.

[ example 3]

A polybiphenyl ether sulfone resin of example 3 was obtained under the same conditions as example 1 except that the amount of diphenyl sulfone was 308.5 parts by mass, the amount of potassium carbonate was 76.5 parts by mass (1.030 mole ratio) and the reaction time at 290 ℃ was 5 hours. Table 1 shows the results of measurement of polymerization concentration, mass average molecular weight Mw, polydispersity Mw/Mn, melt viscosity, and after shrinkage.

[ example 4]

A polybiphenyl ether sulfone resin of example 4 was obtained under the same conditions as example 1 except that the amount of diphenyl sulfone was 308.5 parts by mass, the amount of potassium carbonate was 76.4 parts by mass (1.030 mole ratio) and the reaction time under the condition of 290 ℃ was 4.5 hours. Table 1 shows the results of measurement of polymerization concentration, mass average molecular weight Mw, polydispersity Mw/Mn, melt viscosity, and after shrinkage. Table 2 shows the evaluation results of the impact resistance test and the heat aging test.

[ example 5]

A polybiphenyl ether sulfone resin of example 5 was obtained under the same conditions as example 1 except that the amount of diphenyl sulfone was 307.0 parts by mass and the amount of potassium carbonate was 77.9 parts by mass (1.050 mole ratio). Table 1 shows the results of measurement of polymerization concentration, mass average molecular weight Mw, polydispersity Mw/Mn, melt viscosity, and after shrinkage.

[ example 6]

A polybiphenyl ether sulfone resin of example 6 was obtained under the same conditions as example 1, except that the reaction time was 5.8 hours under the condition of 290 ℃. Table 1 shows the results of measurement of polymerization concentration, mass average molecular weight Mw, polydispersity Mw/Mn, melt viscosity, and after shrinkage.

Comparative example 1

In a polymerization vessel equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser with a receiver at the tip, 100.0 parts by mass (1 molar ratio) of 4, 4 '-dihydroxybiphenyl, 159.0 parts by mass (1.031 molar ratio) of 4, 4' -dichlorodiphenyl sulfone and 213.4 parts by mass of diphenyl sulfone were mixed, and the temperature was raised to 180 ℃ while flowing nitrogen gas in the system, 77.2 parts by mass (1.040 molar ratio) of potassium carbonate was added to the resulting mixed solution, and then the temperature was gradually raised to 290 ℃ to conduct a reaction at 290 ℃ for 4 hours. Next, the obtained reaction mixture solution was cooled to room temperature to solidify it, and after being finely pulverized, it was washed several times by decantation and filtration using warm water and a mixed solvent of acetone and methanol. The solid obtained was dried by heating at 150 ℃ to obtain a polybiphenyl ether sulfone resin of comparative example 1. Table 1 shows the results of measurement of polymerization concentration, mass average molecular weight Mw, polydispersity Mw/Mn, melt viscosity, and after shrinkage. Table 2 shows the evaluation results of the impact resistance test and the heat aging test.

Comparative example 2

A polybiphenyl ether sulfone resin of comparative example 2 was obtained under the same conditions as example 1, except that the amount of diphenyl sulfone was 214.1 parts by mass, the amount of potassium carbonate was 76.4 parts by mass (1.030 mole ratio) and the reaction time under the condition of 290 ℃ was 3 hours. Table 1 shows the results of measurement of polymerization concentration, mass average molecular weight Mw, polydispersity Mw/Mn, melt viscosity, and after shrinkage. Table 2 shows the evaluation results of the impact resistance test and the heat aging test.

TABLE 1

DCDPS: 4, 4-dichlorodiphenyl sulfone

BP: 4, 4-dihydroxybiphenyl

TABLE 2

The polybiphenyl ether sulfone resin of the example was produced by condensation polymerization with a constant polymerization concentration of 42%. As shown in fig. 1, when the mass average molecular weight Mw of the polybiphenyl ether sulfone resin of the example is plotted on the abscissa and the melt viscosity μ is plotted on the ordinate, the plotted points are approximately arranged on a straight line having a slope of "0.0906". The mass average molecular weight Mw and melt viscosity μ [ Pa · s ] of the polybiphenyl ether sulfone resins of the examples satisfy the formula (6) and the formula (7), and the compressed tablets obtained from these polybiphenyl ether sulfone resins have a small change from the original size, i.e., a small post-shrinkage, even when returned to normal temperature after thermal annealing. Further, the composition is excellent in impact resistance, and the impact resistance is less changed before and after thermal annealing, that is, it is difficult to thermally age the composition.

The biphenyl ether sulfone resin of the comparative example was produced by condensation polymerization with a constant polymerization concentration of 51%. As shown in fig. 1, when the mass average molecular weight Mw of the polybiphenyl ether sulfone resin of the comparative example is plotted on the horizontal axis and the melt viscosity μ is plotted on the vertical axis, the plotted point is on a straight line having a slope of about "0.0906". The mass average molecular weight Mw and melt viscosity μ [ Pa · s ] of the biphenyl ether sulfone resins of the comparative examples do not satisfy formula (7), and when the compressed sheets obtained from these biphenyl ether sulfone resins are returned to room temperature after thermal annealing, shrinkage is larger than the original size, that is, post-shrinkage is larger. In addition, when thermal annealing is performed, impact resistance is significantly reduced, that is, thermal aging is easily performed.

It can be understood that: the formula [ μ ═ 0.0906 × Mw-4930] is a boundary line between a molded article with less after-shrinkage and a molded article with large after-shrinkage in a molded article containing a polybiphenyl ether sulfone resin substantially composed of the repeating structure of the formula (1).

Industrial applicability

The molded article obtained from the polybiphenyl ether sulfone resin of the present invention shows little change from the original dimensions, i.e., little post-shrinkage, even when returned to normal temperature after use in a high-temperature environment. The molded article can be expected to be used in a wide range of applications such as electric/electronic materials, automobile parts, medical materials, heat-resistant coatings, separation films, and resin interfaces, and particularly in applications of precision parts used in high-temperature environments.