阅读说明：本技术 聚联苯醚砜树脂及其制造方法以及熔融成型品 (Polybiphenyl ether sulfone resin, process for producing the same, and melt-molded article ) 是由 伊藤和幸 前川健典 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,使用固体试样测定用NMR装置,通过托尔基亚脉冲序列获取～(13)C波谱,通过使所述脉冲序列中的延迟时间τ的值改变,从而根据与化学位移129ppm相应的信号强度I(τ)的衰减而算出的长成分的自旋-晶格弛豫时间T-(1L)为24s以上。[式中,n表示1以上的整数。](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 is obtained by a Torkinje sub-pulse sequence using an NMR apparatus for measuring a solid sample 13 C spectrum, the value of delay time tau in the pulse sequence is changed, and the spin-lattice relaxation time T of the long component calculated from the attenuation of signal intensity I (tau) corresponding to chemical shift 129ppm is calculated 1L Is more than 24 s. [ in the formula, n represents an integer of 1 or more.])

1. A polybiphenyl ether sulfone resin, which is substantially composed of a repeating structure of the following formula (1) and has a spin-lattice relaxation time T_1LSpin-lattice relaxation time T calculated by the calculation method of_1LThe time is more than 24s, and the time is short,

wherein n represents an integer of 1 or more,

spin-lattice relaxation time T_1LThe calculating method of (2): obtaining the polybiphenyl ether sulfone resin by a Turkish-based subpulse sequence using an NMR apparatus for solid sample measurement¹³In the C-NMR spectrum, the value of the delay time tau in the pulse sequence is changed to calculate the spin-lattice relaxation time T of the long component from the attenuation of the signal intensity I (tau) corresponding to the chemical shift 129ppm_1L。

2. A method for producing a polybiphenyl ether sulfone resin, wherein the polybiphenyl ether sulfone resin is substantially composed of a repeating structure of the following formula (1), the method comprising: 4, 4 '-dihalogenodiphenyl sulfone compound and 4, 4' -dihydroxybiphenyl are subjected to polycondensation reaction in an aprotic polar solvent,

wherein n represents an integer of 1 or more,

the polycondensation reaction is carried out so that the calculated mass A of the polybiphenyl ether sulfone resin to be obtained by the polycondensation reaction and the charged mass B of the aprotic polar solvent satisfy the following formula (5),

35≤A×100÷(A+B)≤44 (5)。

3. the method for producing a polybiphenyl ether sulfone resin according to claim 2, wherein the 4, 4 '-dihalodiphenylsulfone compound is 4, 4' -dichlorodiphenylsulfone.

4. A melt-molded article comprising the polybiphenyl ether sulfone resin according to claim 1.

Technical Field

The present invention relates to a polybiphenyl ether sulfone resin, a method for producing the same, and a melt-molded article.

The present application is based on the Japanese patent application No. 2018-180560 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 the impact resistance of a molded article obtained from a conventional polybiphenyl ether sulfone resin is lowered after thermal annealing.

The purpose of the present invention is to provide a polybiphenyl ether sulfone resin which is excellent in impact resistance and is less likely to change in impact resistance before and after thermal annealing, that is, which is, a melt-molded article less likely to thermally age, a method for producing the same, and a melt-molded article having excellent impact resistance and less likely to thermally age.

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 substantially consisting of a repeating structure of the following formula (1) according to the following<Spin-lattice relaxation time T_1LIs calculated by>Calculated spin-lattice relaxation time T_1LIs more than 24 s.

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

< spin-lattice relaxation time T_1LMethod of calculating

Using an NMR apparatus for solid sample measurement, the solid sample was obtained by a Torkia (Torchia) pulse sequence¹³In the C-NMR spectrum, the value of the delay time tau in the pulse sequence is changed to calculate the spin-lattice relaxation time T of the long component from the attenuation of the signal intensity I (tau) corresponding to the chemical shift 129ppm_1L。

[2] A process for producing a polybiphenyl ether sulfone resin by a polycondensation reaction of a 4, 4 '-dihalodiphenylsulfone compound and 4, 4' -dihydroxybiphenyl in an aprotic polar solvent, wherein,

the calculated mass A of the polybiphenyl ether sulfone resin to be obtained by the polycondensation reaction and the charged mass B of the aprotic polar solvent satisfy the following formula (5),

35≤A×100÷(A+B)≤44 (5)。

[3] the method for producing a polybiphenyl ether sulfone resin according to [2], wherein the 4, 4 '-dihalodiphenylsulfone compound is 4, 4' -dichlorodiphenylsulfone.

[4] A melt-molded article comprising the polybiphenyl ether sulfone resin of [1 ].

In addition, the present invention has the following aspects.

<1> a polybiphenyl ether sulfone resin, which isEssentially consisting of a repeating structure of the following formula (1) according to the following<Spin-lattice relaxation time T_1LIs calculated by>Calculated spin-lattice relaxation time T_1LIs more than 24 s.

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

< spin-lattice relaxation time T_1LMethod of calculating

Obtaining the polybiphenyl ether sulfone resin by a Turkish-based subpulse sequence using an NMR apparatus for solid sample measurement¹³In the C-NMR spectrum, the value of the delay time tau in the pulse sequence is changed to calculate the spin-lattice relaxation time T of the long component from the attenuation of the signal intensity I (tau) corresponding to the chemical shift 129ppm_1L。

<2> a method for producing a polybiphenyl ether sulfone resin consisting essentially of a repeating structure of the following formula (1), said method comprising: 4, 4 '-dihalogenodiphenyl sulfone compound and 4, 4' -dihydroxybiphenyl are subjected to polycondensation reaction in an aprotic polar solvent,

[ in the formula, n has the same meaning as described above. ]

The polycondensation reaction is carried out so that the calculated mass A of the polybiphenyl ether sulfone resin to be obtained by the polycondensation reaction and the charged mass B of the aprotic polar solvent satisfy the following formula (5),

35≤A×100÷(A+B)≤44 (5)。

< 3 > the method for producing a polybiphenyl ether sulfone resin <2>, wherein the 4, 4 '-dihalodiphenylsulfone compound is 4, 4' -dichlorodiphenylsulfone.

< 4 > a melt-molded article comprising the polybiphenyl ether sulfone resin of <1 >.

ADVANTAGEOUS EFFECTS OF INVENTION

The melt-molded article obtained from the polybiphenyl ether sulfone resin of the present invention 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.

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.

For the polybiphenyl ether sulfone resin of the present invention, the resin composition<Spin-lattice relaxation time T_1LIs calculated by>Calculated spin-lattice relaxation time T_1LIs more than 24 s.

< spin-lattice relaxation time T_1LMethod of calculating

Acquisition of Polybiphenyl Ether sulfone resin by Torky sub-pulse sequence using NMR apparatus for solid sample measurement¹³In the C-NMR spectrum, the value of the delay time tau in the pulse sequence is changed to calculate the spin-lattice relaxation time T of the long component from the attenuation of the signal intensity I (tau) corresponding to the chemical shift 129ppm_1L。

Obtained on the basis of a tolki sub-pulse sequence¹³The C-NMR spectrum was obtained by the method described in Torchia, D.A., J.Magn.Reson.,30, 613-.

For polybiphenyl ether sulfone resins¹³In the C-NMR spectrum, a main chain peak was detected at a chemical shift of 129ppm, and the spin-lattice relaxation time thereof was separated into a short component and a long component. Relaxation time T_1LRefers to the spin-lattice relaxation time of the long component therein. More specifically, the relaxation time T_1LCan be according to the following¹³Relaxation time T of C-NMR_1LThe calculation of (c) > is calculated using a least squares fit as described in (a).

The measurement sample form of the polybiphenyl ether sulfone resin to be measured may be a powder sample or a melt-molded sample, and a powder sample is preferable from the viewpoint of easiness of sampling at the time of measurement.

Examples of the NMR apparatus for measuring a solid sample include a 400MHz NMR apparatus (manufactured by Bruker Corporation, Agilent Technologies co. ltd., manufactured by japan electronics Corporation, warian Inc.), and the like).

The relaxation time T of the polybiphenyl ether sulfone resin of the present invention_1LIs 24.0s or more, preferably 24.2s or more, more preferably 24.5s or more, and particularly preferably 25.0s or more. By making said relaxation time T_1LThe lower limit or more enables to reduce the reduction in impact resistance even when the thermal annealing is performed in the case of forming a melt-molded product from the polybiphenyl ether sulfone resin. For the relaxation time T_1LThe upper limit of (b) is not particularly limited, but is usually 40 s.

I.e. as said relaxation time T_1LPreferably 24.0s to 40s, 24.2s to 40s, 24.5s to 40s, or 25.0s to 40 s.

The calculated mass A of the polybiphenyl ether sulfone resin to be obtained by the polycondensation and the charged mass B of the aprotic polar solvent are defined as [ A × 100/(A + B)]The relaxation time T can be adjusted to 35% or more and 44% or less of a predetermined polymerization concentration (%)_1LThe control time is controlled to be more than 24.0 s.

The mass average molecular weight (Mw, based on polystyrene) of the polybiphenyl ether sulfone resin of the present invention can be 60000 to 90000, 62000 to 80000, 64000 to 76000, and 67000 to 71000.

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.

In one aspect of the present invention, the resin is a polybiphenyl ether sulfone resin having a mass average molecular weight (Mw, polystyrene basis) of 67000 to 71000 and a polydispersity (Mw/Mn) of 4.5 to 4.8.

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

The method for producing a polybiphenyl ether sulfone resin of the present invention is a method for producing a polybiphenyl ether sulfone resin by a polycondensation reaction of a 4, 4 '-dihalodiphenylsulfone compound and 4, 4' -dihydroxybiphenylsulfone 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 the 4, 4' -dihalodiphenylsulfone compound (2) is excessively polycondensed using an alkali metal carbonate, 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 of the present invention, the calculated mass a of the polybiphenyl ether sulfone resin to be obtained by the polycondensation reaction and the charged 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, when 1 to 1.10 moles, preferably 1.02 to 1.05 moles of the 4, 4 '-dihalodiphenylsulfone compound (2) is used relative to 1 mole of the 4, 4' -dihydroxybiphenyl (3)), the calculated 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 a hydrogen Halide (HX) in an amount corresponding 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) The mass of (3) and the mole number of the hydrogen Halide (HX) equivalent to the equivalent times of the charged mass of the 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 of the present invention, the resin composition is prepared from [ A × 100 ÷ (A + B)]The predetermined polymerization concentration (%) is 35% or more and 44% or less. The relaxation time T of a polybiphenyl ether sulfone resin produced under the condition satisfying the condition of formula (5)_1LCan be set to 24s or more. The polymerization concentration is preferably 43% or less, more preferably 42% or less. The relaxation time T can be set to be equal to or less than the upper limit value by setting the polymerization concentration to be equal to or less than the upper limit value_1LThe content of the polyether sulfone resin is 24s or more, and the reduction of impact resistance before and after thermal annealing is small. 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 the intermolecular structure of the polybiphenyl ether sulfone resin as the reaction product is represented by [ A X100 ÷ (A + B)]When the predetermined polymerization concentrations are different, the polymer molecules can be 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 the relaxation time T can be adjusted by setting the polymerization concentration to the upper limit or less_1LThe amount of the crosslinking agent is set to 24 seconds or more, and a melt-molded article which is excellent in impact resistance and is less in change in impact resistance before and after thermal annealing, that is, which is difficult to be thermally aged can be obtained.

The amount of the 4, 4 '-dihalodiphenylsulfone compound (2) to be used 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 about 1.02 to 1.05 mol or about 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 decreased, and therefore, it is preferable. 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 ℃. The melt-molded article of the present invention 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 age, 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.

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.

One aspect of the polybiphenyl ether sulfone resin of the present invention is that it has characteristics enabling the production of the above melt-molded article.

As another aspect of the polybiphenyl ether sulfone resin of the present invention, the following properties are exhibited: 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 exhibited: 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 another aspect of the polybiphenyl ether sulfone resin of the present invention, it has the following characteristics: the change in the Izod impact resistance of the test piece 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% with respect 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

ChromatographyColumn (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

＜¹³Relaxation time T of C-NMR_1LIs calculated

Acquisition by Torkinje sub-pulse sequence using NMR apparatus for solid sample measurement¹³C-NMR spectrum according to the main chain of poly (biphenyl ether sulfone) resin by changing the value of delay time tau in the pulse sequence¹³The attenuation of the signal intensity I (τ) at a chemical shift of 129ppm corresponding to C was calculated for the polybiphenyl ether sulfone resin to be measured¹³Relaxation time T of C-NMR_1L。

The obtained signal intensity I (τ) can be represented by the following formula (F1), I (τ) is plotted against time τ, and the relaxation time T is calculated from a fitting using the least square method_1L. Relaxation time T_1LIs given in units of seconds [ s ]]。

I(τ)＝a₁×exp(-τ/T_1S)+a₂×exp(-τ/T_1L) (F1) [ in the formula, a₁And a₂Represents: a coefficient calculated by fitting based on the least square method so that the sum of the first term and the second term in the formula (F1) has the same value as the signal intensity I (τ) obtained by measurement. T is_1SAnd T_1LCalculated by fitting based on the least squares method, representing T_1S<T_1LRelaxation time of]

< solid¹³Measurement of C-NMR

In the implementation ofIn the example, for the calculation of the relaxation time T_1LOf (2) a solid¹³C-NMR measurement of¹Magnetization transfer of H¹³C after, using observation¹³The magnetization of C was measured under the following conditions.

A measuring device: PS400WB (made by Wailan corporation)

Static magnetic field intensity: 9.4 Tesla (resonance frequency: 400 MHz: (¹H))

Magic angle rotation: 10kHz (10000 revolutions per second)

Contact time: 2ms

Repetition time: 6s

The accumulation times are as follows: 1024 times

Sample preparation: powder form (ca. 15mg)

Temperature: 25 deg.C

Chemical shift standard substance: adamantane

Delay time τ: 0.02s, 0.054s, 0.15s, 0.4s, 1.09s, 2.98s, 8.1s, 22s

< 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 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 308.5 parts by mass of diphenyl sulfone were mixed, and the temperature was raised to 180 ℃ while flowing nitrogen gas in the system. 76.4 parts by mass (1.030 molar ratio) of potassium carbonate was added to the resulting mixed solution, and then the temperature was gradually raised to 290 ℃ to conduct further reaction at 290 ℃ for 4.5 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 polymerization concentration, the mass-average molecular weight Mw, the polydispersity Mw/Mn, the relaxation times T determined using the polymer powders_1LAnd the results of the impact resistance test and the heat aging test.

When the polymerization concentration was determined in example 1, the calculated 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 number of moles 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 4, 4 ' -dihydroxybiphenyl. The polymerization concentration was calculated from 219.8X 100 ÷ (219.8+ 308.5).

Relaxation time T of Polybiphenyl Ether sulfone resin of example 1_1LThe content of the polyether sulfone resin is 24s or more, and a melt-molded article obtained from the polyether sulfone resin is excellent in impact resistance and is less in change of impact resistance before and after thermal annealing, that is, 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 amount of diphenyl sulfone was 308.9 parts by mass, the amount of potassium carbonate was 76.1 parts by mass (1.025 mole ratio) and the reaction time under the condition of 290 ℃ was 4 hours. Table 1 shows the polymerization concentration and the mass averageThe molecular weight Mw, the polydispersity Mw/Mn, the relaxation time T determined using a polymer powder_1LAnd relaxation time T measured using powder obtained by freeze-pulverizing molded test piece in impact resistance test_1LAnd the results of the impact resistance test and the heat aging test.

The sample was filled in a stainless steel container, and freeze-ground 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

Relaxation time T of Polybiphenyl Ether sulfone resin of example 2_1LA relaxation time T of a melt-molded article obtained from the above-mentioned polybiphenyl ether sulfone resin of 24s or more_1LAlso 24s or more. Namely, it was confirmed that: relaxation time T obtained by measuring the PolyBiphenyl Ether sulfone resin of example 2 in the state of Polymer powder_1LAnd a relaxation time T obtained by melt-extruding the polymer powder and molding the same into pellets, melting the pellets and melt-molding the same, and measuring the melt-molded article obtained by the melt-molding_1LAre substantially the same. The melt-molded article is excellent in impact resistance and is less susceptible to change in impact resistance before and after thermal annealing, i.e., is less susceptible to thermal aging.

[ example 3]

A poly (biphenyl ether sulfone) resin of example 3 was obtained under the same conditions as in example 1 except that the amount of 4, 4' -dichlorodiphenyl sulfone was 158.8 parts by mass (1.030 mole ratio), the amount of diphenyl sulfone was 306.8 parts by mass, the amount of potassium carbonate was 78.0 parts by mass (1.050 mole ratio), and the reaction time under 290 ℃. Table 1 shows the polymerization concentration, the mass-average molecular weight Mw, the polydispersity Mw/Mn, the relaxation times T determined using the polymer powders_1L. Relaxation time T of Polybiphenyl Ether sulfone resin of example 3_1LIs more than 24 s.

Comparative example 1

In a polymerization vessel equipped with a stirrer, a nitrogen inlet tube, a thermometer and a condenser having a receiver at the tip, 100.0 parts by mass (1 mol) of 4, 4' -dihydroxybiphenyl was placedRatio), 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 nitrogen gas was flowed through the system. To the resulting mixed solution, 77.2 parts by mass (1.040 mole ratio) of potassium carbonate was added, and then the temperature was gradually raised to 290 ℃ to conduct further 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 polymerization concentration, the mass-average molecular weight Mw, the polydispersity Mw/Mn, the relaxation times T determined using the polymer powders_1LAnd relaxation time T measured using powder obtained by freeze-pulverizing molded test piece in impact resistance test_1LAnd the results of the impact resistance test and the heat aging test.

Relaxation time T of Polybiphenyl Ether sulfone resin of comparative example 1_1LLess than 24s, and a relaxation time T of a melt-molded article obtained by melt-molding the polybiphenyl ether sulfone resin_1LAnd also less than 24 s. Namely, it was confirmed that: relaxation time T obtained by measuring the PolyBiphenyl Ether sulfone resin of comparative example 1 in the state of Polymer powder_1LAnd a relaxation time T obtained by melt-extruding the polymer powder to form a pellet, melting the pellet to form a melt-molded article, and measuring the melt-molded article_1LAre substantially the same. When the melt-molded article is subjected to thermal annealing, the impact resistance is remarkably lowered, that is, the melt-molded article is easily thermally aged.

Comparative example 2

A polybiphenyl ether sulfone resin of comparative example 2 was obtained under the same conditions as comparative example 1 except that the amount of diphenyl sulfone was 214.9 parts by mass and the amount of potassium carbonate was 75.7 parts by mass (1.020 mole ratio). Table 1 shows the polymerization concentration, the mass-average molecular weight Mw, the polydispersity Mw/Mn, the relaxation times T determined using the polymer powders_1LAnd the results of the impact resistance test and the heat aging test.

Relaxation time T of Polybiphenyl Ether sulfone resin of comparative example 2_1LLess than 24 seconds, the melt-molded article obtained by melt-molding the above-mentioned polybiphenyl ether sulfone resin is significantly reduced in impact resistance, that is, is easily thermally aged when subjected to thermal annealing.

TABLE 1

DCDPS: 4, 4-dichlorodiphenyl sulfone

BP: 4, 4-dihydroxybiphenyl

Based on the calculated mass A of the polybiphenyl ether sulfone resin to be obtained by the polycondensation reaction and the charged mass B of the aprotic polar solvent, the mass of the resin to be obtained is represented by [ A × 100 ÷ (A + B) ]]The predetermined polymerization concentration was adjusted to a constant concentration of 35% to 44%, thereby producing the polybiphenyl ether sulfone resins of examples 1 to 3. Relaxation time T of the PolyBiphenyl Ether sulfone resins of the examples_1LThe content of the polyether sulfone resin is 24s or more, and the melt-molded article obtained from the polyether sulfone resin is excellent in impact resistance, and is less in change of impact resistance before and after thermal annealing, that is, is difficult to be thermally aged.

In contrast, the expression "A × 100 ÷ (A + B)]The polybiphenyl ether sulfone resin of the comparative example produced under the condition that the predetermined polymerization concentration is more than 44% has the same degree of mass average molecular weight as that of the polybiphenyl ether sulfone resin of the example, but the relaxation time T_1LLess than 24 s. In addition, it was confirmed that: the melt-molded article obtained from the polybiphenyl ether sulfone resin of comparative example was inferior in impact resistance to the melt-molded article obtained from the polybiphenyl ether sulfone resin of example, and the impact resistance was remarkably lowered after thermal annealing.

Industrial applicability

The melt-molded article obtained from the polybiphenyl ether sulfone resin of the present invention is excellent in impact resistance, and the change in impact resistance before and after thermal annealing is small, that is, it is difficult to thermally age. The melt-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, various applications assumed to be used in a high-temperature environment.