Polyphenylene ether melt extrusion molded body and method for producing same

Abstract

The purpose of the present invention is to provide: a polyphenylene ether melt extrusion molded body which is excellent in terms of solubility in a solvent and dissolution stability and has excellent heat resistance; and a method for producing the polyphenylene ether melt extrusion molded body. The present invention pertains to a polyphenylene ether melt extrusion molded body which contains a polyphenylene ether component, and the polyphenylene ether melt extrusion molded body is characterized in that: the polyphenylene ether component has a dislocation structure that is bonded at the ortho position in each of consecutive repeating units that are bonded at the para position; the amount of the dislocation structure is 1.2 mol% or more relative to all polyphenylene ether structural units in the polyphenylene ether component; and the weight average absolute molecular weight (Mw) of the polyphenylene ether component is 40,000 g / mol or more.

Description

Polyphenylene ether melt extrusion molding and its manufacturing method

[0001] The present invention relates to a polyphenylene ether melt-extrusion molded product and a method for producing the same.

[0002] Polyphenylene ether (hereinafter also referred to as "PPE") has excellent high-frequency characteristics, flame retardancy, and heat resistance, and is therefore widely used as a material for products and parts in the electrical and electronic fields, automotive fields, food and packaging fields, and various other industrial materials. In particular, in recent years, taking advantage of its low dielectric properties and heat resistance, it has been increasingly used as a modifier in various applications, including electrical and electronic applications such as substrate materials.

[0003] However, high-molecular-weight PPEs having repeating units derived from monohydric phenols, such as 2,6-dimethylphenol, generally have the problem that, although they dissolve in highly toxic solvents such as chloroform, they are poorly soluble in aromatic solvents such as toluene, which are known to be good solvents, and are insoluble in ketone solvents such as methyl ethyl ketone. Therefore, when used as a wiring board material, for example, they are difficult to handle in resin varnish solutions such as toluene or methyl ethyl ketone.

[0004] Patent Document 1 discloses a resin composition containing a low-molecular-weight PPE having a PPE moiety in its molecular structure and having at least one p-ethenylbenzyl group, m-ethenylbenzyl group, or the like at the molecular end, and a crosslinking curing agent.

[0005] Furthermore, Patent Document 2 discloses a curable composition containing a bifunctional PPE having a methacrylic group at the molecular end, an unsaturated polyester resin or a vinyl ester resin, a reactive liquid monomer, and a compatibilizer.

[0006] Furthermore, Patent Document 3 discloses a resin composition containing a low molecular weight PPE component consisting of a polyfunctional phenol having a specific skeleton, obtained by a redistribution reaction between a high molecular weight PPE and a polyfunctional phenol, a crosslinking agent, and an organic peroxide.

[0007] Japanese Patent No. 4211784 Japanese Patent No. 5635973 Japanese Patent Application Laid-Open No. 2020-132764

[0008] Patent Documents 1 to 3 describe dissolving PPE in a solvent such as toluene, but these documents achieve this by lowering the molecular weight of the PPE. However, lowering the molecular weight of the PPE can lead to problems such as insufficient dielectric properties and heat resistance inherent to the PPE skeleton. Furthermore, the low-molecular-weight PPE obtained by the redistribution reaction of high-molecular-weight PPE and polyfunctional phenol described in Patent Document 3 contains organic peroxides, which are commonly used in redistribution reactions. Residual organic peroxides in the product could adversely affect the dielectric properties of the substrate.

[0009] An object of the present invention is to provide a polyphenylene ether melt-extrusion molded product which has excellent solubility in solvents, excellent dissolution stability, and excellent heat resistance, and a method for producing the polyphenylene ether melt-extrusion molded product.

[0010] As a result of extensive research into polyphenylene ether, the present inventors have found that the above-mentioned problems can be solved by preparing a polyphenylene ether melt-extrusion molded product containing a polyphenylene ether component having a specific amount of rearrangement structures and a specific weight-average absolute molecular weight (Mw), and have thus completed the present invention.

[0011] Specifically, the present invention relates to a polyphenylene ether melt-extrusion molded product comprising a polyphenylene ether component, wherein the polyphenylene ether component has a rearrangement structure in which repeating units connected by a bond at an ortho position are connected by a bond at an ortho position in repeating units that are successively connected by a bond at a para position, the amount of the rearrangement structure is 1.2 mol % or more based on all polyphenylene ether structural units in the polyphenylene ether component, and the weight-average absolute molecular weight (Mw) of the polyphenylene ether component is 40,000 g / mol or more.

[0012] The molecular configuration parameter α of the polyphenylene ether component, calculated using the Mark-Houwink-Sakurada equation, is preferably 0.550 or more and 0.650 or less.

[0013] The ratio (Mz / Mw) of the Z-average molecular weight (Mz) calculated from the absolute molecular weight of the polyphenylene ether component to the weight-average absolute molecular weight (Mw) is preferably 2.5 or less.

[0014] The repeating units connected consecutively via the para-position bond are represented by the following general formula (1): (In the formula, R １ , R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent), and the rearrangement structure is a repeating unit represented by the following general formula (2): (In the formula, R １ , R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ ' is the R ３ It is preferable that the structure is a divalent group in which one hydrogen atom has been removed from the group

[0015] The polyphenylene ether melt-extrusion molded product preferably has a glass transition temperature of 205° C. or higher.

[0016] The polyphenylene ether melt extrudate may be polyphenylene ether pellets.

[0017] The present invention also relates to a method for producing the polyphenylene ether melt-extrusion molded product, comprising the step of melt-extruding a raw material, polyphenylene ether, using an extruder equipped with a cylinder and a screw at a screw peripheral speed of 10 m / min or more and an extrusion temperature of 260°C or more.

[0018] The residence time in the extruder is preferably 5 minutes or less.

[0019] High-molecular-weight PPE components typically have low solubility in solvents, and dissolution in solvents such as toluene has been difficult, particularly when the PPE component is present at a high content or solely in the PPE component. The PPE melt-extrusion molded product of the present invention contains a PPE component containing a specific amount of a rearrangement structure (hereinafter also referred to as a methylene bridge rearrangement structure (MBR)) in which ortho-position bonds are connected among repeating units connected by para-position bonds. This improves solubility in solvents such as toluene and provides excellent dissolution stability, despite the PPE component having a very high molecular weight (weight-average absolute molecular weight (Mw) of 40,000 g / mol or more). While the detailed mechanism behind this effect is unclear, it is believed that the presence of a certain amount of rearrangement structures in a molecular structure with long branched chains leads to a spherical shape of the molecular chain, reducing the spread of the molecular chain. As a result, the orientation and re-aggregation of polymer molecules after dissolution in a solvent are reduced, resulting in improved solubility and dissolution stability in the solvent. Furthermore, the PPE melt-extrusion molded product of the present invention has excellent heat resistance because it contains a PPE component with a very high molecular weight, with a weight-average absolute molecular weight (Mw) of 40,000 g / mol or more.

[0020] 1 is a cross-sectional view schematically illustrating one embodiment of the method for producing a PPE melt-extrusion molded product of the present invention.

[0021] 1. PPE melt-extrusion molded product The PPE melt-extrusion molded product of the present invention comprises a PPE component, wherein the PPE component has a rearrangement structure in which repeating units connected by a bond at the ortho position are connected by a bond at the para position, the amount of the rearrangement structure is 1.2 mol % or more relative to all PPE structural units in the PPE component, and the weight-average absolute molecular weight (Mw) of the PPE component is 40,000 g / mol or more.

[0022] <PPE Component> The PPE component used in the present invention contains a PPE having a rearrangement structure connected by a bond at the ortho position in repeating units connected by a bond at the para position. Here, the "rearrangement structure connected by a bond at the ortho position" refers to a structure in which a continuous side chain is formed by connecting repeating units connected by a bond at the ortho position in some of the repeating units connected by a bond at the para position of the main chain. The side chain may be formed from repeating units connected by a bond at the para position, and may also have a portion connected by a bond at the ortho position within the side chain.

[0023] The repeating units having consecutive para-position bonds include those represented by the following general formula (1): (In the formula, R １ , R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent), and the rearrangement structure is a repeating unit represented by the following general formula (2): (In the formula, R １ , R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ ' is the R ３ It is preferable that the compound has a rearrangement structure represented by the following formula (2): (representing a divalent group in which one hydrogen atom has been removed from the group). The "~" in the general formula (2) indicates that the structure following it is not particularly limited. The "~" portion may be formed from consecutive phenylene ether units connected via para-bonds, and may also contain portions connected via bonds at the ortho position.

[0024] The rearrangement structure is formed, for example, by a rearrangement reaction represented by the following formula, which is also called a methylene bridge rearrangement.

[0025] R in the general formulas (1) and (2) １ , R ２ , R ３Examples of the hydrocarbon group having 1 to 10 carbon atoms in the formula (I) include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and decyl; aryl groups having 6 to 10 carbon atoms, such as phenyl, 4-methylphenyl, 1-naphthyl, and 2-naphthyl; and aralkyl groups having 7 to 10 carbon atoms, such as benzyl, 2-phenylethyl, and 1-phenylethyl.

[0026] When the hydrocarbon group has a substituent, examples of the substituent include a halogen atom such as a fluorine atom, an alkoxy group such as a methoxy group, etc. Specific examples of the hydrocarbon group having a substituent include a trifluoromethyl group, etc.

[0027] Among these, R １ , R ２ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom, and R ３ As the alkyl group, a methyl group is preferred.

[0028] The R ３’ is the R ３ represents a divalent group in which one hydrogen atom has been removed from the group, and a methylene group is preferred.

[0029] Specific examples of the repeating unit of general formula (1) include repeating units derived from 2,6-dimethyl-1,4-phenylene ether, 2,6-diethyl-1,4-phenylene ether, 2-methyl-6-ethyl-1,4-phenylene ether, and 2,6-dipropyl-1,4-phenylene ether. Among these, the repeating unit derived from 2,6-dimethyl-1,4-phenylene ether is preferred.

[0030] The PPE component having the rearrangement structure is preferably a homopolymer having a repeating unit of the general formula (1) or a copolymer containing two or more different repeating units of the general formula (1), which has a rearrangement structure represented by the general formula (2).

[0031] Furthermore, the PPE component having the rearrangement structure may contain a repeating unit other than that of the general formula (1) as long as the effects of the present invention are not impaired, and in this case, the rearrangement structure represented by the general formula (2) may be contained in a copolymer containing the repeating unit of the general formula (1) and a repeating unit other than that of the general formula (1). The content of such a repeating unit other than that of the general formula (1) is not particularly limited as long as the effects of the present invention are not impaired, but for example, it is preferably about 5 mol % or less in the copolymer, and more preferably no repeating unit is contained.

[0032] The amount of rearrangement structures in the PPE component having the rearrangement structure (hereinafter also referred to as "rearrangement amount") is 1.2 mol% or more, preferably 1.5 mol% or more, and more preferably 1.8 mol% or more, relative to the total structural units constituting the PPE. Furthermore, the rearrangement amount is preferably 15 mol% or less, more preferably 10 mol% or less, and even more preferably 8 mol% or less. When the rearrangement amount in the PPE component having the rearrangement structure is within the above range, the number of bent structures increases, the orientation and re-aggregation of polymer molecules after dissolution in a solvent is reduced, and the solubility in the solvent is improved. Furthermore, the resulting PPE solution has excellent stability (i.e., excellent dissolution stability).

[0033] The rearrangement structure can be identified by nuclear magnetic resonance spectroscopy ( １ In H-NMR measurement, it is preferable that the PPE exhibits peaks in the range of 3.8 to 4.0 ppm and in the range of 6.8 to 7.0 ppm. Usually, PPE exhibits peaks in the vicinity of 6.4 to 6.6 ppm, which are peaks derived from the hydrogen atoms at the 3rd and 5th positions of the benzene ring in the PPE main chain. The PPE having the rearrangement structure exhibits peaks in the range of 3.8 to 4.0 ppm and in the range of 6.8 to 7.0 ppm, in addition to the peak in the vicinity of 6.4 to 6.6 ppm. The chemical shift in the range of 3.8 to 4.0 ppm is derived from the R in the rearrangement structure. ３’ The chemical shift in the range of 6.8 to 7.0 ppm is due to the protons of the divalent group (for example, a methylene group) represented by the formula: １ , R ２ These are derived from protons of the group (for example, hydrogen atoms at the 3- and 5-positions of a benzene ring bonded via a methylene group at the ortho-position).

[0034] The weight-average absolute molecular weight (Mw) of the PPE component is 40,000 g / mol or more, preferably 42,000 g / mol or more, and more preferably 44,000 g / mol or more. The weight-average absolute molecular weight (Mw) is preferably 150,000 g / mol or less, more preferably 100,000 g / mol or less, and even more preferably 80,000 g / mol or less. Setting the weight-average absolute molecular weight (Mw) within the above range is preferable from the viewpoints of heat resistance, solvent solubility, and dissolution stability. Here, the absolute average molecular weight (Mw) refers to the true weight-average molecular weight of the polymer. The weight-average molecular weight measured by conventional gel permeation chromatography (GPC) is a relative weight-average molecular weight determined using linear polystyrene of known molecular weight as a standard polymer. When a branched structure is present in the polymer, accurate evaluation of the molecular weight may be impossible. The weight-average absolute molecular weight (Mw) is measured using a GPC device equipped with a specified column and a multi-angle light scattering detector, and can accurately measure the molecular weight without being affected by polymer structures such as branched structures. The weight-average absolute molecular weight (Mw) can be measured by any method known in the art, and is not particularly limited thereto. For example, it can be measured by the method described in the Examples below. This weight-average absolute molecular weight (Mw) is different from the weight-average (relative) molecular weight obtained by conventional GPC methods using a polystyrene-equivalent value (relative value).

[0035] The molecular conformation parameter α of the PPE component is preferably 0.550 or more, more preferably 0.552 or more, and even more preferably 0.555 or more. The molecular conformation parameter α is preferably 0.650 or less, more preferably 0.640 or less, even more preferably 0.630 or less, and particularly preferably 0.600 or less. Having the molecular conformation parameter α within the above range is thought to cause the molecular chains to tend to approach a spherical shape despite the high weight-average absolute molecular weight (Mw) of the PPE component, reducing the spread of the molecular chains. As a result, there is less orientation and re-aggregation of polymer molecules after dissolution in a solvent, improving solubility in the solvent, which is preferable. This is also preferable because the resulting PPE solution has excellent dissolution stability. Having the molecular conformation parameter α within the above range is also preferable because it can be dissolved in solvents such as toluene at room temperature. The molecular conformation parameter α, while resulting from the rearrangement structure, is not determined solely by the amount of the rearrangement structure, but is also determined by the structural state of the polymer chain, such as the branched or bent structural state, depending on the position of the rearrangement structure, etc. Here, the molecular shape parameter α is the Mark-Houwink-Sakurada equation ([η] = K M) that is established between the intrinsic viscosity [η] and the molecular weight (M). α , K is a coefficient), the intrinsic viscosity is determined from the slope of a double logarithmic plot with the logarithm of the molecular weight on the horizontal axis and the logarithm of the intrinsic viscosity on the vertical axis. In the present invention, the intrinsic viscosity is determined from the slope of a double logarithmic plot with the logarithm of the weight-average absolute molecular weight (Mw) on the horizontal axis and the logarithm of the intrinsic viscosity on the vertical axis.

[0036] The ratio (Mz / Mw) of the Z-average molecular weight (Mz) calculated from the absolute molecular weight of the PPE component to the weight-average absolute molecular weight (Mw) is preferably 2.5 or less, more preferably 2.48 or less, and even more preferably 2.46 or less. The lower limit of Mz / Mw is not particularly limited, but for example, 2 is preferable. Having Mz / Mw in the above range is preferable because it provides excellent solubility in solvents. In addition, the quality of the obtained PPE solution tends to be stable, which is also preferable. Here, the Z-average molecular weight is the average molecular weight calculated by a weighted average using the square of the molecular weight as the weight. The measurement method can be performed using the method described in the examples.

[0037] The Z-average molecular weight (Mz) of the PPE component is preferably 80,000 g / mol or more, more preferably 90,000 g / mol or more, and even more preferably 100,000 g / mol or more, and is preferably 200,000 g / mol or less, more preferably 190,000 g / mol or less, and even more preferably 180,000 g / mol or less.

[0038] The number-average absolute molecular weight (Mn) of the PPE component is preferably 16,000 g / mol or more, more preferably 17,000 g / mol or more, and even more preferably 18,000 g / mol or more. The number-average absolute molecular weight (Mn) is preferably 100,000 g / mol or less, more preferably 80,000 g / mol or less, and even more preferably 70,000 g / mol or less. Setting the number-average absolute molecular weight (Mn) within the above range is preferable from the viewpoints of heat resistance, solvent solubility, and dissolution stability. Here, the number-average molecular weight (Mn) is the true number-average molecular weight of the polymer, and, like the weight-average absolute molecular weight (Mw), it is measured using a GPC apparatus equipped with a specified column and a multi-angle light scattering detector. This number-average absolute molecular weight (Mn) is different from the number-average (relative) molecular weight obtained using conventional GPC methods, which is calculated using a polystyrene-equivalent value (relative value).

[0039] The PPE component used in the present invention may contain a PPE that does not have a rearrangement structure. Examples of PPE that does not have a rearrangement structure include a homopolymer having a repeating unit of the general formula (1), a copolymer containing two or more different repeating units of the general formula (1), and a copolymer having a repeating unit of the general formula (1) and a repeating unit other than the general formula (1). Examples of the content of the repeating unit of the general formula (1) or below in the copolymer include those mentioned above.

[0040] The PPE component used in the present invention may also contain a low molecular weight PPE, such as a PPE having a weight average absolute molecular weight (Mw) of less than 40,000 g / mol.

[0041] The content of the PPE component is preferably 95% by mass or more, more preferably 98% by mass or more, of all the components forming the molded product, and even more preferably consists essentially of the PPE component (100% by mass). When the content of the PPE component in the PPE melt-extrusion molded product is within the above range, the obtained molded product not only has excellent mechanical strength, but also excellent heat resistance, chemical resistance, flame retardancy, etc., and is therefore preferred.

[0042] <Components Other Than the PPE Component> The PPE melt-extrusion molded product of the present invention may contain resin components other than the PPE component. Examples of resin components other than the PPE component include styrene, polyethylene, polypropylene, polyamides such as polyamide 4, polyamide 6, polyamide 10, polyamide 11, polyamide 66, polyamide 6T, and polyamide 6T / 11, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polycarbonates. However, the content of such components is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably zero (0% by mass).

[0043] Furthermore, additives such as lubricants, plasticizers, antioxidants, ultraviolet absorbers, dulling agents, and antistatic agents may also be added to the PPE melt-extrusion molded product of the present invention, provided that the effects of the present invention are not impaired.

[0044] <PPE melt-extrusion molded product> The PPE melt-extrusion molded product of the present invention can also be produced by the method for producing a PPE melt-extrusion molded product described below.

[0045] The glass transition temperature of the PPE melt-extrusion molded product is not particularly limited, but is preferably 205°C or higher, more preferably 206°C or higher. A glass transition temperature in the above range is preferred because it increases heat resistance. Furthermore, the upper limit of the glass transition temperature is not particularly limited, but is preferably 230°C or lower, more preferably 220°C or lower.

[0046] The shape of the melt-extrusion molded product is not particularly limited, and it can be molded into various shapes such as pellets, films, sheets, plates, pipes, tubes, rods, fibers, nonwoven fabrics, paper, and fabrics.

[0047] The PPE melt-extrusion molded product of the present invention has excellent solubility and dissolution stability in solvents. Examples of solvents that can dissolve the product include alcohol-based solvents such as methanol, ethanol, and isopropyl alcohol; acetate-based solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone-based solvents such as acetone and methyl ethyl ketone; aromatic solvents such as toluene; and cyclic ether-based solvents such as dioxane. The product can be dissolved in these solvents alone or in a mixture of two or more of them.

[0048] Furthermore, the PPE melt-extrusion molded product of the present invention does not require high temperatures when dissolved in the above-mentioned solvent, and can be dissolved at temperatures ranging from room temperature to about 60° C. Furthermore, the solids concentration of the PPE melt-extrusion molded product solution is not particularly limited and can be set appropriately depending on the intended use of the PPE, but the PPE melt-extrusion molded product solution of the present invention can have a solids concentration of about 5 to 80 mass %.

[0049] 2. Method for Producing PPE Melt-Extrusion Molded Product The method for producing a PPE melt-extrusion molded product of the present invention is characterized by comprising a step of melt-extruding the raw material PPE using an extruder equipped with a cylinder and a screw at a screw peripheral speed of 10 m / min or more and an extrusion temperature of 260°C or more.

[0050] Examples of the PPE raw material include a homopolymer having a repeating unit of the general formula (1), a copolymer containing two or more different repeating units of the general formula (1), and a copolymer having a repeating unit of the general formula (1) and a repeating unit other than the general formula (1). The content of the repeating unit other than the general formula (1) in the copolymer can be as described above. Among these, a homopolymer having a repeating unit of the general formula (1) is preferred.

[0051] Specific examples of the homopolymer having the repeating unit of general formula (1) include poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), and poly(2,6-dipropyl-1,4-phenylene ether). Among these, poly(2,6-dimethyl-1,4-phenylene ether) is preferred.

[0052] As the poly(2,6-dimethyl-1,4-phenylene ether), commercially available products can also be suitably used. Specific examples include PPO640, PPO646, and PPOSA120 manufactured by SABIC Innovative Plastics, and ZYLON S201A and ZYLON S202A manufactured by Asahi Kasei Chemicals Corporation.

[0053] The glass transition temperature of the raw material PPE is preferably 170° C. or higher, more preferably 200° C. or higher, and even more preferably 210° C. or higher. There is no particular upper limit to the glass transition temperature, but it is preferably 230° C. or lower. Having the glass transition temperature of the raw material PPE within the above range is preferred because it allows for the production of a PPE melt-extrusion molded product with high heat resistance.

[0054] Furthermore, the raw materials used in the present invention may contain two or more PPEs having different glass transition temperatures, and specifically, in addition to the PPE having a glass transition temperature of 170° C. or higher, a PPE having a glass transition temperature of less than 170° C. Adding a PPE having a glass transition temperature of less than 170° C. reduces the melt viscosity and improves fluidity, but tends to reduce the amount of rearrangement in the PPE.

[0055] The content of PPE having a glass transition temperature of 170°C or higher in the raw material PPE is preferably 80% by mass or higher, more preferably 90% by mass or higher, and even more preferably 95% by mass or higher, and it is particularly preferable that the raw material PPE consists solely of PPE having a glass transition temperature of 170°C or higher. There is no particular upper limit to the content of PPE having a glass transition temperature of 170°C or higher, but it is preferably 100% by mass or lower. In the present invention, it is preferable to include PPE having a high glass transition temperature (i.e., a high molecular weight) in the above range, as this will result in excellent mechanical strength, heat resistance, chemical resistance, flame retardancy, etc., of the resulting PPE melt-extrusion molded product.

[0056] In addition, resin components and additives other than the PPE component may be contained in addition to the raw material PPE. The resin components and additives other than the PPE component are as described above. Furthermore, the content of resin components other than the PPE component in the raw material is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 0% by mass or less.

[0057] The extruder equipped with a cylinder and a screw may be a single-screw extruder or a twin-screw extruder that is commonly used in this field. In the present invention, a twin-screw extruder is preferably used. However, the extruder is not limited to this, and any extruder that can effectively shear the polymer may be used.

[0058] The peripheral speed of the screw must be such that the dislocation structure is generated to an extent necessary for dissolution in the solvent, and is 10 m / min or more, preferably 15 m / min or more, and more preferably 20 m / min or more. The upper limit of the peripheral speed of the screw is not particularly limited, but is preferably 94.2 m / min or less. In the present invention, by increasing the screw rotation speed to a peripheral speed of 10 m / min or more, a PPE can be formed that satisfies the amount of dislocation necessary for dissolution in the solvent.

[0059] The shape of the screw is not particularly limited, and may be any shape that can apply a shearing force sufficient to cause a rearrangement reaction of the raw material PPE.

[0060] The temperature inside the cylinder (extrusion temperature) is 260° C. or higher, preferably 280° C. or higher, and more preferably 300° C. or higher. By keeping the temperature inside the cylinder within this range, it is possible to form a PPE that satisfies the amount of rearrangement required for dissolution in a solvent, which is preferable.

[0061] An example of the production of PPE melt extrusion molded products (pellets) will be described with reference to Figure 1. The raw material PPE is fed from hopper 1 in Figure 1 into extruder 2 equipped with a cylinder and a screw, and the molten PPE is discharged from a nozzle, cooled on air-cooled belt conveyor 3, and pelletized by pelletizer 4.

[0062] The discharge rate from the nozzle is preferably 5 g / min or more, more preferably 10 g / min or more, and even more preferably 15 g / min or more. The upper limit of the discharge rate is not particularly limited, but is preferably 50,000 g / min or less, more preferably 40,000 g / min or less, and even more preferably 30,000 g / min or less. Discharge within this range is preferable because it provides a residence time sufficient for the amount of rearrangement required for dissolution in the solvent.

[0063] The residence time in the extruder is preferably 5 minutes or less, more preferably 3 minutes or less, even more preferably 2 minutes or less, and particularly preferably 1 minute or less. A longer residence time in the extruder is undesirable because it tends to cause molecular chain scission of the PPE, resulting in a smaller weight-average absolute molecular weight (Mw), which in turn tends to deteriorate properties such as heat resistance.

[0064] The obtained PPE melt extrusion molded product has high solubility in solvents, high dissolution stability, and excellent heat resistance, and can therefore be used in a variety of applications, such as wiring board materials, electric wire coating materials, coatings for the interior of lithium ion battery packages, motor coil wire coating materials, heat-resistant paints, can inner surface paints, film capacitors, and insulating paper.

[0065] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The physical properties and other properties in the following examples were evaluated using the following methods.

[0066] (1) Glass Transition Temperature (Tg) Using a differential scanning calorimeter (model: DSC-Q100) manufactured by TA Instruments Inc., 2 mg of the obtained PPE pellets was measured in a nitrogen atmosphere from 30°C to 250°C at a heating rate of 10°C / min, and the temperature at the intersection of an extension of the baseline below the glass transition temperature and a tangent line showing the maximum slope at the transition part was taken as the glass transition temperature (Tg).

[0067] (2) Amount of dislocation structure in PPE Resonance frequency 600 MHz １ The measurement was carried out by H-NMR measurement. The measurement device used was a BRUKER NMR device (device name: AVANCE-NEO600), and the measurement was carried out as follows. 10 mg of the PPE pellets obtained in the examples and comparative examples were dissolved in deuterated chloroform, and the solution was filled into an NMR tube within 2 hours and the measurement was carried out. Deuterated chloroform was used as the lock solvent, the waiting time was 1 second, the data acquisition time was 4 seconds, and the number of accumulations was 64. Deuterated benzene may also be used as the solvent. The analysis of the amount of rearranged structure was carried out as follows. The R at the 3rd and 5th positions of PPE was １ , R ２ The peaks due to the protons of the R group and the R ３’ The peak integral values ​​of the peaks derived from the protons of the divalent group (e.g., methylene group) represented by the formula: A and B were defined as A and B, respectively, and the amount of rearranged structure was calculated by the following formula: Amount of rearranged structure (mol %)=(B / (A+B))×100

[0068] (3) Absolute Molecular Weight The number-average absolute molecular weight (Mn), weight-average absolute molecular weight (Mw), Z-average molecular weight (Mz) calculated from the absolute molecular weight, and molecular weight dispersity (Mz / Mw) were all determined using gel permeation chromatography (GPC). The measurement conditions were as follows: Apparatus: OMNISEC RESOLVE (manufactured by Spectris Co., Ltd.) Detector: OMNISEC REVEAL (differential refractive index detector, light scattering detector, viscosity detector, manufactured by Spectris Co., Ltd.) Column: TSKgel Super HM-H manufactured by Tosoh Corporation (two columns connected in series) Solvent: Chloroform Temperature: 40°C Flow rate: 0.6 mL / min Measurement solution sample concentration: 1.0 mg / mL Injection volume: 20 μL

[0069] (4) Molecular Conformation Parameter α The molecular conformation parameter α, which is calculated by the Mark-Houwink-Sakurada equation that is established between intrinsic viscosity and molecular weight, was determined from the slope of a double logarithmic plot in which the logarithm of the weight-average absolute molecular weight (Mw) obtained by the above-mentioned measurement method is plotted on the horizontal axis and the logarithm of the intrinsic viscosity is plotted on the vertical axis. The analysis range was set to a range in which the signal-to-noise ratio at the base of each detected peak was 3 or more.

[0070] (5) Peripheral speed of screw The peripheral speed of the screw was calculated by the following formula: Peripheral speed of screw (m / min) = screw diameter (mm) × 0.00314 × screw rotation speed (rpm)

[0071] (6) Solvent Solubility and Dissolution Stability The obtained PPE was dissolved in toluene at 40°C to prepare solutions with solid content concentrations of 10% by mass and 30% by mass. The state of the obtained solutions was observed immediately after dissolution and after standing at room temperature for one week to confirm the state of solvent solubility and dissolution stability. (Solubility immediately after dissolution (solvent solubility)) ◯: The solution was clear at both 10% by mass and 30% by mass concentrations. Δ: The solution was dissolved but cloudy at at least one of 10% by mass and 30% by mass concentrations. ×: The solution remained undissolved at at least one of 10% by mass and 30% by mass concentrations. (Dissolution state after standing at room temperature for one week (dissolution stability)) ◯: The solution was clear at both 10% by mass and 30% by mass concentrations. Δ: The solution was cloudy at at least one of 10% by mass and 30% by mass concentrations. ×: The solution solidified at at least one of 10% by mass and 30% by mass concentrations.

[0072] Example 1 Poly(2,6-dimethyl-1,4-phenylene ether) (PPO (registered trademark) 640, glass transition temperature (Tg): 221°C, manufactured by SABIC Innovative Plastics) was extruded using a twin-screw extruder (product name: KZW15TW-45 / 60MG-NH) manufactured by Technovel Co., Ltd. The twin-screw extruder had six cylinder zones, and from the hopper side, the cylinders were numbered 1, 2, 3, 4, 5, and 6. Cylinder 1 was set to 280°C, and cylinders 2 to 6 and the cylinder head were set to 330°C. The screw rotation speed was set to 1000 rpm, and the screw peripheral speed was 33.0 m / min. The extrusion rate was 50 g / min.

[0073] A φ3.0 mm nozzle was attached downstream of the extruder, and the extruded resin was dropped onto a metal conveyor, taken up at 10 m / min, and cut with a strand cutter to obtain pellets. The physical properties of the obtained pellets are shown in Table 1.

[0074] The obtained PPE pellets were subjected to the measurement of the amount of rearranged structures in the PPE based on the measurement method described above in "(2) Amount of rearranged structures in PPE." １H-NMR measurement was carried out. As a result, when the concentration of deuterated chloroform was 7.28 ppm, peaks were observed around 6.9 ppm, around 6.48 ppm, and around 3.87 ppm. The peak around 6.9 ppm corresponds to the protons at the 3- and 5-positions of PPE generated by rearrangement (i.e., in the rearranged structure), the peak around 6.48 ppm corresponds to the protons at the 3- and 5-positions of PPE in the main chain, and the peak around 3.87 ppm corresponds to the methylene of the methylene bridge generated by rearrangement.

[0075] Example 2 and Comparative Examples 1 and 2 Pellets were obtained in the same manner as in Example 1, except that the screw rotation speed, screw peripheral speed, discharge rate, extrusion temperature, and residence time were changed as shown in Table 1. The physical properties of the obtained pellets are shown in Table 1.

[0076]

[0077] As shown in Table 1, the PPE pellets obtained in the examples of the present invention had a high weight-average absolute molecular weight (Mw) of the PPE component of 40,000 g / mol or more, but by having a rearrangement structure of 1.2 mol% or more, aggregation when dissolved in a solvent was suppressed, resulting in PPE pellets with excellent solvent solubility and dissolution stability. Furthermore, the PPE pellets obtained in the examples had a high glass transition temperature and excellent heat resistance. On the other hand, the PPE pellets in the comparative examples were inferior to the examples in solvent solubility, dissolution stability, and heat resistance.

[0078] 1 Hopper 2 Extruder 3 Air-cooled belt conveyor 4 Pelletizer

Claims

1. A polyphenylene ether melt-extrusion molded product comprising a polyphenylene ether component, wherein the polyphenylene ether component has a rearrangement structure in which repeating units connected by a bond at the ortho position are connected by a bond at the para position, the amount of the rearrangement structure is 1.2 mol% or more relative to all polyphenylene ether structural units in the polyphenylene ether component, and the weight-average absolute molecular weight (Mw) of the polyphenylene ether component is 40,000 g / mol or more.

2. The polyphenylene ether melt-extrusion molded product according to claim 1, characterized in that the molecular conformation parameter α of the polyphenylene ether component calculated using the Mark-Houwink-Sakurada equation is 0.550 or more and 0.650 or less.

3. The polyphenylene ether melt-extrusion molded product according to claim 1, wherein the ratio (Mz / Mw) of the Z-average molecular weight (Mz) calculated from the absolute molecular weight of the polyphenylene ether component to the weight-average absolute molecular weight (Mw) is 2.5 or less.

4. The repeating units connected consecutively via the para-position bond are represented by the following general formula (1): (In the formula, R １ , R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent), and the rearrangement structure is a repeating unit represented by the following general formula (2): (In the formula, R １ , R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ ' is the R ３ The polyphenylene ether melt-extrusion molded product according to claim 1, characterized in that it has a structure represented by the following formula:

5. The polyphenylene ether melt-extrusion molded product according to claim 1, which has a glass transition temperature of 205°C or higher.

6. The polyphenylene ether melt extrudate according to claim 1, wherein the polyphenylene ether melt extrudate is a polyphenylene ether pellet.

7. A method for producing a polyphenylene ether melt-extrusion molded product according to any one of claims 1 to 6, comprising the step of melt-extruding a raw material, polyphenylene ether, using an extruder equipped with a cylinder and a screw at a screw peripheral speed of 10 m / min or more and an extrusion temperature of 260°C or more.

8. The method for producing a polyphenylene ether melt extrusion molded product according to claim 7, wherein the residence time in the extruder is 5 minutes or less.

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