CN112812291B - Hydrogenated polyphenylene ether and process for producing the same - Google Patents
Hydrogenated polyphenylene ether and process for producing the same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
Abstract
The present invention relates to a hydrogenated polyphenylene ether and a method for producing the same. The purpose of the present invention is to provide a low molecular weight hydrogenated polyphenylene ether having further improved dielectric characteristics, and a method for producing the same. A hydrogenated polyphenylene ether having a reduced viscosity (. Eta.sp/c) of 0.04 to 0.20dL/g as measured at 30 ℃ using a chloroform solution having a concentration of 0.5g/dL, which is obtained by hydrogenating 10 to 65% of benzene rings contained in a polyphenylene ether raw material having a repeating structure represented by the general formula (1); a process for producing a hydrogenated polyphenylene ether, which comprises the steps of: the benzene ring contained in the polyphenylene ether is subjected to hydrogenation reaction in an organic solvent using a hydrogenation catalyst under hydrogen pressurization.
Description
Technical Field
The present invention relates to a hydrogenated polyphenylene ether and a method for producing the same.
Background
Polyphenylene ether has excellent high-frequency characteristics, flame retardancy and heat resistance, and is thus widely used as a material in the fields of electric/electronic, automotive and other various industrial materials. In recent years, polyphenylene ethers having extremely low molecular weights as compared with normal high molecular weight polyphenylene ethers have been expected to be effective for electronic material applications, and polyphenylene ethers obtained by oxidative polymerization using 2, 6-dimethylphenol as a raw material and having lower dielectric characteristics than normal polyphenylene ethers have been proposed (for example, patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2004-99824
Disclosure of Invention
Problems to be solved by the invention
However, in electronic devices using a high-frequency band, along with an increase in signal transmission speed, a material having a lower dielectric constant than the polyphenylene ether disclosed in patent document 1 is required.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a low molecular weight hydrogenated polyphenylene ether having further improved dielectric characteristics, and a method for producing the same.
Means for solving the problems
The present invention is as follows.
[1]
A hydrogenated polyphenylene ether having a reduced viscosity (. Eta.sp/c) of 0.04 to 0.20dL/g as measured at 30 ℃ using a chloroform solution having a concentration of 0.5g/dL, which is obtained by hydrogenating 10 to 65% of benzene rings contained in a polyphenylene ether raw material having a repeating structure represented by the general formula (1).
[ chemical formula 1]
(in the formula (1), R 1 、R 2 、R 3 、R 4 Each independently is a hydrogen atom or a saturated or unsaturated hydrocarbon group of C1 to C10, and the saturated or unsaturated hydrocarbon may have a substituent as long as the conditions of C1 to C10 are satisfied. )
[2]
The hydrogenated polyphenylene ether according to [1], wherein the above polyphenylene ether raw material is represented by the general formula (4).
[ chemical formula 2]
(in the formula (4),
R 1 、R 2 、R 3 、R 4 each independently is a hydrogen atom or a saturated or unsaturated hydrocarbon group of C1 to C10, and the saturated or unsaturated hydrocarbon may have a substituent within the limits satisfying the conditions of C1 to C10;
x is an optional linking group of valence a;
a is an integer of 2 to 6, R 5 Each independently is an optional substituent;
k is each independently an integer of 1 to 4. ) The method comprises the steps of carrying out a first treatment on the surface of the
M has a partial structure represented by at least one selected from the group consisting of a hydrogen atom, the following formula (8), formula (9), formula (10), and formula (11);
[ chemical 3]
[ chemical formula 4]
[ chemical 5]
(in the formula (10), R6 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the saturated or unsaturated hydrocarbon may have a substituent within the limits satisfying the conditions having 1 to 10 carbon atoms.)
[6] A method for producing a polypeptide
(in the formula (11), R 7 Saturated or unsaturated 2-valent hydrocarbon groups of C1 to C10, and the saturated or unsaturated hydrocarbon groups may have a substituent within the limits satisfying the conditions of C1 to C10; r is R 8 The saturated or unsaturated hydrocarbon group having a hydrogen atom or a C1 to C10 may have a substituent as far as the conditions of C1 to C10 are satisfied. ) The method comprises the steps of carrying out a first treatment on the surface of the
n represents a repetition number and is an integer of 0 to 200 independently of each other. )
[3]
The hydrogenated polyphenylene ether according to [1] or [2], wherein the glass transition temperature is 140 to 180 ℃.
[4]
[1] A process for producing a hydrogenated polyphenylene ether according to any one of [3], comprising the steps of:
the benzene ring contained in the polyphenylene ether is subjected to hydrogenation reaction in an organic solvent using a hydrogenation catalyst under hydrogen pressurization.
[5]
The method for producing a hydrogenated polyphenylene ether according to [4], wherein the hydrogenation catalyst is a palladium-on-activated carbon catalyst or a rhodium-on-activated carbon catalyst.
[6]
The method for producing a hydrogenated polyphenylene ether according to [4] or [5], wherein the organic solvent comprises at least one selected from the group consisting of hydrocarbon solvents and cyclic ether solvents.
[7]
The method for producing a hydrogenated polyphenylene ether according to any one of [4] to [6], wherein in the step of carrying out the hydrogenation reaction, the hydrogen pressure is 3 to 30MPa and the reaction temperature is 50 to 250 ℃.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a low molecular weight hydrogenated polyphenylene ether having further improved dielectric characteristics and a method for producing the same can be provided.
Detailed Description
A specific embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and the present invention is not limited to the embodiment, and can be modified and implemented as appropriate within the scope of the gist thereof.
In the embodiment of the present invention, a (numerical value) to B (numerical value) means a or more and B or less.
< hydrogenated polyphenylene ether >
The hydrogenated polyphenylene ether of the present embodiment is obtained by hydrogenating 10 to 65% of the benzene rings contained in the polyphenylene ether raw material, and has a reduced viscosity (. Eta.sp/c) of 0.04 to 0.20dL/g measured at 30℃using a chloroform solution having a concentration of 0.5 g/dL.
The hydrogenated polyphenylene ether of the present embodiment has a repeating structure described in the general formula (1).
[ chemical 7 ]
In the formula (1), R 1 、R 2 、R 3 、R 4 Each independently is a hydrogen atom or a saturated or unsaturated hydrocarbon group of C1 to C10, and the saturated or unsaturated hydrocarbon may have a substituent as long as the conditions of C1 to C10 are satisfied.
Examples of the saturated or unsaturated hydrocarbon group include groups having preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, phenyl and the like, preferably phenyl, methyl, ethyl, more preferably methyl.
Saturated or unsaturated hydrocarbons may be substituted with 1 or 2 or more substituents within the limits satisfying the conditions of C1 to C10. Examples of such a substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, etc.), an aryl group (for example, a phenyl group, a naphthyl group, etc.), an alkenyl group (for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, etc.), an alkynyl group (for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group, etc.), an aralkyl group (for example, a benzyl group, a phenethyl group, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), and the like.
In this embodiment, it is considered that the double bond of the phenyl group of the repeating unit of the formula (1) or the double bond of the phenyl group contained in the partial structure of the formula (2) described below is hydrogenated by hydrogenating the polyphenylene ether raw material, but the position on the benzene ring to be hydrogenated is not specified, and it is considered that a different position is hydrogenated for each polyphenylene ether molecule. Thus, the polyphenylene ether to be hydrogenated (hydrogenated polyphenylene ether) is not a single compound, but a composition comprising two or more compounds.
In this embodiment, the hydrogenation rate of the benzene ring contained in the polyphenylene ether raw material is 10 to 65%, more preferably 15 to 50%, still more preferably 30 to 45%. By making the hydrogenation rate of the polyphenylene ether raw material 10% or more, the hydrogenated polyphenylene ether tends to have excellent dielectric characteristics as compared with the polyphenylene ether raw material. When the hydrogenation rate of the polyphenylene ether raw material is 65% or less, the heat resistance is excellent, and when the hydrogenation rate is 50% or less, the glass transition temperature tends to be maintained high.
The hydrogenation rate can be measured by comparing and analyzing peaks of the aromatic region before and after hydrogenation by 1H NMR, and specifically, can be measured by the method described in examples.
The hydrogenated polyphenylene ether of the present embodiment has a reduced viscosity (. Eta.sp/c) of 0.04 to 0.20dL/g, preferably 0.06 to 0.18dL/g, more preferably 0.08 to 0.16dL/g, as measured at 30℃using a chloroform solution having a concentration of 0.5 g/dL.
The reduced viscosity (. Eta.sp/c) can be measured using an Ubbelohde viscosity tube, and specifically, can be measured by the method described in examples.
When the reduced viscosity is 0.04dL/g or more, excellent high-frequency characteristics, flame retardancy and heat resistance as a hydrogenated polyphenylene ether can be effectively exhibited. Further, by setting the reduced viscosity to 0.20dL/g or less, the solubility in a general-purpose solvent (for example, toluene, methylene chloride, methyl ethyl ketone, etc.) and the miscibility with other resins can be improved. The reduced viscosity is a value measured by a measurement method in examples described later.
The method for controlling the reduced viscosity is not particularly limited, and may be adjusted by adjusting the polymerization time or the monomer addition time at the time of producing the polyphenylene ether raw material, for example. In addition, in the case of performing polymerization by a slurry polymerization method, the reduced viscosity can be controlled by increasing the proportion of a solvent having a higher poor solvent property.
The hydrogenated polyphenylene ether of the present embodiment has a glass transition temperature of 140 to 220 ℃, preferably 145 to 220 ℃, more preferably 150 to 220 ℃.
The glass transition temperature may be measured using a differential scanning calorimeter DSC, and specifically, may be measured by the method described in examples.
When the glass transition temperature is 140℃or higher, excellent heat resistance as a hydrogenated polyphenylene ether can be effectively exhibited.
< method for producing hydrogenated polyphenylene ether >
The method for producing a hydrogenated polyphenylene ether according to the present embodiment comprises the following steps (hydrogenation step): the benzene ring contained in the polyphenylene ether is subjected to hydrogenation reaction in an organic solvent using a hydrogenation catalyst under hydrogen pressurization.
Polyphenyl ether raw material-
The polyphenylene ether (polyphenylene ether raw material) used in the method for producing a hydrogenated polyphenylene ether of the present embodiment has a repeating structure represented by the general formula (1).
[ chemical formula 8 ]
In the formula (1), R 1 、R 2 、R 3 、R 4 Each independently is a hydrogen atom or a saturated or unsaturated hydrocarbon group of C1 to C10, and the saturated or unsaturated hydrocarbon may have a substituent as long as the conditions of C1 to C10 are satisfied.
Examples of the saturated or unsaturated hydrocarbon group include groups having preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, phenyl and the like, preferably phenyl, methyl, ethyl, more preferably methyl.
Saturated or unsaturated hydrocarbons may be substituted with 1 or 2 or more substituents within the limits satisfying the conditions of C1 to C10. Examples of such a substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, etc.), an aryl group (for example, a phenyl group, a naphthyl group, etc.), an alkenyl group (for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, etc.), an alkynyl group (for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group, etc.), an aralkyl group (for example, a benzyl group, a phenethyl group, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), and the like.
The polyphenylene ether material may be a polyphenylene ether material represented by the general formula (2).
[ chemical formula 9 ]
In the formula (2), each functional group may be as follows.
R 1 、R 2 、R 3 、R 4 Each independently is a hydrogen atom or a saturated or unsaturated hydrocarbon group of C1 to C10, and the saturated or unsaturated hydrocarbon may have a substituent as long as the conditions of C1 to C10 are satisfied.
Z has a partial structure represented by the following formula (3).
[ chemical formula 10 ]
In the formula (3), X is an arbitrary linking group with a valence, a is an integer of 2 to 6, R 5 Each independently is an arbitrary substituent, and k is an integer of 1 to 4.
M has a partial structure represented by at least one selected from the group consisting of a hydrogen atom, the following formula (8), formula (9), formula (10) and formula (11).
[ chemical formula 11 ]
[ chemical formula 12 ]
[ chemical formula 13 ]
In the formula (10), R 6 The saturated or unsaturated hydrocarbon group having a hydrogen atom or a C1 to C10 may have a substituent as far as the conditions of C1 to C10 are satisfied.
[ chemical formula 14 ]
In the formula (11), R 7 Saturated or unsaturated 2-valent hydrocarbon groups of C1 to C10, and the saturated or unsaturated hydrocarbon groups may have a substituent within the limits satisfying the conditions of C1 to C10; r is R 8 The saturated or unsaturated hydrocarbon group having a hydrogen atom or a C1 to C10 may have a substituent as far as the conditions of C1 to C10 are satisfied.
n represents a repetition number and is an integer of 0 to 200 independently of each other.
In this embodiment, the formula (2) is preferably represented by the following formula (4).
[ 15 ] A method of producing a polypeptide
In the formula (4), R is 1 、R 2 、R 3 、R 4 R is the same as R in the above formula (2) 1 、R 2 、R 3 、R 4 The same applies to R 5 R is the same as R in the above formula (3) 5 The same applies.
More specifically, when a is 2 (X is a 2-valent linking group) in the formula (2) and the formula (3), the partial structure of the formula (3) may be represented by the following formula (5).
[ 16 ] the preparation method
In the formula (5), R 9 、R 10 、R 11 、R 12 Each independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-C7 alkyl group, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbyloxy group, and a halohydrocarbonoxy group having at least 2 carbon atoms separating the halogen atom from the oxygen atom.
In the formula (5), X is selected from the group consisting of a single bond, a 2-valent heteroatom, and a C1-C12-valent hydrocarbon group.
As shown in the above formula (5)Including, but not limited to: r is R 9 And R is 10 Is methyl, R 11 And R is 12 A compound wherein hydrogen and X are a single bond directly linking two aryl groups; r is R 9 And R is 10 Is methyl, R 11 And R is 12 A compound in which hydrogen and X are methylene; r is R 9 And R is 10 Is methyl, R 11 And R is 12 A compound wherein hydrogen and X are sulfur; r is R 9 、R 10 And R is 11 Is methyl, R 12 A compound wherein hydrogen and X are ethylene groups; r is R 9 And R is 10 Is methyl, R 11 And R is 12 A compound wherein hydrogen and X are isopropylidene groups; r is R 9 And R is 10 Is methyl, R 11 And R is 12 A compound wherein hydrogen and X are cyclohexylidene groups; r is R 9 、R 10 And R is 11 Is methyl, R 12 A compound wherein hydrogen and X are a single bond directly linking two aryl groups; r is R 9 、R 10 And R is 11 Is methyl, R 12 A compound in which hydrogen and X are methylene; r is R 9 、R 10 And R is 11 Is methyl, R 12 A compound wherein X is a substituted or unsubstituted ethylene group; r is R 9 、R 10 And R is 11 Is methyl, R 12 A compound wherein hydrogen and X are sulfur; r is R 9 、R 10 And R is 11 Is methyl, R 12 A compound wherein hydrogen and X are isopropylidene groups; r is R 9 、R 10 、R 11 And R is 12 A compound wherein methyl is present and X is methylene; r is R 9 、R 10 、R 11 And R is 12 A compound wherein methyl and X are ethylene; r is R 9 、R 10 、R 11 And R is 12 A compound wherein methyl and X are isopropylidene groups; r is R 9 Is tert-butyl, R 10 Is methyl, R 11 And R is 12 A compound wherein X is a substituted or unsubstituted propylene group; etc.
In the case where a=2 in the formulae (2) and (3), the polyphenylene ether raw material of the present embodiment can be obtained by copolymerizing a monophenol compound represented by the following formula (6) with a diphenol compound represented by the following formula (7), for example.
[ chemical formula 17 ]
In the formula (6), R is 13 、R 14 、R 15 、R 16 R is the same as R in the above formula (1) 1 、R 2 、R 3 、R 4 The same applies.
[ chemical formula 18 ]
In the formula (7), R is 17 、R 18 、R 19 、R 20 R is the same as R in the above formula (5) 9 、R 10 、R 11 、R 12 The same applies.
As the phenolic compound represented by the above formula (6), examples thereof include o-cresol, 2, 6-dimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2, 6-diethylphenol, 2-n-propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2, 6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2-phenylphenol 2, 6-diphenylphenol, 2, 6-bis (4-fluorophenyl) phenol, 2-methyl-6-tolylphenol, 2, 6-xylylphenol, 2, 5-dimethylphenol, 2,3, 6-trimethylphenol, 2, 5-diethylphenol, 2-methyl-5-ethylphenol, 2-ethyl-5-methylphenol, 2-allyl-5-methylphenol, 2, 5-diallyl phenol, 2, 3-diethyl-6-n-propylphenol, 2-methyl-5-chlorophenol, 2-methyl-5-bromophenol, 2-methyl-5-isopropylphenol, 2-methyl-5-n-propylphenol, 2-ethyl-5-bromophenol, 2-methyl-5-n-butylphenol, 2, 5-di-n-propylphenol, 2-ethyl-5-chlorophenol, 2-methyl-5-phenylphenol, 2, 5-diphenylphenol, 2, 5-bis (4-fluorophenyl) phenol, 2-methyl-5-tolylphenol, 2, 5-xylylphenol, 2, 6-dimethyl-3-allylphenol, 2,3, 6-triallylphenol, 2,3, 6-tributylphenol, 2, 6-di-n-butyl-3-methylphenol, 2, 6-di-t-butyl-3-methylphenol, 2, 6-dimethyl-3-n-butylphenol, 2, 6-dimethyl-3-t-butylphenol and the like.
Among the above phenol compounds, 2, 6-dimethylphenol, 2, 6-diethylphenol, 2, 6-diphenylphenol, 2,3, 6-trimethylphenol and 2, 5-dimethylphenol are preferred, and 2, 6-dimethylphenol and 2,3, 6-trimethylphenol are more preferred, particularly for reasons of low cost and easy availability.
The above-mentioned phenol compounds may be used alone or in combination of 1 or more than 2.
Examples thereof include a method of using 2, 6-dimethylphenol and 2, 6-diethylphenol in combination, a method of using 2, 6-dimethylphenol and 2, 6-diphenylphenol in combination, a method of using 2,3, 6-trimethylphenol and 2, 5-dimethylphenol in combination, a method of using 2, 6-dimethylphenol and 2,3, 6-trimethylphenol in combination, and the like. In this case, the mixing ratio of the phenolic compounds to be combined may be arbitrarily selected.
The phenol compound used may contain a small amount of m-cresol, p-cresol, 2, 4-dimethylphenol, 2,4, 6-trimethylphenol, and the like, which may be contained as by-products in production.
The dihydric phenol compound represented by the above formula (7) can be industrially advantageously produced by the reaction of the corresponding monohydric phenol compound with an aldehyde (for example, formaldehyde or the like), a ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone or the like), or a dihaloaliphatic hydrocarbon, or by the reaction of the corresponding monohydric phenol compounds with each other, or the like.
In the case of a=3 to 6 in the formulas (2) and (3), the polyhydric phenol compound may have a structural unit derived from the polyhydric phenol compound obtained by copolymerizing the phenolic compound represented by the formula (6) with the polyhydric phenol compound. Examples of the polyhydric phenol compound include compounds having 3 or more and less than 9 phenolic hydroxyl groups in the molecule.
Examples of the polyhydric phenol compound are listed below. Examples thereof include 4,4' - [ (3-hydroxyphenyl) methylene ] bis (2, 6-dimethylphenol), 4' - [ (3-hydroxyphenyl) methylene ] bis (2, 3, 6-trimethylphenol), 4' - [ (4-hydroxyphenyl) methylene ] bis (2, 6-dimethylphenol), 4' - [ (4-hydroxyphenyl) methylene ] bis (2, 3, 6-trimethylphenol), 4' - [ (2-hydroxy-3-methoxyphenyl) methylene ] bis (2, 6-dimethylphenol), 4' - [ (4-hydroxy-3-ethoxyphenyl) methylene ] bis (2, 3, 6-trimethylethylphenol) 4,4' - [ (3, 4-dihydroxyphenyl) methylene ] bis (2, 6-dimethylphenol), 4' - [ (3, 4-dihydroxyphenyl) methylene ] bis (2, 3, 6-trimethylphenol), 2' - [ (4-hydroxyphenyl) methylene ] bis (3, 5, 6-trimethylphenol), 4' - [4- (4-hydroxyphenyl) cyclohexylidene ] bis (2, 6-dimethylphenol), 4' - [ (2-hydroxyphenyl) methylene ] -bis (2, 3, 6-trimethylphenol), 4,4'- [1- [4- [1- (4-hydroxy-3, 5-dimethylphenyl) -1-methylethyl ] phenyl ] ethylidene ] bis (2, 6-dimethylphenol), 4' - [1- [4- [1- (4-hydroxy-3-fluorophenyl) -1-methylethyl ] phenyl ] ethylidene ] bis (2, 6-dimethylphenol), 2, 6-bis [ (4-hydroxy-3, 5-dimethylphenyl) ethyl ] -4-methylphenol, 2, 6-bis [ (4-hydroxy-2, 3, 6-trimethylphenyl) methyl ] -4-methylphenol, 2, 6-bis [ (4-hydroxy-3, 5, 6-trimethylphenyl) methyl ] -4-ethylphenol, 2, 4-bis [ (4-hydroxy-3-methylphenyl) methyl ] -6-methylphenol, 2, 6-bis [ (4-hydroxy-3-methylphenyl) methyl ] -4-methylphenol, 2, 4-bis [ (4-hydroxy-3-cyclohexylphenyl) methyl ] -6-methylphenol, 2, 4-hydroxy-3-methylphenyl ] -4-methylphenyl, 2, 6-hydroxy-cyclohexyl-methyl ] -4-methylphenol 2, 4-bis [ (4-hydroxy-2, 3, 6-trimethylphenyl) methyl ] -6-cyclohexylphenol, 3, 6-bis [ (4-hydroxy-3, 5-dimethylphenyl) methyl ] -1, 2-benzenediol, 4, 6-bis [ (4-hydroxy-3, 5-dimethylphenyl) methyl ] -1, 3-benzenediol, 2,4, 6-tris [ (2-hydroxy-3, 5-dimethylphenyl) methyl ] -1, 3-benzenediol, 2 '-methylenebis [6- [ (4/2-hydroxy-2, 5/3, 6-dimethylphenyl) methyl ] -4-methylphenol ], 2' -methylenebis [6- [ (4-hydroxy-3, 5-dimethylphenyl) methyl ] -4-methylphenol ], 2 '-methylenebis [6- [ (4/2-hydroxy-2, 3,5/3, 6-trimethylphenyl) methyl ] -1, 3-benzenediol, 2, 6-tris [ (2-hydroxy-3, 5-dimethylphenyl) methyl ] -1, 3-dimethylphenyl ] phenol, 2' -methylenebis [6- [ (4/2-hydroxy-2, 3, 5-trimethylphenyl ] methyl ] -4, 4-trimethylphenyl ] phenol 4,4 '-methylenebis [2- [ (2, 4-dihydroxyphenyl) methyl ] -3, 6-dimethylphenol ], 4' -methylenebis [2- [ (2, 4-dihydroxy-3-methylphenyl) methyl ] -3, 6-dimethylphenol ], 4 '-methylenebis [2- [ (2, 3, 4-trihydroxyphenyl) methyl ] -3, 6-dimethylphenol ], 6' -methylenebis [4- [ (4-hydroxy-3, 5-dimethylphenyl) methyl ] -1,2, 3-benzenetriol ]: 4,4 '-Cyclohexylidenebis [ 2-cyclohexyl-6- [ (2-hydroxy-5-methylphenyl) methyl ] phenol ], 4' -Cyclohexylidenebis [ 2-cyclohexyl-6- [ (4-hydroxy-3, 5-dimethylphenyl) methyl ] phenol ], 4 '-Cyclohexylidenebis [ 2-cyclohexyl-6- [ (4-hydroxy-2-methyl-5-cyclohexylphenyl) methyl ] phenol ], 4' -Cyclohexylidenebis [ 2-cyclohexyl-6- [ (2, 3, 4-trihydroxyphenyl) methyl ] phenol ], 4', 4' - (1, 2-ethylbinary) tetrakis (2, 6-dimethylphenol), 4',4", 4' - (1, 4-phenylene dimethylidene) tetrakis (2, 6-dimethylphenol), 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 1, 3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, and the like, but are not limited thereto.
The number of phenolic hydroxyl groups in the polyhydric phenol compound is not particularly limited as long as it is 3 or more, but if the number of polyphenylene ether terminals is increased, the molecular weight change upon heating may be increased, and thus the number of phenolic hydroxyl groups is preferably 3 to 6, more preferably 3 to 4.
Most preferred polyhydric phenol compounds are 4,4'- [ (4-hydroxyphenyl) methylene ] bis (2, 6-dimethylphenol), 4' - [ (3-hydroxyphenyl) methylene ] bis (2, 6-dimethylphenol), 4'- [ (4-hydroxyphenyl) methylene ] bis (2, 3, 6-trimethylphenol), 4' - [ (3-hydroxyphenyl) methylene ] bis (2, 3, 6-trimethylphenol), 4',4", 4'" - (1, 4-phenylene-dimethylidene) tetrakis (2, 6-dimethylphenol), 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 1, 3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
The polyphenylene ether raw material of the present embodiment may be produced by allowing a monofunctional polyphenylene ether to react with a dihydric phenol and a polyhydric phenol in a redistribution manner in the presence of an oxidizing agent, as the case may be. Redistribution reactions are well known in the art, for example, as described in U.S. Pat. No. 3,496,236 to Cooper et al and U.S. Pat. No. 5,880,221 to Liska et al.
The hydrogenation step of the polyphenylene ether starting material will be described in detail below.
The solvent used in the hydrogenation step is preferably a solvent which has good solubility of the polymer before and after the hydrogenation reaction and good solubility of hydrogen and does not have a site to be hydrogenated. As such a solvent, hydrocarbon solvents such as cyclohexane, ether solvents such as ethylene glycol dimethyl ether, cyclic ether solvents such as tetrahydrofuran and 1, 4-dioxane, and the like are preferable. The solubility of the polyphenylene ether material is preferably a cyclic ether solvent such as tetrahydrofuran or 1, 4-dioxane.
The concentration of the polyphenylene ether raw material in the solution at the time of hydrogenation reaction is preferably 5 to 50% by mass, more preferably 7 to 30% by mass, and still more preferably 10 to 25% by mass. When the amount is within the above range, the operational inconvenience caused by a decrease in reaction rate and an increase in viscosity of the solution can be avoided.
As the hydrogenation catalyst, a catalyst which has a high hydrogenation reaction rate, does not reduce the molecular weight of the starting material due to molecular cleavage or the like, and does not react with the solvent under hydrogenation conditions is selected. Specifically, a solid catalyst in which palladium (Pd) and rhodium (Rh) are supported on a carrier is suitable because a large metal surface area can be obtained by the support. As the catalyst carrier, activated carbon and alumina (Al 2 O 3 ) Silicon oxide (SiO) 2 ) Silicon oxide-aluminum oxide (SiO) 2 -Al 2 O 3 ) Diatomaceous earth, titanium oxide, zirconium oxide, and the like. Among them, palladium-supported activated carbon catalyst and rhodium-supported activated carbon catalyst are preferable.
The amount of the hydrogenation catalyst to be used is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, still more preferably 7 to 25 parts by mass, based on 100 parts by mass of the polyphenylene ether raw material.
As for the hydrogenation reaction conditions, it is preferable to conduct the hydrogenation reaction at 50 to 250℃for 3 to 48 hours under a hydrogen pressurizing pressure of 3 to 30 MPa. More preferably, the reaction is carried out at a hydrogen pressure of 5 to 20MPa at 70 to 200℃for 4 to 24 hours, and still more preferably at a hydrogen pressure of 5 to 20MPa at 90 to 160℃for 5 to 12 hours. When the reaction temperature is within the above range, a sufficient reaction rate can be obtained, and decomposition of the raw material and the hydride can be avoided. In addition, if the hydrogen pressure is within the above range, a sufficient reaction rate can be obtained.
In the case of obtaining the hydrogenated polyphenylene ether in which M is a substituent other than a hydrogen atom, it is preferable to have a step (modification step) of introducing a substituent other than a hydrogen atom into a terminal phenol unit of the hydrogenated polyphenylene ether after hydrogenation of the polyphenylene ether raw material in which m=h is performed in order to avoid decomposition of the terminal substituent M.
In the modification step, an ester, an acid chloride, an acid anhydride, a halogenated hydrocarbon, or the like may be brought into contact with or reacted with the hydrogenated polyphenylene ether in a solution.
Examples of the acid anhydride include acetic anhydride, succinic anhydride, maleic anhydride, salicylic anhydride, phthalic anhydride, acrylic anhydride, and methacrylic anhydride.
Examples of the halogenated hydrocarbon include chloromethylstyrene (p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, and mixtures thereof), epichlorohydrin, and allyl bromide.
After the hydrogenation reaction, the catalyst is separated by a known method such as filtration or centrifugation. The residual metal concentration in the obtained hydrogenated polyphenylene ether is preferably as low as possible. The residual metal concentration is preferably 100ppm or less, more preferably 10ppm or less, and still more preferably 1ppm.
After the catalyst is separated, the solvent is removed from the solution of the hydrogenated polyphenylene ether, thereby separating the hydrogenated polyphenylene ether. For example, the following method may be used: a method in which a concentrated solution obtained by removing a solvent from a solution of a hydrogenated polyphenylene ether is extruded in a molten state and then pelletized; and a known method in which a poor solvent is added to a solution of a hydrogenated polyphenylene ether to precipitate the hydrogenated polyphenylene ether and then the solution is separated.
Examples
The present embodiment will be described in more detail below based on examples, but the present embodiment is not limited to the following examples.
First, the measurement method and evaluation standard of each physical property and evaluation are described below.
(1) Method for measuring reduced viscosity (. Eta.sp/c)
The polyphenylene ether raw material or hydrogenated polyphenylene ether obtained in each example was prepared into a chloroform solution of 0.5g/dL, and the reduced viscosity (. Eta.sp/c) at 30℃was determined using an Ubbelohde viscosity tube. The unit is dL/g.
(2) Determination of hydrogenation Rate
The hydrogenation rate of the hydrogenated polyphenylene ether of (2-1) was determined by 1H NMR. The measurement solution was prepared by dissolving 10mg of the polyphenylene ether raw material before hydrogenation and 10mg of methylene chloride as an internal standard substance in deuterated chloroform. 1H NMR was measured using JNM-ECZ500 (measurement frequency 500MHz, integration number 512) manufactured by Japan electronics using the measurement solution. The integral ratio of methylene chloride (5.3 ppm) was set to 100, and the signal integral value (A) in the aromatic region (6.0 to 8.0 ppm) was confirmed.
(2-2) 1H NMR of the hydrogenated polyphenylene ether was measured in the same manner as in (2-1) above, and the signal integrated value (B) in the aromatic region (6.0 to 8.0 ppm) was confirmed by setting the integral ratio of methylene chloride (5.3 ppm) to 100.
(2-3) Using the decrease in the signal integral value of the aromatic region before and after hydrogenation (A-B) and the signal integral value of the aromatic region before hydrogenation (A), the hydrogenation ratio (%) was defined as (A-B)/(A). Times.100.
It was observed that the signal of the proton shifted from the aromatic region to the aliphatic region by hydrogenation overlapped with the signal of the proton of the aliphatic region originally present in the main chain and side chain of the polyphenylene ether.
(3) Determination of relative permittivity
The polyphenylene ether raw material or hydrogenated polyphenylene ether to be measured was press-molded by a press molding machine (test press YSR-10 type) manufactured by the metal industry of shenteng, ltd.) using a mold having a diameter of 150mm×150mm×2 mm. The relative dielectric constant (-) at 1GHz was measured according to IEC 62810 using a part of the obtained compressed tablets. As the measurement device, PNA-L network analyzer N5230A manufactured by Agilent Technologies Co., ltd was used.
(4) Determination of glass transition temperature (Tg)
The glass transition temperature of the polyphenylene ether starting material was measured using a differential scanning calorimeter DSC (Pyrasl, manufactured by Perkinelmer). After heating from room temperature to 200℃at a heating rate of 20℃per minute in a nitrogen atmosphere, the glass transition temperature was measured at a heating rate of 20℃per minute after cooling to 50℃at 20℃per minute. The glass transition temperature (. Degree. C.) of the hydrogenated polyphenylene ether was also determined in the same manner as described above.
The polyphenylene ether raw materials and the method for producing hydrogenated polyphenylene ether of each example are described below.
Production example 1
To a jacketed reactor (equipped with a nozzle for introducing an oxygen-containing gas, a turbine stirrer, and a deflector at the bottom of the reactor, and a reflux cooler on the exhaust line at the upper part of the reactor), 0.2512g of copper chloride dihydrate, 1.1062g of 35% hydrochloric acid, 9.5937g of N, N, N ', N' -tetramethylpropanediamine, 354.5g of N-butanol, and 354.5g of methanol, 151.7g of 2, 6-dimethylphenol (referred to as "2, 6-xylenol" in the table), and 28.25g of 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane (referred to as "bisphenol") were added. The composition mass ratio of the solvent used was n-butanol: methanol=50:50. Then, oxygen introduction into the reactor was started at a rate of 180 mL/min by a shower head while vigorously stirring, and the polymerization temperature was kept at 45℃and a heat medium was circulated through the jacket to adjust the temperature. The polymerization liquid gradually assumes the state of slurry.
After starting the introduction of oxygen for 120 minutes, the introduction of an oxygen-containing gas was stopped, and to the polymerization mixture was added a 50% aqueous solution in which 1.30g of tripotassium ethylenediamine tetraacetate (a reagent manufactured by Tokugaku Kogyo Co., ltd.) was dissolved, followed by adding 1.62g of hydroquinone (a reagent manufactured by Wako pure chemical industries, ltd.) in small portions, and reacting at 45℃for 1 hour until the slurry-like polyphenylene ether became white. After the reaction was terminated, filtration was carried out, and washing was carried out 3 times with a washing liquid (b) in an amount such that the mass ratio (b/a) of methanol washing liquid (b) to polyphenylene ether (a) to be washed was 4, to obtain a wet polyphenylene ether. Then vacuum-dried at 120℃for 1 hour to obtain a dried polyphenylene ether. The analysis results of the obtained polyphenylene ether raw material are shown in Table 1.
Production example 2
Polyphenylene ether was obtained in the same manner as in production example 1 except that 709.0g of n-butanol was used as the solvent. The analysis results of the obtained polyphenylene ether raw material are shown in Table 1.
Production example 3
To a jacketed reactor (having a nozzle for introducing an oxygen-containing gas, a turbine stirrer, and a deflector at the bottom of the reactor, and a reflux condenser at the upper exhaust line of the reactor), a mixture of 0.1026g of cuprous oxide and 0.7712g of 47% hydrogen bromide, which was prepared in advance, was added together with 0.2471g of N, N' -di-t-butylethylenediamine, 3.6407g of dimethyl-N-butylamine, 1.1962g of di-N-butylamine, 894.04g of toluene, 73.72g of 2, 6-dimethylphenol, and 26.28g of 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane (manufactured by ADEKA: AO-30).
Then, the introduction of air into the reactor was started at a rate of 1.05L/min by means of a shower head while vigorously stirring, and the polymerization temperature was adjusted by flowing a heat medium through a jacket so as to maintain the polymerization temperature at 40 ℃. After 160 minutes from the start of the introduction of air, the introduction of air was stopped, 1.1021g of ethylenediamine tetraacetic acid tetrasodium salt tetrahydrate (reagent manufactured by the same chemical research institute) was added to the polymerization mixture as a 100g aqueous solution, and the mixture was heated to 70 ℃.
After the catalyst was extracted and the by-produced diphenoquinone was removed by incubating at 70℃for 2 hours, the mixture was transferred to a centrifuge made by Sharples company and separated into a polyphenylene ether solution (organic phase) and an aqueous phase in which the catalyst metal had been transferred. The obtained polyphenylene ether solution was transferred to a jacketed concentration tank, toluene was distilled off and concentrated until the solid content in the polyphenylene ether solution reached 55 mass%.
Then, toluene was further distilled off by using an oil bath and a rotary evaporator set at 230℃to dry and fix the solid content, thereby obtaining a polyphenylene ether raw material.
The analysis results of the obtained polyphenylene ether raw material are shown in Table 1.
[ Table 1]
Example 1
Into a 50mL autoclave, 20g of Tetrahydrofuran (THF) was charged, and 5.0g of the polyphenylene ether raw material described in production example 1 was slowly charged and dissolved while stirring with a magnetic stirrer. 0.5g of 5% Rh/C was charged, the vessel was closed and filled with argon, and the inside of the system was made to be an inert atmosphere. Then, hydrogen was filled so that the hydrogen pressure was 10MPa. The hydrogenation was carried out at a temperature of 150℃for 4 hours. The reaction solution was cooled to room temperature, rh/C was removed by filtration, and the obtained filtrate was concentrated under reduced pressure by a rotary evaporator and dried under reduced pressure at 100℃for 12 hours. The analysis results of the obtained hydrides are shown in table 2.
Example 2
Hydrogenation was carried out in the same manner as in example 1 except that the catalyst was changed to 1.0g of 5% Pd/C. The analysis results of the obtained hydrides are shown in table 2.
Example 3
Hydrogenation was performed in the same manner as in example 1 except that hexane was used as the solvent. The analysis results of the obtained hydrides are shown in table 2.
Example 4
Hydrogenation was carried out in the same manner as in example 1 except that 5.0g of the polyphenylene ether starting material described in production example 2 was used. The analysis results of the obtained hydrides are shown in table 2.
Example 5
Hydrogenation was carried out in the same manner as in example 1 except that the hydrogen pressure was set to 5 MPa. The analysis results of the obtained hydrides are shown in table 2.
Example 6
Hydrogenation was carried out in the same manner as in example 1 except that the reaction temperature was set to 100 ℃. The analysis results of the obtained hydrides are shown in table 2.
Example 7
Hydrogenation was carried out in the same manner as in example 1 except that the catalyst was changed to 1.0g of 5% Rh/C, the reaction temperature was 200℃and the reaction time was 52 hours. The analysis results of the obtained hydrides are shown in table 2.
Example 8
Hydrogenation was carried out in the same manner as in example 1 except that 5.0g of the polyphenylene ether starting material described in production example 3 was used. The analysis results of the obtained hydrides are shown in table 2.
Example 9
The hydrogenated polyphenylene ether obtained in example 1 was subjected to methacryloyl modification.
80g of toluene and 26g of hydrogenated polyphenylene ether were mixed and heated to about 85 ℃. 0.55g of dimethylaminopyridine was added. At the time when the solids were considered to be completely dissolved, 4.9g of methacrylic anhydride was slowly added. The resulting solution was continuously mixed while being maintained at 85℃for 3 hours. Subsequently, 120g of a toluene solution of methacrylate-modified polyphenylene ether cooled to room temperature was added dropwise over 30 minutes to 360g of methanol vigorously stirred in a 1L beaker using a magnetic stirrer. The obtained precipitate was filtered under reduced pressure by means of a membrane filter and dried to obtain 38g of a polymer. The appearance of the peak of olefin from methacryloyl group was confirmed around 5.8 ppm. Since the peaks derived from dimethylaminopyridine, methacrylic anhydride and methacrylic acid were substantially disappeared by GC measurement, it was found that the peak derived from methacryloyl group by NMR was a peak of methacryloyl group bonded to the polyphenylene ether terminal. The reduced viscosity of the obtained product was 0.09dL/g, and the relative dielectric constant was 2.40.
Example 10
The hydrogenated polyphenylene ether obtained in example 1 was subjected to styryl modification.
26g of hydrogenated polyphenylene ether, 4.4g of chloromethylstyrene (the ratio of p-chloromethylstyrene to m-chloromethylstyrene: 50/50, manufactured by Tokyo chemical industry Co., ltd.), 0.2g of tetra-n-butylammonium bromide and 80g of toluene were charged into a 300mL three-necked flask equipped with a temperature regulator, a stirring apparatus, a cooling device and a dropping funnel. The mixture was stirred to dissolve and the liquid temperature was 75 ℃. To the mixture was added dropwise an aqueous sodium hydroxide solution (sodium hydroxide 2.2 g/water 3 g) over 20 minutes, and stirring was continued for 4 hours at 75 ℃. Next, after the flask contents were neutralized with 10% aqueous hydrochloric acid, 120g of the polymer solution was added dropwise over 30 minutes to 360g of methanol vigorously stirred in a 1L beaker using a magnetic stirrer. The obtained precipitate was filtered under reduced pressure by means of a membrane filter and dried to obtain 39g of a polymer. 1H NMR measurement was conducted to confirm that the peak derived from the hydroxyl group of the polyphenylene ether disappeared, and that of the proton derived from the styryl group of the olefin was confirmed. Further, since the chloromethylstyrenes peaks substantially disappeared by GC measurement, the NMR-derived styryl group peaks were observed to be the styryl group peaks bonded to the polyphenylene ether terminal. The reduced viscosity of the obtained product was 0.09dL/g, and the relative dielectric constant was 2.40.
Example 11
Using the hydrogenated polyphenylene ether obtained in example 8, methacryloyl modification of the hydrogenated polyphenylene ether was carried out in the same manner as in example 9. The reduced viscosity of the obtained product was 0.09dL/g, and the relative dielectric constant was 2.40.
As shown in tables 1 and 2, in examples 1 to 8, hydrogenated polyphenylene ethers having a lower relative dielectric constant than the polyphenylene ether raw material used were obtained.
Industrial applicability
The hydrogenated polyphenylene ether of the present invention has further improved dielectric characteristics as compared with conventional polyphenylene ether, and therefore has industrial utility as an electronic material.
Claims (27)
1. A hydrogenated polyphenylene ether obtained by hydrogenating 30 to 65% of benzene rings contained in a polyphenylene ether raw material having a repeating structure represented by the general formula (1), wherein the reduced viscosity eta sp/c measured at 30 ℃ using a chloroform solution having a concentration of 0.5g/dL is 0.04dL/g to 0.20dL/g,
[ chemical formula 1]
In the formula (1), R 1 、R 2 、R 3 、R 4 Each independently is a hydrogen atom or a saturated or unsaturated hydrocarbon group of C1 to C10, which may or may not have a substituent, within the limits satisfying the conditions of C1 to C10.
2. The hydrogenated polyphenylene ether according to claim 1, wherein the polyphenylene ether starting material is represented by the general formula (4),
[ chemical formula 2]
In the formula (4), the amino acid sequence of the compound,
R 1 、R 2 、R 3 、R 4 each independently is a hydrogen atom or a saturated or unsaturated hydrocarbon group of C1 to C10, which may or may not have a substituent, within the limits satisfying the conditions of C1 to C10;
x is an optional linking group of valence a;
a is an integer of 2 to 6;
R 5 each independently is an optional substituent;
k is each independently an integer of 1 to 4;
m has a partial structure represented by at least one selected from the group consisting of a hydrogen atom, the following formula (8), formula (9), formula (10), and formula (11);
[ chemical 3]
[ chemical formula 4]
[ chemical 5]
In the formula (10), R 6 Saturated or unsaturated hydrocarbon groups which are hydrogen atoms or C1 to C10, and which have or do not have substituents within the limits satisfying the conditions of C1 to C10;
[6] A method for producing a polypeptide
In the formula (11), R 7 Saturated or unsaturated 2-valent hydrocarbon groups of C1 to C10, which have or do not have substituents within the limits satisfying the conditions of C1 to C10; r is R 8 Saturated or unsaturated hydrocarbon groups which are hydrogen atoms or C1 to C10, and which have or do not have substituents within the limits satisfying the conditions of C1 to C10;
n represents a repetition number and is an integer of 0 to 200 independently of each other.
3. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein 30 to 50% of benzene rings contained in the polyphenylene ether raw material are hydrogenated.
4. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein 30 to 45% of benzene rings contained in the polyphenylene ether raw material are hydrogenated.
5. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein the reduced viscosity ηsp/c measured at 30℃using a chloroform solution having a concentration of 0.5g/dL is from 0.06dL/g to 0.18dL/g.
6. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein the reduced viscosity ηsp/c measured at 30℃using a chloroform solution having a concentration of 0.5g/dL is from 0.08dL/g to 0.16dL/g.
7. The hydrogenated polyphenylene ether according to claim 2, wherein a is 2.
8. The hydrogenated polyphenylene ether according to claim 2, wherein a is an integer of 3 to 6.
9. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein R 1 、R 2 、R 3 、R 4 Each independently is a C1-C6 saturated or unsaturated hydrocarbon group.
10. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein R 1 、R 2 、R 3 、R 4 Each independently is a C1-C3 saturated or unsaturated hydrocarbon group.
11. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein the saturated or unsaturated hydrocarbon has a substituent selected from the group consisting of a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, an alkynyl group, an aralkyl group and an alkoxy group.
12. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein the saturated or unsaturated hydrocarbon has a substituent selected from the group consisting of fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, naphthyl group, vinyl group, 1-propenyl group, 2-propenyl group, ethynyl group, 1-propynyl group, 2-propynyl group, benzyl group, phenethyl group, methoxy group, ethoxy group.
13. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein the glass transition temperature is 140 to 220 ℃.
14. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein the glass transition temperature is 145 to 180 ℃.
15. The hydrogenated polyphenylene ether according to claim 1 or 2, wherein the glass transition temperature is 150℃to 171 ℃.
16. The method for producing a hydrogenated polyphenylene ether according to any one of claims 1 to 15, comprising the steps of:
the benzene ring contained in the polyphenylene ether is subjected to hydrogenation reaction in an organic solvent using a hydrogenation catalyst under hydrogen pressurization.
17. The method for producing a hydrogenated polyphenylene ether according to claim 16, wherein the hydrogenation catalyst is a palladium activated carbon supported catalyst or a rhodium activated carbon supported catalyst.
18. The method for producing a hydrogenated polyphenylene ether according to claim 16 or 17, wherein the organic solvent comprises at least one selected from the group consisting of hydrocarbon solvents and cyclic ether solvents.
19. The method for producing a hydrogenated polyphenylene ether according to claim 18, wherein the hydrocarbon solvent is hexane or cyclohexane.
20. The method for producing a hydrogenated polyphenylene ether according to claim 18, wherein the cyclic ether solvent is tetrahydrofuran or 1, 4-dioxane.
21. The method for producing a hydrogenated polyphenylene ether according to claim 16 or 17, wherein the concentration of the polyphenylene ether raw material in the solution at the time of the hydrogenation reaction is 5 to 50% by mass.
22. The method for producing a hydrogenated polyphenylene ether according to claim 16 or 17, wherein the concentration of the polyphenylene ether raw material in the solution at the time of the hydrogenation reaction is 7 to 30% by mass.
23. The method for producing a hydrogenated polyphenylene ether according to claim 16 or 17, wherein the concentration of the polyphenylene ether raw material in the solution at the time of the hydrogenation reaction is 10 to 25% by mass.
24. The method for producing a hydrogenated polyphenylene ether according to claim 16 or 17, wherein in the step of carrying out the hydrogenation reaction, the hydrogen pressurizing pressure is 3MPa to 30MPa and the reaction temperature is 50℃to 250 ℃.
25. The method for producing a hydrogenated polyphenylene ether according to claim 24, wherein the hydrogenation step is carried out for a reaction time of 3 to 48 hours.
26. The method for producing a hydrogenated polyphenylene ether according to claim 24, wherein in the step of hydrogenation, the hydrogen pressurizing pressure is 5MPa to 20MPa, the reaction temperature is 70 ℃ to 200 ℃, and the reaction time is 4 hours to 24 hours.
27. The method for producing a hydrogenated polyphenylene ether according to claim 24, wherein in the step of hydrogenation, the hydrogen pressurizing pressure is 5MPa to 20MPa, the reaction temperature is 90 ℃ to 160 ℃, and the reaction time is 5 hours to 12 hours.
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| JP2004099824A (en) * | 2002-09-12 | 2004-04-02 | Asahi Kasei Chemicals Corp | Low molecular weight polyphenylene ether powder |
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| US6211327B1 (en) * | 1999-02-05 | 2001-04-03 | General Electric Company | Process for the manufacture of low molecular weight polyphenylene ether resins |
| JP5439700B2 (en) * | 2005-08-11 | 2014-03-12 | 三菱瓦斯化学株式会社 | Polyfunctional phenylene ether oligomer, epoxy resin, and resin composition |
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| US9127160B2 (en) * | 2012-05-29 | 2015-09-08 | Basf Se | Process for producing high-performance thermoplastics with improved intrinsic color |
| TWI510517B (en) * | 2013-04-30 | 2015-12-01 | Ind Tech Res Inst | Polyphenylene ether oligomer and article employing the same |
| EP3004208A4 (en) * | 2013-06-03 | 2017-01-04 | PolyOne Corporation | Low molecular weight polyphenylene ether prepared without solvents |
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| US6417287B1 (en) * | 1997-12-18 | 2002-07-09 | Bayer Aktiengesellschaft | Method for hydrogenating aromatic polymers |
| JP2004099824A (en) * | 2002-09-12 | 2004-04-02 | Asahi Kasei Chemicals Corp | Low molecular weight polyphenylene ether powder |
| JP2009275057A (en) * | 2008-05-12 | 2009-11-26 | Sumitomo Seika Chem Co Ltd | Method for decoloring phenylene ether oligomer |
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