JPH10273521A - Production of copolymer containing phenylene group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soluble resin having excellent resistance to heat, by copolymerizing one or more selected from specific compounds containing a phenylene group with a compound copolymerizable therewith in the presence of a catalyst system containing a transition metal compound. SOLUTION: One or more of the compounds represented by the formula, wherein X is -CYY'-, wherein each of Y and Y' is a halogenated alkyl, H or the like, or fluorenylene, each of R<1> to R<8> is H, a halogen or the like, and each of R<9> to R<10> is a halogen or -OSC2 Z, wherein z is an alkyl, an aryl or the like, such as 2,2-bis(4-methylsulfonyloxyphenyl)hexafluoropropane, and another compound copolymerizable with it are copolymerized in a polymerization solvent in the presence of a catalyst system containing a transition metal compound to produce a phenylene group-containing copolymer. As a catalyst system, use is made of a system comprising a combination of a transition metal salt such as nickel chloride and a ligand such as 2,2'-bipyridine or a transition metal salt co-ordinated with the ligand, and a reducing agent such as zinc as essential components and optionally another salt such as sodium bromide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a phenylene group-containing copolymer which is excellent in heat resistance, low dielectric properties, processability and transparency and is soluble in an organic solvent.

[0002]

2. Description of the Related Art Large-scale integrated circuits (LSIs) have become highly integrated, multifunctional, and high-performance, reflecting the progress of fine processing technology. As a result, the circuit resistance and the capacitance between the wirings (hereinafter, also referred to as “parasitic resistance” and “parasitic capacitance”, respectively) increase, which not only increases the power consumption, but also increases the delay time. This is a major factor in lowering the signal speed. Therefore, it is required to reduce the parasitic resistance and the parasitic capacitance. One of the solutions is to cover the periphery of the wiring with an interlayer insulating film to reduce the parasitic capacitance and respond to the speeding up of the device. I have. However, the interlayer insulating film needs to have excellent heat resistance that can withstand post-processes such as a thin-film forming process at the time of manufacturing a mounting board and chip connection and pinning.

[0003] Polyimide is widely known as the organic material having high heat resistance. However, since it contains a highly polar imide group, no satisfactory material has been obtained in terms of low dielectric property and low water absorption. On the other hand, polyphenylene is known as a high heat-resistant organic material containing no polar group. This polyphenylene is excellent in heat resistance, but is inferior in the solubility in an organic solvent. Therefore, it is common to introduce a side chain. As such polyphenylene, for example, USP 52140
44, WO96 / 28491, EP629217 and the like. These polymers basically have a polyparaphenylene structure and partially copolymerize a flexible monomer, but are soluble only in a specific organic solvent and have poor processability. Further, many side chains are polar groups or alkyl groups, and thus do not sufficiently satisfy heat resistance and low dielectric properties. Further, these polymers are mainly produced from aromatic dichloro compounds such as paradichlorobenzene derivatives as raw materials. If an attempt is made to introduce a fluoroalkyl group or an aryl group into a side chain in order to produce a heat-resistant, low-dielectric material from such an aromatic dichloro compound, the synthesis becomes complicated, and a monomer cannot be stably obtained, There is an inconvenience that the degree of polymerization is not sufficiently increased due to steric hindrance of the chain. As described above, polyphenylene that sufficiently satisfies heat resistance, low dielectric properties, and workability and that can be manufactured by an inexpensive process has not been found so far.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a phenylene group-containing compound in which a bending group is introduced into the main chain and another compound copolymerizable with the phenylene group-containing compound.
An object of the present invention is to obtain a soluble resin having excellent low dielectric properties, workability, and transparency.

[0005]

According to the present invention, at least one compound selected from phenylene group-containing compounds represented by the following general formula (I) and another compound copolymerizable therewith are used as a transition metal compound. The present invention provides a method for producing a phenylene group-containing copolymer, which is copolymerized in the presence of a catalyst system containing phenylene group.

[0006]

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[Where X is -CYY '-(where Y to
Y 'are the same or different, a halogenated alkyl group, a hydrogen atom or a group represented by aryl group indicates a) or fluorenylene group,, R ¹ to R ⁸ are the same or different, a hydrogen atom, a halogen atom, an alkyl group , halogenated alkyl group, an allyl group or an aryl group,, R ⁹
To R ¹⁰ are the same or different and are each a halogen atom, or -O
SO ₂ Z (where Z represents an alkyl group, a halogenated alkyl group or an aryl group). Here, as the other copolymerizable compound, at least one of the compounds represented by the following general formulas (II) to (V) is preferable.

[0008]

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Wherein R ^{11 to} R ¹² are the same or different;
R ^{9 to} R ^{10 in} the general formula (I) are the same or different, and R ^{13 to} R ²⁰ are the same or different, and are the same as R ^{1 to} R ^{8 in} the general formula (I). ]

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a phenylene group-containing compound having a bending group introduced into the main chain represented by the above general formula (I), and another compound copolymerizable therewith. By copolymerizing in a polymerization solvent in the presence of a catalyst system containing a transition metal compound, a phenylene group-containing copolymer that is excellent in heat resistance, low dielectric properties, processability, and transparency and is soluble in an organic solvent is obtained. It is manufactured. Here, Y of —CYY′— of the repeating structural unit represented by the above general formula (I)
Among Y to Y ′, the halogenated alkyl group includes a trifluoromethyl group and a pentafluoroethyl group, and the aryl group includes a phenyl group, a biphenyl group, a tolyl group and a pentafluorophenyl group. In R ^{1 to} R ^{8 in} the general formula (I), the halogen atom is a fluorine atom, the alkyl group is a methyl group or an ethyl group, and the halogenated alkyl group is trifluoro. Methyl group, pentafluoroethyl group, etc., as the allyl group, propenyl group, etc.,
Examples of the aryl group include a phenyl group, a pen, R ⁹ ~
R ¹⁰ are the same or different and are each a halogen atom or —OS
O ₂ Z (where Z represents an alkyl group, a halogenated alkyl group or an aryl group). Examples of the halogen atom of R ^{9 to} R ¹⁰ include a chlorine atom, a bromine atom and an iodine atom. In addition, the general formula (I)
In the formula, -OSO ₂ Z includes Z, wherein the alkyl group is a methyl group or an ethyl group, the halogenated alkyl group is a trifluoromethyl group or the like, and the aryl group is a phenyl group or p-tolyl group. Is mentioned. As X in the general formula (I), especially _{-C (CF 3) 2 -,} - C
_{(CF 3) (C 6 H} 5) -, and fluorenylene group.

Specific examples of the phenylene group-containing compound represented by the general formula (I) include 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane and bis (4-methylsulfonyloxyphenyl) ) Methane, bis (4-methylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4-methylsulfonyloxy-3-methylphenyl) hexafluoropropane,
2,2-bis (4-methylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9- Screw (4-
Methylsulfonyloxyphenyl) fluorene, 9,9
-Bis (4-methylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) fluorene,
9,9-bis (4-methylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-methylsulfonyloxy-3) -Methylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3) -Fluorophenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (4
-Methylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4
-Methylsulfonyloxyphenyl) methane, bis (4
-Methylsulfonyloxy-3-methylphenyl) methane, bis (4-methylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-methylsulfonyloxy-3-propenylphenyl) methane, bis (4 -Methylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-methylsulfonyloxyphenyl) phenylmethane and the like.

Specific examples of the phenylene group-containing compound represented by the general formula (I) include 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane and bis (4-trifluoro Methylsulfonyloxyphenyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) diphenylmethane,
2,2-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) hexafluoropropane,
2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (4-trifluoromethylsulfonyloxyphenyl) fluorene, 9,9-bis (4-
Trifluoromethylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfur) Phonyloxy-3-propenylphenyl) fluorene,
9,9-bis (4-trifluoromethylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy) -3,5-dimethylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) diphenylmethane,
Bis (4-trifluoromethylsulfonyloxy-3-
(Fluorophenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl) fluorene, 9,9 -Bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4-trifluoromethylsulfonyloxyphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) ) Methane, bis (4-trifluoromethylsulfonyloxy-3,5-)
Dimethylphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4
-Trifluoromethylsulfonyloxyphenyl) and the like.

Further, specific examples of the phenylene group-containing compound represented by the general formula (I) include 2,2-bis (4-phenylsulfonyloxyphenyl) hexafluoropropane and bis (4-phenylsulfonyl). Loxyphenyl) methane, bis (4-phenylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfonyl) Roxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9-bis (4-phenylsulfonyloxyphenyl) fluorene , 9,9-bis (4-phenylsulfonyloxy-3-methyl) Phenyl) fluorene, 9,9
-Bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-phenylsulfonyl) Roxy
3-phenylphenyl) fluorene, bis (4-phenylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3,5
-Dimethylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4
-Phenylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (4-phenylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-
3,5-difluorophenyl) fluorene, bis (4-
Phenylsulfonyloxyphenyl) methane, bis (4
-Phenylsulfonyloxy-3-methylphenyl) methane, bis (4-phenylsulfonyloxy-3,5-
Dimethylphenyl) methane, bis (4-phenylsulfonyloxy-3-propenylphenyl) methane, bis (4-phenylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-phenylsulfonyloxyphenyl) phenylmethane, etc. Is mentioned.

Further, specific examples of the phenylene group-containing compound represented by the general formula (I) include 2,2-bis (p-tolylsulfonyloxyphenyl) hexafluoropropane and bis (p-tolylsulfate). Phonyloxyphenyl) methane, bis (p-tolylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfate) Phonyloxy-3-propenylphenyl) hexafluoropropane,
2,2-bis (p-tolylsulfonyloxy-3,5-
Dimethylphenyl) hexafluoropropane, 9,9-
Bis (p-tolylsulfonyloxyphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-)
Methylphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy)
3-propenylphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-phenylphenyl) fluorene, bis (p-tolylsulfonyloxy)
3-methylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy)
3-propenylphenyl) diphenylmethane, bis (p
-Tolylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (p-tolylsulfonyloxy)
3,5-difluorophenyl) diphenylmethane, 9,
9-bis (p-tolylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (p-tolylsulfonyloxyphenyl) Methane, bis (p-tolylsulfonyloxy-3-methylphenyl) methane, bis (p-tolylsulfonyloxy)-
3,5-dimethylphenyl) methane, bis (p-tolylsulfonyloxy-3-propenylphenyl) methane,
Bis (p-tolylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (p-tolylsulfonyloxyphenyl) phenylmethane and the like can be mentioned.

The other copolymerizable compound used in the present invention is preferably at least one of the compounds represented by the above general formulas (II) to (V). Here, as other copolymerizable compounds represented by the general formula (II), for example, p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, p-dimethylsulfonyloxybenzene, , 5-dichlorotoluene, 2,5-
Dibromotoluene, 2,5-diiodotoluene, 2,5
-Dimethylsulfonyloxybenzene, 2,5-dichloro-p-xylene, 2,5-dibromo-p-xylene,
2,5-diiodo-p-xylene, 2,5-dichlorobenzotrifluoride, 2,5-dibromobenzotrifluoride, 2,5-diiodobenzotrifluoride, 1,4-dichloro-2,3,5 6-tetrafluorobenzene, 1,4-dibromo-2,3,5,6-tetrafluorobenzene, 1,4-diiodo-2,3,5
Examples thereof include 6-tetrafluorobenzene and the like, and preferred are p-dichlorobenzene, p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, and 2,5-dichlorobenzotrifluoride.

Other copolymerizable compounds represented by the above general formula (III) include 4,4'-dimethylsulfonyloxybiphenyl and 4,4'-dimethylsulfonyloxy-3,3'-di Propenyl biphenyl, 4,4'-dibromobiphenyl, 4,4'-diiodobiphenyl, 4,
4'-dimethylsulfonyloxy-3,3'-dimethylbiphenyl, 4,4'-dimethylsulfonyloxy-
3,3'-difluorobiphenyl, 4,4'-dimethylsulfonyloxy-3,3 ', 5,5'-tetrafluorobiphenyl, 4,4'-dibromooctafluorobiphenyl, 4,4-methylsulfoni Roxyoctafluorobiphenyl and the like, preferably 4,4'-
Dimethylsulfonyloxybiphenyl, 4,4'-dibromobiphenyl, 4,4'-diiodobiphenyl, 4,
4'-dimethylsulfonyloxy-3,3'-dipropenylbiphenyl.

Other copolymerizable compounds represented by the general formula (IV) include m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, and 2,4. -Dichlorotoluene,
2,4-dibromotoluene, 2,4-diiodotoluene, 3,5-dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene 2,6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxytoluene, 2,
4-dichlorobenzotrifluoride, 2,4-dibromobenzotrifluoride, 2,4-diiodobenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5-diiodobenzo Trifluoride, 1,3-dibromo-
Examples thereof include 2,4,5,6-tetrafluorobenzene and the like, and preferably m-dichlorobenzene, 2,4-dichlorotoluene, 3,5-dimethylsulfonyloxytoluene, and 2,4-dichlorobenzotrifluoride. .

Other copolymerizable compounds represented by the above general formula (V) include o-dichlorobenzene, o-dibromobenzene, o-diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3 -Dichlorotoluene,
2,3-dibromotoluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, 3,4 -Dimethylsulfonyloxybenzene, 3,4-dichlorobenzotrifluoride, 3,4-dibromobenzotrifluoride, 3,
Examples thereof include 4-diiodobenzotrifluoride and 1,2-dibromo-3,4,5,6-tetrafluorobenzene, and preferably o-dichlorobenzene and 3,4-dichlorobenzotrifluoride.

Among the other copolymerizable compounds, the compounds represented by the above general formulas (IV) to (V) are preferred in view of solubility and high molecular weight.
It is preferable to use at least one of the compounds represented by

The copolymerization ratio of at least one compound selected from the phenylene group-containing compounds represented by the general formula (I) and the other copolymerizable compounds represented by the general formulas (II) to (V) Is preferably at least 1 mol%,
More preferably, it is at least 10 mol%. On the other hand, if the copolymerization ratio is less than 1 mol%, problems such as a decrease in the solubility of the obtained copolymer and a decrease in the molecular weight occur. In particular, when another copolymerizable compound represented by the general formula (II) is used, its proportion is preferably 1 to 49 mol% in the phenylene group-containing compound and the other copolymerizable compound. ,
More preferably, it is 10 to 49 mol%, particularly preferably 1 to 49 mol%.
0 to 40 mol%. Within this range, good solubility and high molecular weight can be obtained. When another copolymerizable compound represented by the general formula (III) is used, its proportion is preferably 1 to 24 mol% in the phenylene group-containing compound and the other copolymerizable compound. And more preferably 5 to 20 mol%. Within this range, good solubility and high molecular weight can be obtained. Furthermore, the general formula (IV)
Alternatively, when another copolymerizable compound represented by (V) is used, the proportion thereof is 5 to 80 mol%, preferably 5 to 80 mol% in the phenylene group-containing compound and the other copolymerizable compound. It is 50 mol%, more preferably 0 to 45 mol%.

The catalyst used for producing the phenylene group-containing copolymer of the present invention is a catalyst system containing a transition metal compound. The catalyst system includes a transition metal salt and a ligand, or a coordinator. A transition metal salt to which a coordinator is coordinated and a reducing agent are essential components, and a “salt” may be added to increase the polymerization rate. Here, as the transition metal salt, nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate; palladium compounds such as palladium chloride, palladium bromide and palladium iodide; iron chloride and iron bromide And iron compounds such as iron iodide, and cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Of these, nickel compounds such as nickel chloride and nickel bromide are particularly preferred. Examples of the ligand include triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene, and 1,3-bis (diphenylphosphino) propane. 2'-bipyridine is preferred.

Further, examples of the transition metal salt to which a ligand is coordinated in advance include, for example, nickel chloride 2 triphenylphosphine, nickel bromide 2 triphenylphosphine, nickel iodide 2 triphenylphosphine, and nickel nitrate 2-triphenylphosphine. Phenylphosphine, nickel chloride 2,
2 'bipyridine, nickel bromide 2,2' bipyridine, nickel iodide 2,2 'bipyridine, nickel nitrate 2,
2 'bipyridine, bis (1,5-cyclooctadiene)
Nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like can be mentioned, with preference given to nickel chloride2triphenylphosphine and nickel chloride 2,2'bipyridine.

The catalyst used for producing the phenylene group-containing copolymer of the present invention is a catalyst system containing a transition metal compound. The catalyst system includes a transition metal salt and a ligand, or a coordinator. A transition metal (salt) to which a ligand is coordinated and a reducing agent are essential components, and a “salt” may be added in order to increase the polymerization rate. Here, as the transition metal salt, nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate; palladium compounds such as palladium chloride, palladium bromide and palladium iodide; iron chloride and iron bromide And iron compounds such as iron iodide, and cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Of these, nickel chloride and nickel bromide are particularly preferred. Examples of the ligand include triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene, and 1,3-bis (diphenylphosphino) propane. 2 '
-Bipyridine is preferred. The above-mentioned ligands may be used alone.
Alternatively, two or more kinds can be used in combination.

Further, as the transition metal (salt) to which a ligand has been previously coordinated, for example, nickel chloride 2 triphenylphosphine, nickel bromide 2 triphenylphosphine, nickel iodide 2 triphenylphosphine, nickel nitrate 2 -Triphenylphosphine, nickel chloride 2,2 'bipyridine, nickel bromide 2,2' bipyridine, nickel iodide 2,2 'bipyridine, nickel nitrate 2,2' bipyridine, bis (1,5-cyclooctadiene) nickel , Tetrakis (triphenylphosphine)
Nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like can be mentioned, and nickel chloride 2 triphenylphosphine and nickel chloride 2,2 ′ bipyridine are preferable.

The reducing agent that can be used in the catalyst system of the present invention includes, for example, iron, zinc, manganese, aluminum, magnesium, sodium, and calcium, and zinc and manganese are preferred. These reducing agents can be used after being activated by contact with an acid or an organic acid. The “salt” that can be used in the catalyst system of the present invention includes sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, and sodium sulfate, potassium fluoride, potassium chloride, and bromide. Potassium compounds such as potassium, potassium iodide, and potassium sulfate; ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate; and sodium bromide, iodine Sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide are preferred.

The proportion of each component used in the catalyst system is such that the transition metal salt or the transition metal (salt) to which the ligand is coordinated is the compound represented by the above general formula (I) and the general formula (II)
Usually, 0.0001 to 10 with respect to 1 mol of the total amount of at least one other copolymerizable compound represented by (V).
Mole, preferably 0.01 to 0.5 mole. 0.0
If the amount is less than 001 mol, the polymerization reaction does not proceed sufficiently, while if it exceeds 10 mol, there is a problem that the molecular weight is reduced. When a transition metal salt and a ligand are used in the catalyst system, the use ratio of the ligand is usually 0.1 to 100 mol, preferably 1 to 1 mol per mol of the transition metal salt.
0 mol. If the amount is less than 0.1 mol, the catalytic activity becomes insufficient, while if it exceeds 100 mol, there is a problem that the molecular weight decreases. The proportion of the reducing agent used in the catalyst system is the sum of at least one of the compound represented by the general formula (I) and the other copolymerizable compound represented by the general formulas (II) to (V). Usually, 0.1 mol per mol of
１００100 mol, preferably 1-10 mol. 0.1
If the amount is less than 100 moles, the polymerization does not proceed sufficiently. On the other hand, if the amount exceeds 100 moles, there is a problem that purification of the obtained copolymer becomes difficult. Further, when a “salt” is used in the catalyst system, the proportion of the compound is represented by the compound represented by the general formula (I) and the other copolymerizable compound represented by the general formulas (II) to (V). Is usually 0.001 to 100 mol, preferably 0.01 to 1 mol, per mol of at least one kind of
Is a mole. If the amount is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient.
There is a problem that purification of the obtained copolymer becomes difficult.

Examples of the polymerization solvent that can be used in the present invention include, for example, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2
-Pyrrolidone, γ-butyrolactone, γ-butyrolactam, etc., and tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide,
-Methyl-2-pyrrolidone is preferred. These polymerization solvents are preferably used after being sufficiently dried. In the polymerization solvent, the concentration of at least one of the compound represented by the general formula (I) and the other copolymerizable compound represented by the general formulas (II) to (V) is usually 1 to 100% by weight. %, Preferably 5 to 40% by weight. Further, the polymerization temperature when polymerizing the copolymer of the present invention is usually 0 to 200.
° C, preferably 50-80 ° C. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.

At least one of the phenylene group-containing compounds represented by the general formula (I), and the compound represented by the general formula (II)
An example of a model reaction formula for obtaining a phenylene group-containing copolymer using at least one of the other copolymerizable compounds represented by (V) to (V) is as follows. However,
The following reaction formula shows a case where a phenylene group-containing compound represented by the general formula (I) and another copolymerizable compound represented by the general formula (II) are used. In the model reaction formula, m and n indicate the number of repeating units. The phenylene group-containing copolymer obtained by the copolymerization of the present invention may be a random copolymer or a block copolymer. Here, in order to obtain a random copolymer, a phenylene group-containing compound represented by the above general formula (I) and another compound copolymerizable with the phenylene group-containing compound are present in the polymerization system immediately before, immediately after or immediately after the start of polymerization. There is a method to make it. In order to obtain a block copolymer, various compounds containing a phenylene group represented by the general formula (I) and other compounds copolymerizable with the phenylene group are prepared by using a catalyst system containing a transition metal compound in advance. Below, a method of mixing the reaction solution after polymerization, or
A method of purifying the reaction solution and polymerizing it again in the presence of a catalyst system containing a transition metal compound, a phenylene group-containing compound represented by the above general formula (I), and another polymerizable with the phenylene group-containing compound. A method in which any one of the compounds is polymerized in advance in the presence of a catalyst system containing a transition metal compound in advance, and another copolymerization component is added in the middle to perform polymerization.

[0029]

Embedded image

The phenylene group-containing copolymer obtained according to the present invention has a weight average molecular weight in terms of polystyrene of 1,000.
0 to 1,000,000, preferably 1,500 to 20
It is 0000. If it is less than 1,000, the coating properties and strength are insufficient, while if it exceeds 1,000,000, the solubility becomes insufficient.

The structure of the phenylene group-containing copolymer of the present invention is 900 to 675 c
m ^-1 , 1,300 to 1,000 cm ^-1 , 1,500 to
1,400Cm ^-1, confirmed by the absorption of 3,100～3,000Cm ^-1, these composition ratio can be determined by elemental analysis. Further, the structure can be confirmed from a peak at 6.0 to 8.5 ppm by a nuclear magnetic resonance spectrum.

Examples of uses of the phenylene group-containing copolymer of the present invention include an interlayer insulating material, a protective film, a low refractive material,
Examples include an optical waveguide material, an antireflection film, a sealing material, a liquid crystal alignment film, a printed circuit board material, and a gas permeable film.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In Examples,% and parts are by weight unless otherwise specified. Various measurement items in the examples were obtained as follows.

The weight average molecular weight (Mw ) was determined by gel permeation chromatography (GPC) in terms of polystyrene. 5% weight loss temperature (Td5 ) The temperature was measured by a TG method in a nitrogen atmosphere at a heating rate of 10 ° C./min. The coatable polymer was dissolved in a predetermined solvent, applied to a glass substrate by spin coating, baked under predetermined conditions, and visually observed for appearance. Relative Dielectric Constant (ε ) A polymer film was formed on a SUS substrate in the same manner as described above, and then a gold electrode was formed by mask evaporation to obtain a sample for relative dielectric constant measurement. The capacitance of this sample was measured with an LCR meter, and the relative dielectric constant was determined from the following equation. ε = C · d / ε ₀ · S Here, ε is a relative permittivity, C is a capacitance, ε ₀ is a permittivity in a vacuum, and S is an upper electrode area. 90 parts of a solvent was added to 10 parts of the soluble polymer, stirred at room temperature, and observed visually. ◎ indicates easy solubility, ○ indicates soluble, △ indicates partially soluble, and × indicates insoluble.

Example 1 Internal volume 500 equipped with an argon gas inlet tube and a thermometer
7.5 g of sodium iodide in a 3-ml three-necked flask,
1.3 g of anhydrous nickel chloride, triphenylphosphine 1
5.7 g, 45.8 g of zinc dust contacted with acetic acid, and 9,9-bis (4-methylsulfonyloxyphenyl)
42.6 g of fluorene (hereinafter also referred to as “BMsFL”)
(84 mmol) and dried under vacuum for 24 hours, and then the inside of the three-necked flask was filled with argon gas. Subsequently, 150 ml of dry N, N-dimethylacetamide
Was added and stirred under a stream of argon at 70 ° C.
The reaction turned brown. Here, 2,4-dichlorobenzotrifluoride (hereinafter also referred to as “mDCBTf”)
3.44 g (16 mmol) was poured into a three-necked flask using a syringe and reacted at 70 ° C. for 20 hours. The reaction solution was poured into a mixture of 500 ml of 36% hydrochloric acid and 2,000 ml of methanol, and precipitated. The thing was collected. The obtained precipitate was suspended in chloroform.
After extraction with a normal hydrochloric acid aqueous solution, the chloroform layer was poured into acetone, and the precipitate was recovered and dried to obtain 15 g of a white powdery copolymer. Further, 20 parts of the obtained copolymer is dissolved in 80 parts of cyclohexanone, applied to a glass substrate by a spin coating method, and baked at 80 ° C., 120 ° C., and 160 ° C. for 30 minutes each to obtain a uniform coating film. Was. Table 1 shows the weight average molecular weight, 5% weight loss temperature, appearance of the coating film, and relative dielectric constant of the obtained copolymer, and Table 2 shows the solubility. FIG. 1 shows the ¹ H-NMR spectrum of the obtained copolymer.
FIG. 2 shows the IR spectrum.

Example 2 Except that the charging ratio of the monomers was changed to the composition shown in Table 1,
A copolymer was obtained in the same manner as in Example 1. Tables 1 and 2 show the results.
Shown in FIG. 3 shows the ¹ H-NMR spectrum and FIG. 4 shows the IR spectrum of the obtained copolymer. Example 3 A copolymer was obtained in the same manner as in Example 1, except that the charging ratio of the monomers was set to the composition shown in Table 1, and hexane was used instead of acetone in the purification of the copolymer. The results are shown in Tables 1 and 2.

[0037]

[Table 1]

[0038]

[Table 2]

Example 4 Internal volume 500 equipped with an argon gas inlet tube and a thermometer
7.5 g of sodium iodide in a 3-ml three-necked flask,
1.3 g of anhydrous nickel chloride, triphenylphosphine 1
5.7 g, zinc powder in contact with acetic acid 45.8 g, 2,2
29.52 g (60 mmol) of -bis (4-methylsulfonyloxyphenyl) hexafluoropropane and 23.28 of 3,3'-diallyl-4,4'-bis (4-fluorobenzenesulfonyloxy) biphenyl
g (40 mmol) was added and dried under vacuum for 24 hours, and then the inside of the three-necked flask was filled with argon gas. Subsequently, 150 ml of dry N, N-dimethylacetamide
Was added and stirred under a stream of argon at 70 ° C.
The reaction turned brown. After allowing the reaction to proceed at 70 ° C. for 20 hours, the reaction solution was poured into a mixture of 500 ml of 36% hydrochloric acid and 2,000 ml of methanol to collect a precipitate.

The obtained precipitate is added to and suspended in chloroform, extracted with a 2N aqueous hydrochloric acid solution, and then the chloroform layer is poured into acetone, and the precipitate is collected and dried.
As a result of GPC measurement, a copolymer having a weight average molecular weight in terms of polystyrene of 20,800 was obtained. The 5% decrease temperature of this copolymer was 470 ° C. Further, 25 parts of the obtained copolymer was dissolved in 75 parts of propylene glycol-1-monomethyl ether-2-acetate, applied to a glass substrate by a spin coating method, and further heated at 80 ° C. and 120 ° C. for 2 minutes each. 30 at 280 ° C under nitrogen
After baking for minutes, a colorless and transparent coating film was obtained. The obtained coating film,
Propylene glycol-1-monomethyl ether-2-
Acetate, dimethyl sulfoxide, 1-methyl-2-
When each was immersed in pyrrolidone for 1 hour to evaluate the solvent resistance, no change was observed in any of them. Further, when the relative dielectric constant was measured, it was 2.3 (1 MHz). The ¹ H-NMR spectrum and IR spectrum of the obtained copolymer are shown in FIG. 5 and FIG. 6, respectively.

[0041]

The phenylene group-containing copolymer obtained according to the present invention is excellent in heat resistance, low dielectric properties and transparency, and is soluble in organic solvents. It can be very suitably used for a wide range of applications as an optical material.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of a copolymer obtained in Example 1.

FIG. 2 is an IR spectrum of the copolymer obtained in Example 1.

FIG. 3 is a ¹ H-NMR spectrum of the copolymer obtained in Example 2.

FIG. 4 is an IR spectrum of the copolymer obtained in Example 2.

FIG. 5 is a ¹ H-NMR spectrum of the copolymer obtained in Example 4.

FIG. 6 is an IR spectrum of the copolymer obtained in Example 4.

Claims (5)

[Claims] At least one compound selected from phenylene group-containing compounds represented by the following general formula (I) and another compound copolymerizable therewith are copolymerized in the presence of a catalyst system containing a transition metal compound. A method for producing a phenylene group-containing copolymer, characterized by polymerizing. Embedded image Wherein, X is -CYY '- (wherein, Y～Y' are identical or different, halogenated alkyl group, a hydrogen atom or an aryl group) represents a group represented by or fluorenylene group,, R ¹ R ⁸ to R ⁸ are the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, an allyl group, or an aryl group; R ^{9 to} R ¹⁰ are the same or different and are a halogen atom, or —OSO ₂ Z
(Where Z represents an alkyl group, a halogenated alkyl group or an aryl group). ] 2. In the general formula (I), X is —C (CF ₃ ) ₂
The method for producing a phenylene group-containing copolymer according to claim 1, wherein 3. X in the general formula (I) is —C (CF ₃ )
(C ₆ H ₅₎ - a method for producing a phenylene group-containing copolymer according to claim 1, wherein. 4. The method for producing a phenylene group-containing copolymer according to claim 1, wherein X in the general formula (I) is a fluorenylene group. 5. The method for producing a phenylene group-containing copolymer according to claim 1, wherein the other copolymerizable compound is at least one of compounds represented by the following general formulas (II) to (V). Embedded image [Wherein, R ^{11 and} R ¹² are the same or different, and have the general formula (I)
Is the same as R ⁹ to R ¹⁰ of, R ¹³ to R ²⁰ are the same or different, is the same as R ¹ to R ⁸ of general formula (I). ]