JP3061671B2 - Fluorinated maleimide derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to surface modifiers such as intermediates for pharmaceuticals and agricultural chemicals, resins and the like, especially in the field of electronics, which have a low relative dielectric constant, moldability, oil resistance and water resistance (environmental resistance characteristics). ) And a fluorine-containing maleimide derivative useful as a resin raw material having excellent mechanical strength (mechanical properties), and a resin thereof.

[0002]

2. Description of the Related Art Maleimide resins have excellent heat resistance and electrical properties, and have been widely used as various industrial materials. However, maleimide resins are particularly suitable for miniaturization and high precision of products in the field of electronics. At the same time, development of a multifunctional maleimide-based resin has been advanced. For example, laminates and high-frequency substrates in the electronics field have electrical characteristics,
In addition to thermal properties, excellent moisture resistance, water and oil repellency and mechanical properties are required. As a method for imparting moisture resistance, a method of introducing a fluorine group can be considered, but generally, the introduction of the fluorine group tends to lower the heat resistance of the maleimide resin. As a method of preventing a decrease in the heat resistance of a maleimide resin by introducing a fluorine group, a technique of introducing a short-chain fluorine-containing group having a large amount of a trifluoromethyl group into an aromatic maleimide is known (Japanese Unexamined Patent Publication No.
-1028260). However, in the compound obtained by this method, there is a problem that the rigidity of the aromatic maleimide becomes evident and lacks in flexibility, resulting in inferior workability and impact resistance.

[0003]

SUMMARY OF THE INVENTION The present invention provides a fluorinated maleimide derivative which has excellent heat resistance and electrical properties as well as excellent processability and impact resistance.

[0004]

That is, the present invention provides a compound represented by the following general formula (1):

[0005]

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(Wherein, Rf represents a perfluoroalkenyl group or a perfluoroalkyl group. Y represents-
O-, or, -CH ₂ - shows a. Ar represents a monocyclic or polycyclic aromatic group. n shows the integer of 1-4. )).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), Rf represents a perfluoroalkenyl group or a perfluoroalkyl group. In particular, carbon numbers of 6 to 12 are preferable. In general, the following are exemplified.

[0008]

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Y represents —O— or —CH ₂ —. Ar is a monocyclic ring which may have a substituent such as a lower alkyl group, a lower alkoxy group, or a halogen group, or
Shows a polycyclic aromatic group.

The substitution number n of the maleimide residue is an integer of 1 to 4, preferably an integer of 1 to 3. The bonding position of the maleimide residue to Ar, for example, the bonding position to the phenyl group is preferably p-position to CH ₂ O—, but o-
Position or m-position.

The method for producing the fluorine-containing maleimide derivative represented by the general formula (1) is not particularly limited, but a preferred method is the following general formula (2):

[0012]

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(Wherein, Y has the same meaning as Y in the general formula (1), and Rf also has the same meaning. N
Is also equivalent. X represents a halogen atom. A) a halogenated methyl compound containing a perfluoroalkyl group represented by the general formula (3):

[0014]

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This is a method of reacting hydroxyphenylmaleimide represented by the formula (1) in an organic solvent in the presence of a catalyst.

The reaction between the compounds represented by the general formulas (2) and (3) is carried out in the range of -20 to 100 ° C. in the presence of a catalyst. Catalysts include hydroxides of alkali metals,
Carbonates and the like. In particular, K ₂ CO ₃ is preferred.
It is preferable to use 1 equivalent or more of the compound (formula 3). In particular, 1-2 equivalents are preferred. This reaction can be carried out without a solvent, but a solvent is generally used, and examples thereof include tetrahydrofuran, dioxane, ether, and acetone. Particularly, tetrahydrofuran and dioxane are preferable. The fluorine-containing aromatic maleimide derivative represented by the general formula (1) is represented by the following general formula (4)
Can be produced by a method of reacting a compound represented by the formula (1) with a fluorinating agent, for example, a hexafluoropropene oligomer, or a method of maleimidating the compound represented by the general formula (5). It is not common because the preparation of the starting material is not easy and there are many by-products.

[0017]

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Wherein Ar and n are as defined above, and Z is
Is a —OH group or a —CH ₂ group. X is a halogen atom. )

[0019]

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(Wherein, Y, Ar and n are as defined above)

The compounds of the present invention can be polymerized using one kind or two or more kinds. Furthermore, it can be polymerized using the compound of the present invention and another polymerizable substance. Examples of the substance capable of reacting with the compound of the present invention include a maleimide compound, a dicyanamide compound, a cyanato compound, an isocyanato compound, an epoxy compound, a vinyl compound, and the like.

[0022]

The present invention will be described below with reference to a method for producing the compound of the present invention, but the present invention is not limited thereto. Example 1- (3 ′, 3 ′, 4 ′, 4 ′, 5 ′, 5 ′, 5′-heptafluoro-
Synthesis of 2 ', 2'-bis (trifluoromethyl))-3,5-di (4 "-maleylimino phenoxymethyl) benzene 3,5-bis (bromomethyl) -alpha- (3', 3 ', 4 ′, 4 ′, 5 ′, 5 ′,-Heptafluoro-2 ′, 2′-bis (trifluoromethyl)) toluene 20.2 g was placed in a reaction flask equipped with a thermometer, a stirrer, and a condenser. In addition to this, 4-male Louis Mifenol 1
4.8 g, 15.2 g of potassium carbonate and 100 ml of tetrahydrofuran were added, and the mixture was heated and stirred at 60 to 65 ° C. for 2 hours to carry out a reaction. After cooling, the reaction solution was filtered and the solvent was removed under reduced pressure. Then, warm chloroform 200m
Extract with 1 and filter the chloroform solution. Next, the chloroform solution was concentrated to 30 to 40 ml, which was separated and purified using a silica gel column and chloroform as a solvent. 6.3 g of the desired product (formula 6) was obtained. Table 1 shows the physical property values of the target product.

[0023]

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[0024]

[Table 1]

[0025]

The fluorine-containing maleimide derivative according to the present invention has excellent mechanical properties, dimensional properties and environmental resistance as well as excellent low dielectric constant, and thus is useful as a printed circuit board or a high-frequency board in the electronics field. .

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 207/00-207/50 C08F 22/40 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. General formula (1): (Wherein, Rf is a perfluoroalkenyl group, or
Shows a perfluoroalkyl group. Y is, -O-, or, -CH ₂ - shows a. Ar represents a monocyclic or polycyclic aromatic group. n shows the integer of 1-4. A) a fluorine-containing maleimide derivative represented by the formula: 2. A resin obtained by polymerizing one or more compounds represented by the general formula (1) according to claim 1.