JP3080684B2 - Reactive polyarylate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multifunctional polyarylate having a reactive residue.

[0002]

2. Description of the Related Art Hitherto, polyarylate has been used in various fields because of its relatively excellent heat resistance, flame retardancy, spring recovery characteristics, dimensional stability and weather resistance. In the fields of electronic materials and precision parts,
In addition to high heat resistance and dimensional stability, an excellent low thermal expansion coefficient and the like are required.

[0003]

SUMMARY OF THE INVENTION The present invention meets these demands and has extremely high heat resistance and dimensional stability.
The purpose of the present invention is to provide a reactive polyarylate having a small coefficient of thermal expansion and which can be widely used in various fields.

[0004]

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

Embedded image (Wherein, X is _{-C (CH 3) 2 -,} - C (CF 3) 2 -, - O
_{-, - CH 2 -, -} SO 2 -, - CO- or a single bond, Y represents a hydrogen atom, a halogen atom or a methyl group, the repeating unit n is expressed by the number of 1-1000) Having at the terminal a general formula (II):

Embedded image (Wherein m represents a number of 1 to 3) or a carboxylic acid residue represented by the following general formula (III):

Embedded image (Wherein m has the same meaning as described above), and relates to a reactive polyarylate having at least one phenol residue.

In the above general formula (I), X is -C (C
_{H 3) 2 -, - C} (CF 3) 2 -, - O -, - CH 2 -, - SO
₂ -, - CO- or a single bond, Y (preferably, fluorine atom) is hydrogen atom, a halogen atom indicates or a methyl group, n represents 1 to 1000, preferably indicates the number of 3-100. When n is larger than 1000, it is difficult to obtain the effect of the terminal group.

The reactive polyarylate according to the present invention has at least one carboxylic acid residue or phenol residue represented by the general formula (II) or (III) having a thermosetting reactive group at the terminal. Have.

Embedded image (Wherein, m is as defined above)

Embedded image (Wherein, m is as defined above)

The method for producing the reactive polyarylate according to the present invention is not particularly limited, but a preferred production method is represented by the general formula
(IV):

Embedded image Aromatic dicarboxylic acid dichloride represented by the general formula
(V):

Embedded image (Wherein X and Y are as defined above) and a carboxylic acid chloride or phenol having a thermosetting reactive group, for example, a compound of the general formula (V)
Or (VII):

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Embedded image (Wherein m is as defined above), in which aromatic carboxylic acid chloride or phenol is reacted in the presence of a deoxidizing agent.

Examples of the compound represented by the general formula (IV) include terephthalic acid chloride and isophthalic acid chloride.

The following compounds (1) to (10) are exemplified as the bisphenols represented by the general formula (V).

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The compounds represented by the general formulas (VI) and (VII) include the following compounds (11) to (14):

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The deoxidizing agent is used to neutralize hydrogen chloride generated in the condensation reaction, and examples thereof include alkali metal or alkaline earth metal hydroxides and tertiary amines. In the case of legality, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide are preferred,
In the case of solution polymerization, tertiary amines such as triethylamine and pyridine are preferred.

When the compound represented by the general formula (IV) is used in combination, for example, when terephthalic acid dichloride and isophthalic acid dichloride are used in combination, the use ratio of these components is not particularly limited, but the former and the latter are used. Molar ratio of 1:
It is preferably 9 to 9: 1.

Further, the carboxylic acid chloride or phenol having a thermosetting reactive group represented by the general formulas (VI) and (VII) is obtained by mixing the aromatic dicarboxylic acid dichloride represented by the general formula (IV) with the general formula (V) The desired purpose cannot be achieved unless the molar ratio is at least 0.001 with respect to the structural unit derived from the bisphenol represented by the formula (1), but it is usually preferred that the content be 0.01 or more.

Further, the ratio can be changed according to the purpose of use. In other words, when the proportion of the carboxylic acid residue or phenol having a terminal thermosetting reactive group is small, the characteristics of the thermoplastic polyarylate remain much. Many remain.

The proportions of the acid chlorides represented by the formulas (IV) to (VII) and phenol are not particularly limited, but are preferably equal.

The above reaction is preferably carried out by an interfacial polymerization method. In the interfacial polymerization method, an organic solvent insoluble in water, for example, a halogen-containing solvent, a hydrocarbon-based solvent, an aromatic-based solvent, a ketone-based solvent (particularly, a chlorine-containing solvent such as dichloromethane, chloroform, and 1,2-dichloroethane is preferable. ) In which an aromatic dicarboxylic acid dichloride represented by the above formula (IV) and / or a carboxylic acid chloride having a thermosetting reactive group represented by the formula (VI) is dissolved. In the following, an aqueous solution of a bisphenol represented by the formula (V) and / or a phenol having a thermosetting reactive group represented by the formula (VII) is brought into contact, and the reaction is carried out on both surfaces of the two solutions.

In the above reaction, an aromatic dicarboxylic acid dichloride represented by the formula (IV) and a bisphenol represented by the formula (V) are first reacted, and then the compounds represented by the formulas (VI) to (VI):
A carboxylic acid chloride represented by (VII) and / or phenol may be added. In this interfacial polymerization method, a quaternary ammonium salt, a surfactant and the like can be present in the reaction system to allow the reaction to proceed stably.

Examples of the quaternary ammonium salt include tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide and the like.

As the surfactant, various neutral surfactants can be used, and polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene perfluoroalkyl ether and the like are preferable.

The above reaction may be performed by a solution polymerization method in an organic solvent in addition to the interfacial polymerization method. The organic solvent is not particularly limited, and any solvent can be used as long as it is an active hydrogen-free solvent that dissolves the above-mentioned monomers.Aprotic amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexa Methyl phosphorylamide or dimethyl sulfoxide and the like are preferred.

The reactive polyarylate according to the present invention comprises
In addition to the above method, aromatic dicarboxylic acid and / or carboxylic acid having a thermosetting reactive group, or dicarboxylic acid, diester of carboxylic acid can be converted to bisphenol acid and / or phenol having a thermosetting reactive group or Alternatively, the polymer may be polymerized by a melt polymerization method in which the biepphenol and / or an ester of a phenol having a thermosetting reactive group are reacted in a high-temperature molten state. However, in this melt polymerization method, a terminal reactive residue may react, so that it should be selected according to the purpose.

[0022]

The present invention will be described below with reference to examples.Example 1  10.26 g (0.045 mol) of bisphenol A,
1.89 g of 4-hydroxymaleimide (0.01 mol
), 4.4 g (0.11 mol) of sodium hydroxide and
0.2 g of tetrabutylammonium bromide and 50
0 ml of the aqueous solution was placed in the reaction vessel,
To the solution was added 10.15 g of terephthaloyl chloride (0.02 g).
5 mol), 10.15 g of isophthaloyl chloride (0.
025 mol) in 500 ml of chloroform.
Add the solution with vigorous stirring.After the addition is complete, stir the reaction.
The stirring was continued for another 2 hours. Yes from the reaction mixture
The machine layer was washed three times using 500 ml of ion-exchanged water.
Later, it was added to a large amount of methanol. The precipitated solid is collected by filtration.
After washing several times with methanol, dry
By doing so, a polyary having a reactive residue at the end
21 g of rate (A) were obtained. The physical properties of the product (A) are as follows
Is shown in Table 1.

[0023]Example 2  13.44 g (0.04 mol) of bisphenol AF,
3.78 g of 4-hydroxyphenylmaleimide (0.0
2 mol), 4.4 g (0.11 mol) of sodium hydroxide
And 0.2 g of tetrabutylammonium bromide in water
Example 1 except that an aqueous solution dissolved in 500 ml was used.
Having a reactive residue at the end according to the procedure of
22 g of rate (B) were obtained. The physical properties of the product (B) are as follows
Is shown in Table 1.

[Table 1]

[0024]

Industrial Applicability The reactive polyarylate according to the present invention exhibits characteristics of a polyarylate and has particularly improved heat resistance, dimensional stability, thermal expansion coefficient, etc., so that it can be widely used in various fields. But in particular,
It is useful in fields such as electronic materials and precision parts that require high heat resistance and dimensional stability. In this case, since the thermal curing rate can be freely designed, characteristics such as heat resistance and thermal expansion coefficient can be appropriately adjusted according to the application.

Continuation of the front page (56) References JP-A-61-130335 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 CA (STN) REGISTRY ( STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (I): (Wherein, X is _{-C (CH 3) 2 -,} - C (CF 3) 2 -, - O
_{-, - CH 2 -, -} SO 2 -, - CO- or a single bond, Y represents a hydrogen atom, a halogen atom or a methyl group, the repeating unit n is expressed by the number of 1-1000) Having at the terminal a general formula (II): (Wherein m is a number from 1 to 3) or a carboxylic acid residue represented by the general formula (III): (Wherein m is as defined above). A reactive polyarylate having at least one phenol residue.