JPH04345615A - Reactive polyarylate - Google Patents

Abstract

PURPOSE:To obtain the title compound having excellent heat resistance and dimensional stability and comprising specified repeating units and terminated with a carboxyl acid or phenol residue having a thermosetting reactive group. CONSTITUTION:A reactive polyarylate which comprises repeating units of formula I[wherein X is-C(CH3)2-,-C(CF3)-, -O-,-CH2-,-CO-or a single bond; Y is H, halogen or Ch3; and n is 1-1000] and is terminated with at least one carboxylic acid residue, desirably a residue of formula II (wherein m is 1-3) or a phenolic residue, desirably a residue of formula III, each of which has a thermosetting reactive group.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to multifunctional polyarylates having reactive residues.

0002

[Prior Art] Polyarylates have been used in various fields due to their relatively excellent heat resistance, flame retardancy, spring recovery characteristics, dimensional stability, weather resistance, etc. In the fields of electronic materials and precision parts,
In addition to higher heat resistance and dimensional stability, excellent low thermal expansion coefficients are required.

0003

[Problems to be Solved by the Invention] The present invention meets these demands and has extremely high heat resistance and dimensional stability.
This was done to provide a reactive polyarylate that has a low coefficient of thermal expansion and can be used in a wide variety of fields.

0004

[Means for Solving the Problem] That is, the present invention solves the problem by the general formula (I)

[Formula 4] (wherein, X is -C(CH3)2-, -C(CF3)2-
, -O-, -CH2-, -SO2-, -CO- or a single bond, Y represents a hydrogen atom, a halogen atom or a methyl group, and n represents a number from 1 to 1000). and at least one carboxylic acid residue or phenol residue having a thermosetting reactive group at the end.
The invention relates to reactive polyarylates.

In the above general formula (I), X is -C(C
H3)2-, -C(CF3)2-, -O-, -CH2-
, -SO2-, -CO- or a single bond, Y represents a hydrogen atom, a halogen atom (preferably a fluorine atom) or a methyl group, and n is 1 to 1000, preferably 3 to
Shows the number 100. When n is larger than 1000, it becomes difficult to obtain the effect of the terminal group.

[0006] The reactive polyarylate according to the present invention is
It has at least one carboxylic acid residue or phenol residue having a thermosetting reactive group at the end. Particularly suitable residues of this type include those represented by the following general formulas (II) and (III):

[C5
]

[C6] (In the formula, m represents a number from 1 to 3)

[0007] Although the method for producing the reactive polyarylate according to the present invention is not particularly limited, a preferred production method is to produce the reactive polyarylate according to the general formula (IV):

Aromatic dicarboxylic acid dichloride represented by [Chemical formula 7], general formula (
V):

Bisphenols represented by the formula (wherein X and Y have the same meanings as above) and carboxylic acid chlorides or phenols having a thermosetting reactive group, for example,
V) or (VII):

[Chemical formula 9]

This is a method in which aromatic carboxylic acid chloride or phenol represented by the formula (wherein m has the same meaning as above) 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.

[0009] As the bisphenols represented by the general formula (V), the following compounds (1) to (10) are exemplified.

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

[Chemical formula 14]

[Chemical formula 15]

[Chemical formula 16]

[Chemical formula 17]

[Chemical formula 18]

[Chemical formula 19]

[C20]

In addition, as compounds represented by general formulas (VI) and (VII), the following compounds (11) to (14) are used.
) is exemplified:

[C21]

[C22]

[C23]

[C24]

[0011] A deoxidizing agent is used to neutralize hydrogen chloride produced in the condensation reaction, and examples include alkali metal or alkaline earth metal hydroxides and tertiary amines. Where legal, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred;
In the case of solution polymerization, tertiary amines such as triethylamine and pyridine are preferred.

[0012] 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 together, the proportions of these components to be used are not particularly limited; molar ratio 1
:9 to 9:1 is preferable.

Furthermore, general formulas (VI) and (VII)
A carboxylic acid chloride or phenol having a thermosetting reactive group represented by the formula (IV) is a structural unit derived from an aromatic dicarboxylic acid dichloride represented by the general formula (IV) and a bisphenol represented by the general formula (V). Although the intended purpose cannot be achieved unless the molar ratio is at least 0.001, it is usually preferable that the molar ratio is 0.01 or more.

[0014] Furthermore, the proportion can be changed depending on the purpose of use. In other words, if the proportion of carboxylic acid residues or phenols with terminal thermosetting reactive groups is small, many of the characteristics of thermoplastic polyarylates will remain, and conversely, if the above proportion is high, the characteristics due to thermosetting reactive groups will remain. remains.

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

The above reaction is preferably carried out by interfacial polymerization. In the interfacial polymerization method, organic solvents insoluble in water, such as halogen-containing solvents, hydrocarbon solvents, aromatic solvents, and ketone solvents (chlorine-containing solvents such as dichloromethane, chloroform, and 1,2 dichloroethane are particularly preferred) .) in the presence of the deoxidizing agent described above, 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. Bisphenols represented by formula (V) below and/or formula (VII)
The mixture is brought into contact with an aqueous solution of phenol having a thermosetting reactive group represented by , and a reaction is carried out on both sides of both solutions.

In the above reaction, the aromatic dicarboxylic acid dichloride represented by the formula (IV) and the bisphenol represented by the formula (V) are first reacted, and then the aromatic dicarboxylic acid dichloride represented by the formula (V) is reacted with the bisphenol represented by the formula (V).
Carboxylic acid chlorides and/or phenols represented by I) to (VII) may be added. In this interfacial polymerization method, a quaternary ammonium salt, a surfactant, or 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, and tetrabutylammonium bromide.

Various neutral surfactants can be used as the surfactant, including polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether,
Polyoxyethylene perfluoroalkyl ether and the like are preferred.

The above reaction may be carried out 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 active hydrogen-free solvent that dissolves the monomers mentioned above can be used, but aprotic amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexane, etc. Methylphosphorylamide or dimethyl sulfoxide are preferred.

The reactive polyarylate according to the invention comprises:
In addition to the above method, aromatic dicarboxylic acids and/or carboxylic acids having thermosetting reactive groups, or bisphenolic acids and/or phenols having thermosetting reactive groups, , the biphenols and/or the phenol having a thermosetting reactive group may be polymerized by a melt polymerization method in which they are reacted in a high-temperature molten state. However, in this melt polymerization method, terminal reactive residues may react, so the choice should be made depending on the purpose.

[0022]

[Examples] The present invention will be explained below with reference to Examples. Example 1 Bisphenol A 10.26g (0.045mol)
, 1.89 g (0.01 mol) of 4-hydroxymaleimide, 4.4 g (0.11 mol) of sodium hydroxide, and 0.2 g of tetrabutylammonium bromide in 500 g of water.
ml of the aqueous solution was put into a reaction container, and 10.15 g (0.025
mole), isophthaloyl chloride 10.15g (0.0
A solution of 25 mol) dissolved in 500 ml of chloroform was added with vigorous stirring, and after the addition was complete the reaction was continued for a further 2 hours with stirring. After washing the organic layer separated from the reaction mixture three times using 500 ml of ion-exchanged water,
Added to a large amount of methanol. The precipitated solid was collected by filtration,
After washing several times using methanol, the product was subjected to a drying treatment to obtain 21 g of polyarylate (A) having reactive residues at the ends. The physical properties of product (A) are shown in Table 1 below.

Example 2 Bisphenol AF 13.44g (0.04mol)
, 3.78 g of 4-hydroxyphenylmaleimide (0.
The reactive residues were prepared according to the procedure of Example 1, except that an aqueous solution of 4.4 g (0.11 mol) of sodium hydroxide and 0.2 g of tetrabutylammonium bromide dissolved in 500 ml of water was used. 22g of polyarylate (B) having terminals was obtained. The physical properties of product (B) are shown in Table 1 below.

[Table 1]

[0024]

Effects of the Invention The reactive polyarylate according to the present invention not only exhibits the characteristics of polyarylate, but also has particularly improved heat resistance, dimensional stability, thermal expansion coefficient, etc., so it can be used widely in a wide variety of fields. However, it is particularly useful in fields such as electronic materials and precision parts that require high heat resistance and dimensional stability. In this case, since the thermosetting rate can be freely designed, properties such as heat resistance and coefficient of thermal expansion can be adjusted as appropriate depending on the application.

Claims (3)

[Claims] Claim 1 General formula (I): [Formula 1] (wherein, X is -C(CH3)2-, -C(CF3)2-
, -O-, -CH2-, -SO2-, -CO- or a single bond, Y represents a hydrogen atom, a halogen atom or a methyl group, and n represents a number from 1 to 1000). and at least one carboxylic acid residue or phenol residue having a thermosetting reactive group at the end.
A unique reactive polyarylate. [Claim 2] A claim in which the carboxylic acid residue having a thermosetting reactive group is a residue represented by the general formula (II): [Claim 2] (wherein m represents a number from 1 to 3) 1. The reactive polyarylate according to 1. 3. The phenol residue having a thermosetting reactive group is a residue represented by the general formula (III): [Image Omitted] (wherein m has the same meaning as defined above) reactive polyarylates.