JPH03277633A - polyetherimide - Google Patents

Abstract

PURPOSE:To obtain a polyetherimide which has excellent heat resistance and good moldability and can be desirably used as a molding, a film or a coating material for electrical and electronic components, etc., having repeating units of a specified formula. CONSTITUTION:A polyetherimide having repeating units of formula I (wherein X and Y are bivalent organic groups). It is desirable that, in formula I, X is a bivalent siloxane-containing group of formula II (wherein R1 to R4 are each a monovalent hydrocarbon group; R5 is a bivalent hydrocarbon group; and n is 1-50). The above polyetherimide can be obtained, for example, by reacting a bis(halogenonaphthalimide) compound of formula III (wherein X is as defined above; and Hal is halogen) with a dihydric phenol. This polyetherimide has excellent heat resistance and good moldability and can be desirably used as a molding, a film or a coating material for electrical and electronic components, automobiles, aircraft components, etc.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a novel polyetherimide that has excellent moldability and can be melt-molded. The present invention relates to polyetherimide which is useful as a molded product for parts, particularly electric/electronic parts, automobile/aircraft parts, etc., and furthermore, as a material for adhesive films.

[Conventional technology]

Polyimide resins have been widely used in various molded products, films, varnishes, etc. due to their high heat resistance, electrical properties, and excellent mechanical properties. A specific example of such a product is an aromatic polyetherimide using an aryloxy dianhydride (JP-A-1-2
52.635).

However, despite their good heat resistance, many polyimide resins have insufficient thermoplasticity, poor flexibility, and are insoluble in various solvents, making them difficult to handle. .

Therefore, as a solution to these problems, polyetherimide has been proposed as a polyimide resin that has good moldability and is soluble in various solvents [Polymer
Preprints, 18.831 (1977)]
Another problem with this polyetherimide is that its heat resistance is inferior to that of conventional polyimide resins.

[Problem to be solved by the invention]

Therefore, the present inventors conducted extensive research to solve the above problems, and found that by using naphthalic anhydride as an acid anhydride compound, which is one of the monomer components, and introducing an ether bond, It was discovered that a polyetherimide resin having high heat resistance, good flexibility, and solvent solubility can be obtained, and the present invention was completed.

Therefore, the object of the present invention is to
The object of the present invention is to provide a novel well-balanced polyimide resin having good flexibility and solvent solubility.

[Means to solve the problem]

That is, the present invention relates to the following general formula (1) (wherein X
, Y each represents a divalent organic group).

In the above general formula (1), X is a divalent organic group,
It is a divalent organic residue derived from a diamine compound or a diisocyanate compound. Such divalent organic residues may be aromatic organic groups or aliphatic organic groups, or combinations thereof.

In the case of aromatic organic residues, the corresponding diamine compounds include, for example, p-phenyl diamine, 〇-phnyl diamine, m-phnyl diamine, ll5-naphthalenediamine, p-amino diamine, etc. Benzylamine, m-aminobenzylamine, 3,3°-dimethylbenzidine, 3,3
'-Dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4.4'-diaminodiphenyl ether, 3,3-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4.4' -diaminodiphenylsulfide, 3,3°-diaminodiphenylsulfone, 3.
4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfoxide, 3,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 3,
3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4-diaminobenzophenone, 3,
3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4'4'-diaminodiphenylmethane, 3,3'-diaminodiphenylpropane, 3,4-
Diaminodiphenylpropane, 4,4'-diaminodiphenylpropane, bis[4-(4-aminophenoxy)
Phenyl 1methane, 1,1-bis[4-(3-aminophenoxy)phenyl 1methane, 1,1-bis[4-(4
-aminophenoxy)phenyl 1-ethane, ■, 2-bis[4-(3-aminophenoxy)phenyl 1-ethane, 1
,2-bisE4-C4-aminophenoxy)phenyl 1
Ethane, 2,2-bis[4-(3-aminophenoxy)
Examples include phenyl-1propane, 2,2-bis[4(4-aminophenoxy)phenyl-1propane, m-xylylenediamine, p-xylylenediamine, 2°4-diaminotoluene, 2,6-diaminotoluene, and the like. In addition, examples of the diisocyanate compound include diisocyanates corresponding to the above-mentioned diamine compounds. When these aromatic organic residues are used, high heat resistance can be imparted to the polyetherimide of the present invention.

Further, in the case of an aliphatic organic residue, corresponding diamine compounds include hexamethylene diamine, dodecamethylene diamine, etc., and diisocyanate compounds include diisocyanate compounds corresponding to the above-mentioned diamine compounds. When these aliphatic organic residues are used, the heat resistance is slightly lower than when aromatic organic residues are used, but the solubility in solvents can be further improved.

In addition, in the above general formula (1), as a diamine compound corresponding to the divalent organic group It is preferable to use a diamine compound containing a siloxane represented by the group R5 represents a divalent hydrocarbon group and n represents an integer of 1 to 50. By using such a diamine compound containing siloxane, good flexibility can be imparted to the polyetherimide of the present invention. In addition, R1, R2, R2 in this general formula (5)
, R4 is, for example, a methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 1so-
Examples include butyl group, tert-butyl group, etc.
Further, as R5, for example, a methylene group, an ethylene group,
Examples include propylene group, butylene group, and phenylene group. Specific examples of diamine compounds containing siloxane represented by the above general formula (5) include 1,
Examples include 3-bis(3-aminopropyl)tetramethyldisiloxane and bis(3-aminopropyl)polysiloxane.

In the present invention, the divalent organic group represented by X above may be appropriately selected depending on the purpose, and two or more thereof may be used in combination.

Further, in the polyetherimide represented by the general formula (1), Y is not particularly limited as long as it is a divalent organic group, but for example, a phenylene group, a biphenylene group,
Aromatic groups such as biphenyl ether group, biphenylpropane group, biphenyl ketone group, aliphatic groups such as methylene group, ethylene group, propylene group, isopropylene group, butylene group, amide bond, ether bond, ester in the structure Examples thereof include organic groups having a bond, a ketone bond, and the like.

The polyetherimide represented by the general formula (1) can be produced by conventionally known methods, such as (a) a method using a nucleophilic substitution reaction between a bis(halogenonaphthalimide) compound and a dihydric phenol; (Polymer.

25, 1827-1836. (1984) ), (b
) bis to tronaphthalimide) and a dihydric phenol alkali metal salt (Journ)
al of Polymer 5science, 18
．． 3069-3080 (1980)), (C) Method of reacting bis(naphthalic anhydride) ether tocyamine (Polymer Prepins
, 18° 831-834 (1977)), but the invention is not particularly limited thereto.

A more detailed explanation of each of these methods (a) to (C) is as follows.

The above method (a) consists of 2 equivalents of naphthalic anhydride substituted with a halogen atom at the 4- or 3-position and 1 equivalent of an organic diamine compound.
The bis(halogenonaphthalimide) compound is synthesized by reacting the equivalent amount of the bis(halogenonaphthalimide) in a polar solvent, followed by dehydration and ring closure.
halogenonaphthalimide) and the dihydric phenol compound in dimethylacetamide in the presence of anhydrous potassium carbonate.
Temperature 1 in the presence of an azeotropic solvent in a polar solvent such as sulfolane.
Polyetherimide is produced by reacting at a temperature of 00 to 280°C, preferably 160 to 240°C.

In the above method (b), 2 equivalents of naphthalic anhydride substituted with a nitro group at the 4- or 3-position are reacted with 1 equivalent of an organic diamine compound in a polar solvent, followed by dehydration and ring closure to form bis(tronaphthalimide). Polyetherimide is produced by synthesizing a bis(tronaphthalimide) compound and reacting the bis(tronaphthalimide) compound with an alkali metal salt of a dihydric phenol in a polar solvent.

The above method (C) involves synthesizing a bistephthalic anhydride ether represented by the following general formula (6) (wherein Z represents a divalent organic group), and reacting this with an organic diamine compound. This process produces polyetherimide. Note that this method can be carried out either in a solvent or in a molten state.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on Examples.

Example 1 1.27 g of the following bis(bromonaphthalimide) compound (0
,002 mol) and 4,4'-dihydroxybiphenyl ether 0°4
0 g (0,002 mol) and anhydrous potassium carbonate were dissolved in a mixed solvent of 30-dimethylacetamide and 101 nl of toluene, and this was charged into a reaction vessel equipped with a reflux condenser and Dean-Stark vessel. , and reacted at 140° C. for 41 hours under a nitrogen atmosphere.

After the reaction was completed, toluene was distilled off under reduced pressure, and the reaction mixture was allowed to reach room temperature, and then poured into water to obtain a brown polymer (yield: 86%).

This material was soluble in toluene and had good flexibility when formed into a film.

In addition, the reduced viscosity and thermal decomposition temperature were measured. Results first
Shown in the table.

Example 2 1.10 g of the following bis(chloronaphthalimide) compound (
0,002 mol) and bisphenol A 0. 456 g (0,002
mole) and anhydrous potassium carbonate were dissolved in 30-mol sulfolane, 15-xylene was added, and the mixture was reacted at 210° C. for 18 hours in the same manner as in Example 1.

After the reaction was completed, cooled to room temperature, water:methanol-1
:L mixed solvent to obtain a polymer (yield: 81%). The reduced viscosity and thermal decomposition temperature of this polymer were measured. The results are shown in Table 1. In addition, the infrared absorption spectrum of this polymer was measured. The results are shown in Figure 1.

Example 3 The following bis(chloronaphthalimide) form 1 was used in place of the bis(chloronaphthalimide) form in Example 2 above.
A polymer (yield: 84%) was obtained in the same manner as in Example 2 above, except that 35 g (0,002 mol) was used.

Table 1 shows the reduced viscosity and thermal decomposition temperature of this polymer.

Example 4 1.70 g of tronaphthalimide (0
,002 mol) and the following sodium phenolide of bisphenol A 0
．． 5 4 g (0,002 mol) CH.

The reaction was carried out at 80° C. for 40 hours in the same manner as in Example 1 above, except that the mixture was dissolved in 201 nl of dimethylformamide.

After the reaction was completed, the reaction mixture was poured into water to obtain a polymer (yield: 99%). The glass transition temperature of the obtained polymer was 3
The temperature was 50°C. In addition, the reduced viscosity and thermal decomposition temperature of this polymer were measured. The results are shown in Table 1.

Table [Effects of the Invention] The polyetherimide of the present invention not only has excellent heat resistance but also good moldability, and is used in molded bodies and films in electrical and electronic parts, automobile and aircraft parts, etc. Alternatively, it can be suitably used as a coating material.

[Brief explanation of drawings]

FIG. 1 is a graph showing the infrared absorption spectrum of the polymer obtained in Example 2.

Claims (4)

[Claims] (1) It is characterized by having a repeating unit represented by the following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, X and Y each represent a divalent organic group) Polyetherimide. (2) In general formula (1), X is the following general formula (2)▲
There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R_1, R_2, R_3, R_4 represent a monovalent hydrocarbon group, R_5 represents a divalent hydrocarbon group,
2. The polyetherimide according to claim 1, wherein n is a divalent group containing siloxane (n is an integer of 1 to 50). (3) The following general formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, X represents a divalent organic group, and Hal. represents a halogen group.) 1. A method for producing polyetherimide, which comprises reacting a phthalimide with dihydric phenol. (4) The following general formula (4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, X represents a divalent organic group) Bis(nitronaphthalimide) body and divalent phenol alkali A method for producing polyetherimide, characterized by reacting it with a metal salt.