JPH0335022A - New polyimide resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title resin having excellent low-temperature moldability and solvent resistance by reacting [phenylenebis(methylethylidene)]bisaniline with [phenylenebis(methylethylidene)]bisphenylbistrimellitate dianhydride. CONSTITUTION:(A) 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline is reacted with 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenylbistrimellitate dianhydride or (B) 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline is reacted with 4,4'-[1,3- phenylenebis(1-methylethylidene)]bisphenylbistrimellitate dianhydride to give the aimed resin having a repeating unit shown by formula I (R is group shown by formula II or formula III).

Description

[Detailed Description of the Invention] [Industrial Application Field] [Prior Art] Polyimide resin has the best heat resistance among various resins, but since it is usually infusible and insoluble, it has poor moldability. is inferior. In order to improve moldability, attempts have been made to obtain polyimides that are solvent soluble and have a low softening point using various monomers.

For example, JP-A-60-258228, JP-A-63
-152630, JP 64-22963, JP 63-72755, and Special Publication 1982-50
Publication No. 0870 describes a diamine of the following formula (A), 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, and 3.3'4 as diamine components.
゜4'-benzophenonetetracarboxylic dianhydride.

Polyimides obtained from acid dianhydrides such as 2.2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propanihydride 1 are exemplified, and these polyimides are
- It is clear that it is soluble in organic solvents such as methylpyrrolidone and methylene chloride. Furthermore, these polyimides have a relatively low glass transition point and therefore a relatively low softening point.

Formula (A) [Problem to be Solved by the Invention] The polyimide disclosed in the above publication is solvent soluble, but this means that the solvent resistance of the molded article is poor. Generally, it is difficult to simultaneously achieve solvent resistance and a low softening point in polyimide, but the present invention provides a polyimide with excellent solvent resistance while maintaining a low softening point.

[Means to solve the problem]

The present invention relates to general formula (I) (however, During the ceremony.

R is Formula (a) CH.

CH.

or expression () ) It has a repeating unit represented by This invention relates to polyimide resin.

The polyimide resin preferably has a softening point of 130 to 1
It is at 80°C. If the softening point is too low, the physical properties of the 7-limide resin tend to deteriorate.

The polyimide resin of the present invention comprises 4.4'-(1°4-phenylenebis(1-methylethylidene))bisaniline (BAP) and 4.4'-(1,4-phenylenebis(1-methylethylidene)).
1-methylethylidene)] bisphenylbistrimellitate dianhydride (BAPBT), or 4.4'
-(1,3-phenylenebis(1-methyleneethylidene)] bisaniline (BAM) and 4.4' -(1,
It can be produced by reacting 3-phenylenebis(1-methylethylidene)]bisphenylbistrimeritate dianhydride (BAMBT). In this case, (1) a method of obtaining a polyamic acid from BAP or BAM, which is a diamine, and BAPBT or BAMBT, which is an acid dianhydride, and then ring-closing it by heating, or chemically ring-closing it using a ring-closing agent; (2) the above diamine or this method; There is a method of obtaining a polyimide in one step by heating a diisocyanate corresponding to the above and an acid derivative such as the above-mentioned acid dianhydride or its diester.

These methods will be described in more detail.

When diamines are used as reaction partners with acid dianhydrides, they are heated at 100°C or higher, preferably at 180°C, in an organic solvent, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, or triphenyl phosphite. A method of directly obtaining polyimide by heating to the above temperature and imidization (the catalyst is

The acid dianhydride and the diamine are mixed in an organic solvent at 100°C.
A varnish of polyamic acid, which is a precursor of polyimide, is produced by reacting with less than
Acid anhydrides such as benzoic anhydride, ring-closing agents such as carbodiimides such as dicyclohexylcarbodiimide, and optionally pyridine, isoquinoline, and trimethylamine.

A method of chemically closing the ring (imidization) by adding a ring-closing catalyst such as aminopyridine or imidazole (the ring-closing agent and the ring-closing catalyst are each used in an amount of 1 to 8 mol per 1 mol of the acid anhydride). preferred) etc.

As the organic solvent, N-methyl-pyrrolidone (NM
P), N, N'-dimethylacetamide, N, N-
Dimethylformamide (DMF), dimethyl sulfoxide, sulfolane, hexamethyl phosphoric triamide, 1
, aprotic polar solvents such as 3-dimethyl-2-imidazolitone, phenol, cresol, xylenol, p
- Phenolic solvents such as chlorophenol and the like can be mentioned.

These solvents include benzene, toluene, and xylene.

Methyl ethyl ketone, acetone, tetrahydrofuran,
Dioxane, monoglyme, diglyme.

A mixture of solvents such as methyl cellosolve, cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride, chloroform, trichlene, and tetrachloroethane can be used.

When producing the above-mentioned polyimide and its predecessor, polyamic acid, solid phase reaction, melt reaction at 300° C. or lower, etc. can be used depending on the case.

Further, when a diisocyanate is used as a reaction partner of the acid dianhydride, it can be carried out according to the method for directly obtaining the polyimide described above. However, it is sufficient that the reaction temperature is at least room temperature, especially at least 60°C.

In the present invention, the acid dianhydride and its reaction partner are preferably used in approximately equimolar amounts, but an excess of either one of them is allowed up to 10 mol%, particularly preferably up to 5 mol%.

The polyimide resin according to the present invention also includes N, N'-(4
,4'-(1,4-phenylenebis(1-methylethylidene)]bisaniline]bistrimeritimide (hereinafter referred to as "imidodicarboxylic acid I") and 4.4'-(
1,4-phenylenebis(l-methylethylidene))bisphenol or N,N'-(4,4'
-(1,3-phenylenebis(1-methylethylidene)]bisaniline]bistrimeritimide (hereinafter referred to as “
It can also be produced by reacting imidodicarboxylic acid 1) with 4,4'-(1°3-)22binpis(l-methylethylidene)]bisphenol. In this case, ■ heating polycondensation reaction of the imidodicarboxylic acid ■ or ■ and the above bisphenol or direct polycondensation reaction using a condensing agent such as phosphite or tosyl chloride, ■ the above imidodicarboxylic acid! Alternatively, low-temperature polymerization reaction between diacid chloridone and the above-mentioned bisphenol (2) can be used.

Methods ① and ③ can be carried out in the same manner as the usual polyester polycondensation method. For direct polycondensation, see Mitsuru Ueda, Kobunshi 35 (2) 128 (1986), Higashifukuji 9, Japan Adhesive Association Journal. , Dan (12) 504 (1988),
Takashi Takazawa et al., Polymerpreprints,
Japan, 3 Sat. (6) 1345 (1985).

Further, one resin according to the present invention includes trimellitic anhydride, BA
It can be obtained by a method in which polyamic acid is obtained in the same container using P or BAM and the above-mentioned bisphenol using a condensing agent such as tosyl chloride, and then thermal ring closure or chemical ring closure is performed. For such methods, see Hozumi
Tanaka et al.

Proceedings/Abstracts of
Th1rd International Conference
ence on Polyimide p, 64 (
1988).

The polyimide according to the present invention can be used as molded products, adhesives, and the like.

The polyimide according to the present invention can be appropriately produced from its precursor and used.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples.

The present invention is not limited to these ranges.

Example 1 3.44 g of RAM was placed in a four-loaf flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a downward cooling tube.

BAMBT6.94g, N-methylpyrrolidone 42
g, add 0.3 g of triphenyl phosphite, 20
When heating and stirring was continued at 0°C, resin began to precipitate.

After continuing heating and stirring for another 1 hour, it was cooled to room temperature.
A resin was obtained by filtration. After repeated washing with methanol, the resin powder was dried to obtain resin powder.

Example 2 3.44 g of RAM was placed in a four-loaf flask equipped with a stirrer, a thermometer, a calcium chloride tube, and a nitrogen gas inlet tube.

After 41.5 g of N,N-dimethylformamide was added and dissolved, 6.94 g of BAPBT was added little by little at a temperature below 5°C. After reacting at 10° C. or lower for 3 hours, 2.6 g of acetic anhydride and 2.0 g of pyridine were added. When stirring was continued at room temperature, resin precipitated, but stirring was continued for an additional hour. The resin obtained by filtration was washed repeatedly with methanol and then dried to obtain resin powder.

Comparative Example 1 A homogeneous solution of polyimide was obtained by reacting in the same manner as in Example 1 except that 6.94 g of BAPBT was used instead of BAMBT. After pouring into water and reprecipitating, pulverization and washing with methanol were repeated, followed by drying to obtain resin powder.

Comparative Example 2 2,2-bis(p-trimellitoxyphenyl)propanoic dianhydride 5.76 instead of BAM B'T
A homogeneous solution of polyimide was obtained by carrying out the reaction in the same manner as in Example (2) except that g was used. After pouring into water and reprecipitating, pulverization and washing with methanol were repeated, followed by drying to obtain resin powder.

Example 1. Example 2. The solubility and softening point of the resin powders obtained in Comparative Example 1 and Comparative Example 2 were measured.

The solubility was determined visually after mixing 5% by weight of resin powder and 95% by weight of the solvent shown in the topsoil, and then leaving the mixture at room temperature for one day.

The evaluation was as follows: 0: dissolution, Δ: swelling, ×: insoluble.

The softening point was measured using a Shimadzu Koka type flow tester with a diameter of 1
m, using a nozzle with a length of 10 mm, and a load of 50 kg/
J, measured at a temperature increase rate of 5° C./win.

The results are shown in Table 1.

The physical properties of the resins obtained in Example 1 and Example 2 are as follows.

Resin obtained in Example 1: (1) Thermal decomposition temperature 418℃ (2) IR spectrum (KBr method) As shown in Figure 1.

Resin obtained in Example 2: (1) Thermal decomposition temperature 431℃ (2) IR spectrum (KBr method) As shown in Figure 2.

From the above, the resin obtained in Example (1) is a polyimide resin having a repeating unit in which R is represented by formula (a) in general formula (1).

The resin obtained in Example 2 was a polyimide resin having a repeating unit in which R is represented by the formula (b) in the general formula ('').

〔Effect of the invention〕

The polyimide resin according to claim 1 or obtained according to claim 2 has excellent solvent resistance while maintaining a low softening point.

[Brief explanation of drawings]

FIG. 1 shows the IR spectrum of the resin obtained in Example 1, and FIG. 2 shows the IR spectrum of the resin obtained in Example 2.

Claims (1)

[Claims] 1. The present invention is based on the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R is the formula (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A polyimide resin having a repeating unit represented by (a) or formula (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(b)). 2,4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline and 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenylbistrimelitate dianhydride thing or 4,4'-[1,3-
A polyimide resin characterized by reacting phenylenebis(1-methylethylidene)]bisaniline and 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenylbistrimelitate dianhydride. Manufacturing method.