JP2852921B2 - Polyamide imide resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyamide-imide resin.

[0002]

2. Description of the Related Art Polyimide resins and polyamide resins have been used in many fields, for example, as films, wire coatings, adhesives, paints, and laminates, utilizing their excellent properties such as heat resistance. On the other hand, the development of polyamideimide resins, polyester resins, polyetherimide resins, etc. has been widely promoted in order to expand their versatility while utilizing these characteristics.

[0003]

However, polyimide resins, polyamide resins, polyamideimide resins, and the like, which are currently widely used, have good heat resistance, but have drawbacks in moldability and the like. Therefore, in order to balance these advantages and disadvantages, the compounding of a polyimide resin, a polyamide resin, a polyamideimide resin, or the like with another reactive resin or the like has been studied, but it is still insufficient. The main obstacle is that these polyimide resins, polyamide resins, polyamideimide resins have insufficient solvent solubility, and these polyimide resins, polyamide resins, polyamideimide resins and other reactive resins have a desired composition. The problem was that they were not mixed uniformly and that the expected properties were not exhibited. Therefore, an object of the present invention is to provide a novel polyamideimide resin that can be dissolved in an organic solvent, has a reactive site for another reactive resin, and can be uniformly mixed with another reactive resin. .

[0004]

According to the present invention, there is provided a compound of the general formula

Embedded image (Where Ar is a divalent aromatic group, R ² is a group

Embedded image And R is a group

Embedded image Or C ₁ -C ₁₂ represents an alkylene group, where R ¹ represents a hydrogen atom, a methyl group, a halogen atom, a nitrile group, a nitro group or a hydroxyl group, R ^3, R ⁴ and R ⁵ is different from R ² 2 A divalent aliphatic group, a divalent aromatic group, a divalent alicyclic group,
l, m, n, x and y are l ≧ 2 (m + n), and l ≦ 5 satisfying the formula of x ≧ 2y, and represent a positive integer of x ≦ 6). is there.
Examples of the divalent aromatic group represented by the substituents Ar, R ³ , R ⁴ and R ⁵ include a phenylene group, Ph-O-Ph, and Ph-SO _2-.
Ph (Ph is a phenylene group) and the like are preferable.

The polyamide-imide resin of the formula I has the general formula

Embedded image (Wherein R has the above-mentioned meaning) and a diamine compound different therefrom and a polycondensation reaction with trimellitic acid, trimellitic anhydride or a reactive derivative thereof.

The compounds of formula II include, for example, the following compounds: N, N'-bis (2-, 3- or 4-aminophenyl) -5-hydroxyisophthalamide,
N, N'-bis (2-, 3- or 4-aminophenyl)
-5-hydroxyterephthalamide, N, N'-bis (2-, 3- or 4-aminophenyl) -2-hydroxyphthalamide, N, N'-bis (3-amino-2-methylphenyl) -5 -Hydroxyisophthalamide,
N, N'-bis (2-, 3- or 4-aminophenyl)
-3-hydroxyterephthalamide, N, N'-bis (4-amino-3,5'-dimethylphenyl) -5-hydroxyisophthalamide, N, N'-bis (4-amino-3,5'-dimethyl Phenyl) -2-hydroxyterephthalamide, N, N'-bis (4-amino-3,
5'-dimethylphenyl) -2-hydroxyphthalamide, N, N'-bis (4-amino-3,5'-dimethylphenyl) -3-hydroxyphthalamide, N, N'-
Bis (4-amino-n-butyl) -5-hydroxyisophthalamide, N, N'-bis (4-amino-n-hexyl) -5-hydroxyisophthalamide, N, N'-
Bis (4-amino-n-dodecyl) -5-hydroxyisophthalamide and the like.

The polyamide-imide resin is obtained by, for example, a known imidation reaction from trimellitic anhydride and a diamine of the formula II by a general imidation reaction.

Embedded image (Wherein R has the meaning described above), and can be produced by reacting the compound with a diamine of the formula II and another diamine. Amide-forming derivatives, such as alkyl esters, aryl esters, acid halides, etc., of the compound of formula III, and amide-forming derivatives thereof, such as N, N'-diacyldiamino derivatives, may be used in place of the diamine of formula II, if desired. You may.

Other diamines other than the diamine of the formula II include, for example, the following compounds. N, N'-bis (2-, 3- or 4-aminophenyl) isophthalamide, N, N'-bis (2-, 3- or 4-aminophenyl) terephthalamide, N, N'-bis (2 -, 3- or 4-aminophenyl) phthalamide, N, N'-bis (4-amino-3,5-dimethylphenyl) terephthalamide, N, N'-bis (4-amino-3,5-dimethylphenyl) ) Phthalamide, N, N'-bis (4-amino-n-butyl) isophthalamide, N, N'-bis (4-amino-n-hexyl) isophthalamide,
N'-bis (4-amino-n-dodecyl) -isophthalamide, meta or paraphenylenediamine, metatolylenediamine, 4,4'-, 3,3'- or 3,4'-diaminodiphenyl ether, 3, 3'-dimethyl-4,
4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3 '
-Or 4,4'-diaminophenylmethane, 3,3'-
Dimethoxy-4,4'-diaminodiphenylmethane,
2,2'-bis (3- or 4-aminophenylpropane, 4,4'-diaminodiphenylsulfoxide, 3,
3'- or 4,4'-diaminodiphenylsulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-
Dimethoxybenzidine, 3,3'-diaminobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4
-Aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4-
(4-aminophenoxy) phenyl] propane, 2,2
-Bis [3-chloro-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- ( 4-aminophenoxy) phenyl] methane,
Piperazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p- or m-xylenediamine, 3-methylheptamethylenediamine and the like.
It is preferred that the other diamine be 50 mol% or less, especially 30 mol% or less, based on 100 mol% of the compound of the formula II.

In the preparation of polyamideimides, ie in the polycondensation reaction of a dicarboxylic acid component based on an imidedicarboxylic acid of the formula III with a diamine of the formula II,
If desired, some of the imidodicarboxylic acids of formula III and / or their amide-forming derivatives can be substituted with other dicarboxylic acids and / or
Alternatively, these amide-forming products can be substituted.
Examples of other dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, succinic acid, adipic acid, sebacic acid, and cyclohexanedicarboxylic acid.
The imidodicarboxylic acid used in the present invention can be easily produced by a known imidization reaction. N, N-
In an inert polar solvent such as dimethylformamide, N, N-dimethylacetamidoamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone and hexamethylphosphoric triamide , 0.4 to 0.6 equivalents of the diamine is added to 1 equivalent of trimellitic anhydride,
The reaction is preferably performed at a temperature in the range of 20 to 300 ° C., preferably 0 to 60 ° C. for several tens of minutes to several days, to produce an amic acid, which is further preferably imidized.

[0010] Examples of the imidation method include a method of dehydrating a ring by heating and a method of chemically closing a ring using a dehydration catalyst. When the ring is dehydrated by heating,
The reaction temperature is 150 to 400 ° C, preferably 180 to 350.
° C, and the reaction time is 30 seconds to 10 hours, preferably 5 minutes to 5 hours. When a dehydration ring-closing catalyst is used, the reaction temperature is 0 to 180 ° C., preferably 10 to 80 ° C., and the reaction time is tens of minutes to several days, preferably
2 hours. Acid anhydrides such as acetic acid, propionic acid, butyric acid, and benzoic acid are used as the dehydration ring-closing catalyst, and it is preferable to use pyridine and the like in combination as a compound that promotes the cyclization reaction. The amount of the dehydration ring-closing catalyst used is 200 mol% or more, preferably 300 to 1000 mol%, based on the total amount of the diamine. The amount of the compound that promotes the cyclization reaction is preferably 150 to 500 mol% based on the total amount of the diamine.

The polycondensation reaction between the dicarboxylic acid component having an imide dicarboxylic acid of the formula III as a main component and the diamine component having a diamine of the formula II as a main component for forming the polyamideimide of the present invention is carried out by the above-mentioned carboxylic acid component. It is preferable to mix one equivalent of the diamine component with respect to one equivalent, add a condensing agent, and perform the reaction in a solvent. As the solvent, toluene, benzene, chlorobenzene, dichlorobenzene, acetonitrile, pyridine, tetrahydrofuran, acetic anhydride, dichloromethane, hexane, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide and the like are used. If necessary, inorganic salts such as lithium chloride and calcium chloride can be added to the reaction system in order to increase the solvating power of the protic solvent and to suppress side reactions.

As the condensing agent, triphenyl phosphite,
Diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, tri-m-tolyl phosphite, di-m-tolyl phosphite, tri-p-tolyl phosphite, Di-p-tolyl phosphite, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-phosphite
p-Chlorophenyl, dicyclohexylcarbodiimide, triphenyl phosphate, diphenyl phosphonate and the like are used. The reaction time is preferably in the range of 60 to 150 ° C. The reaction is usually completed in a few minutes to 24 hours. Depending on the case, the reaction conditions may be such that the reaction solution is heated to a high temperature or the generated water is removed to shift the equilibrium to the production system. The resulting polyamideimide resin has an intrinsic viscosity (0.5 g / dl concentration in N-methyl-2-pyrrolidone, 30 ° C.) of 0.1 to 5.0 dl / g, preferably 0.1 to 5.0 dl / g.
2 to 1.5 dl / g.

[0013]

【Example】

Example 1 N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide 14.4 g (40 mmol), m-
1.1 g (10 mmol) of phenylenediamine and 32 g (100 mmol) of trimellitic anhydride were combined with N-methyl-
The polyamic acid was dissolved in 150 ml of 2-pyrrolidone and reacted at room temperature for 6 hours under a nitrogen atmosphere to obtain a polyamic acid solution. This polyamic acid solution was heated at 200 ° C. for 2 hours to perform a dehydration cyclization reaction. After cooling, N, N'-
18 g (50 mmol) of bis (3-aminophenyl) -5-hydroxyisophthalamide, 25 ml of pyridine,
31 g (100 mmol) of triphenyl phosphite and 5 g (125 mmol) of lithium chloride were added sequentially,
For 6 hours. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid was separated by filtration, and the filtrate was washed with hot methanol and dried, and had an intrinsic viscosity of 0.4.
9 dl / g (in N-2-methylpyrrolidone, 0.5 g / g
dl concentration, 30 ° C, the same applies hereinafter). Infrared spectral analysis absorption of the phenolic hydroxyl group was observed at 3213cm ^-1 by, absorption by imide bond is observed at 1779cm ^-1, absorption of a carbonyl group by an amide bond to 1676cm ^-1 were observed. From these results, it was confirmed that this was a polyamide imide comprising a repeating unit described below.

EXAMPLE 2 18 g (50 mmol) of N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide and 32 g (100 mmol) of trimellitic anhydride were combined with N-methyl-2.
-Dissolved in 150 ml of pyrrolidone and reacted for 6 hours at room temperature under a nitrogen atmosphere to obtain a polyamic acid solution. This polyamic acid solution was heated at 200 ° C. for 2 hours to perform a dehydration cyclization reaction. After cooling, 1.7 g (10 mmol) of isophthalic acid and N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide were added to the reaction mixture solution.
6 g (60 mmol), 30 ml of pyridine, 37.2 g (120 mmol) of triphenyl phosphite, and 6 g (150 mmol) of lithium chloride were sequentially added, followed by stirring at 100 ° C. for 6 hours. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid is separated by filtration, and the filtrate is washed with hot methanol and dried, and has an intrinsic viscosity of 0.45 dl.
/ G of a polyamide-imide resin.

EXAMPLE 3 18 g (50 mmol) of N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide and 32 g (100 mmol) of trimellitic anhydride were combined with N-methyl-2.
-Dissolved in 150 ml of pyrrolidone and reacted for 6 hours at room temperature under a nitrogen atmosphere to obtain a polyamic acid solution. This polyamic acid solution was heated at 200 ° C. for 2 hours to perform a dehydration cyclization reaction. After cooling, 14.4 g (40 mmol) of N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide, 1.1 g (10 mmol) of m-phenylenediamine, 25 ml of pyridine were added to the reaction mixture.
31 g (100 mmol) of triphenyl phosphite and 5 g (125 mmol) of lithium chloride were added sequentially,
For 6 hours. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid was filtered off, and the filtrate was washed with hot methanol and dried, and had an intrinsic viscosity of 0.5.
1 dl / g of polyamide-imide resin was obtained.

The repeating units of the polyamideimide resins obtained in Examples 1 to 3 are shown below. Ar 'in the formula is as follows.

Embedded image

Embodiment 1

Embedded image

Embodiment 2

Embedded image

Embodiment 3

Embedded image

[0020]

The polyamideimide resin of the present invention has excellent heat resistance and solvent solubility and can be mixed with other reactive resins. This polyamideimide resin is useful as a material for films, electric wire coatings, adhesives, paints, laminates and the like used at high temperatures.

Claims (1)

(57) [Claims] [Claim 1] Wherein Ar is a divalent aromatic group, R ² is a group Wherein R is a group Or C ₁ -C ₁₂ represents an alkylene group, where R ¹ represents a hydrogen atom, a methyl group, a halogen atom, a nitrile group, a nitro group or a hydroxyl group, R ^3, R ⁴ and R ⁵ is different from R ² 2 A divalent aliphatic group, a divalent aromatic group, a divalent alicyclic group,
l, m, n, x and y are l ≧ 2 (m + n) and l is a positive integer of l ≦ 5 and x ≦ 6 satisfying the formula of x ≧ 2y).