JP2844566B2 - Polyamide resin and its resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel heat-meltable aromatic polyamide having high heat resistance.

Further, the present invention relates to a novel polyamide resin composition having excellent dimensional stability and mechanical properties and excellent workability.

[Conventional technology]

Conventionally, aromatic polyamides obtained by reacting an aromatic diamine or an aromatic diisocyanate with an aromatic dicarboxylic acid or a derivative thereof have a variety of excellent physical properties and good heat resistance. Is expected to be widely used in the field where is required.

However, although there have been many aromatic polyamides which have been developed so far, they have excellent mechanical properties and heat resistance.

For example, formula (III) An aromatic polyamide having a basic skeleton represented by the following formula (a product of DuPont: Kevlar) has excellent properties such as flame retardancy, heat resistance, high tensile strength and high elastic modulus. However, this aromatic polyamide does not have a clear glass transition temperature, has a thermal decomposition temperature of about 430 ° C, and is close to the processing temperature and the thermal decomposition temperature, so it is difficult to process it as a molding material. There were drawbacks. Therefore, it is only used in the field of fibers by wet spinning or pulp. Further, the water absorption rate is as high as 4.5%, and it is apparent that such a material adversely affects dimensional stability, insulation properties, solder heat resistance and the like when used as a substrate for electric / electronic parts.

[Problem to be solved by the present invention]

An object of the present invention is to provide a novel resin composition which improves the mechanical strength and dimensional stability of a polyamide and further has excellent processability.

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve the above-mentioned object, and as a result, have found a novel aromatic polyamide having desired performance and a resin composition thereof, and have completed the present invention.

That is, the present invention provides: (1) Formula (I) (Wherein X is a condensed polycyclic aromatic group or Or one or more groups selected from the group consisting of Wherein Y is a direct bond, -O-, -S-, R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. The polyamide obtained by reacting an aromatic polyamide and / or a diamine with a dicarboxylic acid or a dicarboxylic acid derivative represented by the following formula (I): (Wherein X is a condensed polycyclic aromatic group or Or one or more groups selected from the group consisting of Where Y is a direct bond R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group,
Or a halogen group, a phenyl group, a is 0, 1 or 2, b
Represents 0 or an integer of 1 to 4. N represents an integer of 1 to 1000. ) As a basic skeleton, the polycondensation reaction is carried out in the presence of a monovalent carboxylic acid or a carboxylic acid derivative, and the amount of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative is reduced to the aromatic diamine. It is obtained by reacting a polyamide and / or a diamine with good heat stability, which is obtained by reacting at a ratio of 0.001 to 1.0 mole per mole of diamine per mole of diamine. The polyamide represented by the following formula (I) (Wherein X is a condensed polycyclic aromatic group or Or one or more groups selected from the group consisting of Where Y is a direct bond R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group,
Or a halogen group, a phenyl group, a is 0, 1 or 2, b
Represents 0 or an integer of 1 to 4. N represents an integer of 1 to 1000. ) As a basic skeleton, and the polycondensation reaction is performed in the presence of a monovalent amine;
The amount of the aromatic diamine is 0.7 to 1.0 mol per 1 mol of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative, and the amount of the monovalent amine is 1 mol of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative. 100 parts by weight of a polyamide having good thermal stability and a fibrous reinforcing material of 5 to 1 which are obtained by reacting at a ratio of 0.001 to 1.0 mol.
It is a polyamide resin composition comprising 100 parts by weight.

The aromatic polyamide of the present invention is a diamine represented by the formula (II) as a diamine component, that is, 1,4-bis [4-
(4-aminophenoxy) -α, α-dimethylbenzyl] benzene and / or 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and an aromatic dicarboxylic acid Alternatively, it can be obtained by polymerizing a derivative thereof. Further, the polyamide resin composition of the present invention can be obtained by adding a fibrous reinforcing material to the polyamide of the present invention. That is, the polyamide of the present invention and its resin composition contain 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and / or 1,3-bis [4- (4- Aminophenoxy) -α, α-dimethylbenzyl] benzene is used as a diamine component, and originally has excellent workability in addition to the heat resistance of an aromatic polyamide.
A thermoplastic aromatic polyamide and a resin composition thereof.

Since the aromatic polyamide and its resin composition are thermoplastic in addition to excellent heat resistance, they can be extrusion-molded and injection-molded. Furthermore, it can be expected to be used for multipurpose applications as a raw material for high-strength, high heat-resistant fibers by a melt spinning method, and is extremely useful.

Although the polyamide of the present invention is a polyamide using the above-mentioned diamine as a raw material, other diamines can be mixed and used as long as good properties of the polyamide are not impaired.

Examples of the diamine that can be used by mixing include, for example, o-
Phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 2-chloro-1,2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 2,3 −
Diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 2-methoxy-1,4-phenylenediamine,
4-methoxy-1,2-phenylenediamine, 4-methoxy-1,3-phenylenediamine, benzidine, 3,3'-dichlorobenzidine, 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'-diaminodiphenyl sulfide, 3,3'-
Diaminodiphenylsulfoxide, 3,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone,
4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminebenzophenone,
3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4 '
-Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3 -Aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4-
(3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane,
2,2-bis [4- (3-aminophenoxy) phenyl]
Propane, 2,2-bis [4- (4-aminophenoxy)
Phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] butane, 2,2-bis [4
-(3-aminophenoxy) phenyl] -1,1,1,3,3,3
-Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy)
Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4
-Bis (4-aminophenoxy) benzene, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3
-Aminophenoxy) phenyl] ketone, bis [4-
(4-aminophenoxy) phenyl] ketone, bis [4
-(3-Aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl ] Sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- ( 4-aminophenoxy) phenyl] ether, 1,4-bis [4
-(3-aminophenoxy) benzoyl] benzene, 1,
3-bis [4- (3-aminophenoxy) benzoyl]
Benzene, 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- ( 4-amino-α, α
-Dimethylbenzyl) phenoxy] benzophenone, 4,
4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4-
{4- (4-aminophenoxy) phenoxy} phenyl] ketone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, etc., and these may be used alone or in combination of two or more. used.

The method for producing the aromatic polyamide of the present invention is not particularly limited, and a conventionally known method can be employed.

For example, the method according to claims 2 to 4 is described. The aromatic diamine used in this method is 1,4-bis [4- (4-
Aminophenoxy) -α, α-dimethylbenzyl] benzene and / or 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene. The aromatic dicarboxylic acids used include:
In the method according to the second aspect, an aromatic dicarboxylic acid dihalide is used. For example, phthalic dichloride, phthalic dibromide, methyl phthalic dichloride, methyl phthalic dibromide, ethyl phthalic dichloride, ethyl phthalic dibromide, methoxy phthalic dichloride, methoxy phthalic dibromide, ethoxy phthalic dichloride, ethoxy phthalate Acid dibromides, chlorophthalic dichlorides, chlorophthalic dibromides, bromophthalic dichlorides, bromophthalic dibromides, isophthalic dichlorides, isophthalic dibromides, methyl isophthalic dichlorides, methyl isophthalic dibromides, ethyl isophthalic dichlorides, Ethyl isophthalic dibromide, meoxy isophthalic dichloride, methoxy isophthalic dibromide, ethoxy isophthalic dichloride , Ethoxy Lee perilla phthalic acid dibromide such, chloroisophthalic acid dichloride such, chloroisophthalic acid dibromide such, bromo isophthalic acid dichloride such, bromo isophthalic acid dibromide such,
Terephthalic acid dichloride, terephthalic acid dibromide, methyl terephthalic acid dichlorides, methyl terephthalic acid dibromide, ethyl terephthalic acid dichloride, ethyl terephthalic acid dibromide, methoxy terephthalic acid dichloride, methoxy terephthalic acid dibromide, ethoxy terephthalic acid dichloride, Ethoxyterephthalic acid dibromide, chloroterephthalic acid dichloride, chloroterephthalic acid dibromide, bromoterephthalic acid dichloride, bromoterephthalic acid dibromide, 4,4'-biphenyldicarboxylic acid dichloride, 4,4'-biphenyldicarboxylic acid dibromide, 4,4'-diphenyl ether dicarboxylic acid dichloride, 4,4'-diphenyl ether dicarboxylic acid dibromide, 4,4'-benzophenone dicarboxylic acid dichloride, 4,4'- Nzophenone dicarboxylic acid dibromide, 4,4'-diphenyl sulfide dicarboxylic acid dichloride, 4,4'-diphenyl sulfide dicarboxylic acid dibromide, 4,4'-diphenyl sulfone dicarboxylic acid dichloride, 4,4'-diphenyl sulfone dicarboxylic acid dibromide 4,4'-diphenylmethanedicarboxylic acid dichloride, 4,4'-diphenylmethanedicarboxylic acid dibromide, 2,2-bis (4-chloroformylphenyl) propane, 2,2-bis (4-bromoformylphenyl) propane, 2 , 2-Bis (4-chloroformylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-
Bis (4-bromoformylphenyl) -1,1,1,3,3,3-
Hexafluoropropane, 1,4-naphthalenedicarboxylic dichloride, 1,4-naphthalenedicarboxylic dibromide, 2,3-naphthalenedicarboxylic dichloride, 2,3-naphthalenedicarboxylic dibromide, 2,6-naphthalenedicarboxylic dichloride, 2 , 6-naphthalenedicarboxylic acid dibromide and the like. These aromatic dicarboxylic dihalides are used alone or in combination of two or more.

In the method according to the third aspect, an aromatic dicarboxylic acid is used. For example, phthalic acid, methylphthalic acids,
Ethylphthalic acids, methoxyphthalic acids, ethoxyphthalic acids, chlorophthalic acids, bromophthalic acids, isophthalic acid, methylisophthalic acids, ethylisophthalic acids, methoxyisophthalic acids, ethoxyisophthalic acids, chloroisophthalic acids, bromoisophthalic acids, terephthalic acid, methylterephthalic acids , Ethyl terephthalic acids, methoxy terephthalic acids, ethoxy terephthalic acids, chloroterephthalic acids, bromoterephthalic acids, 2,
2'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid,
4,4'-diphenyl sulfide dicarboxylic acid, 4,4'-benzophenone carboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenyl methane dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane ,
2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-
Examples include hexafluoropropane, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. These aromatic dicarboxylic acids are used alone or in combination of two or more.

In the method according to claim 4, for example, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, isophthalic acid Diisopropyl, dibutyl isophthalate, diisobutyl isophthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisopropyl terephthalate,
Dibutyl terephthalate, diisobutyl terephthalate, 4,
Dimethyl 4'-biphenyldicarboxylate, diethyl 4,4'-biphenyldicarboxylate, dipropyl 4,4'-biphenyldicarboxylate, diisopropyl 4,4'-diphenyldicarboxylate, dibutyl 4,4'-biphenyldicarboxylate, Diisobutyl 4'-biphenyldicarboxylate, 4,
Dimethyl 4'-diphenyletherdicarboxylate, 4,4 '
-Diethyl diphenyl ether dicarboxylate, 4,4'-
Dipropyl diphenyl ether dicarboxylate, 4,4'-
Diisopropyl diphenyl ether dicarboxylate, 4,
Dibutyl 4'-diphenyl ether dicarboxylate, 4,
Diisobutyl 4'-zinphenyl ether dicarboxylate, dimethyl 4,4'-diphenyl sulfide dicarboxylate, diethyl 4,4'-diphenyl sulfide dicarboxylate, dipropyl 4,4'-diphenyl sulfide dicarboxylate, 4,4'-diphenyl sulfide Diisopropyl dicarboxylate, dibutyl 4,4'-diphenyl sulfide dicarboxylate, diisobutyl 4,4'-diphenyl sulfide dicarboxylate, dimethyl 4,4'-benzophenone dicarboxylate, diethyl 4,4'-benzophenone dicarboxylate, 4,4 ' -Dipropyl benzophenone dicarboxylate,
Diisopropyl 4,4'-benzophenonedicarboxylate,
4,4'-benzophenone dicarboxylate dibutyl, 4,4'-
Diisobutyl benzophenone dicarboxylate, dimethyl 4,4'-diphenylsulfonedicarboxylate, diethyl 4,4'-dinphenylsulfondicarboxylate, dipropyl 4,4'-diphenylsulfonedicarboxylate, diisopropyl 4,4'-diphenylsulfonedicarboxylate, 4,4'-
Dibutyl sulfonyl dicarboxylate, diisobutyl 4,4'-diphenyl sulfone dicarboxylate, 4,4'-
Dimethyl diphenylmethane dicarboxylate, diethyl 4,4'-diphenylmethane dicarboxylate, dipropyl 4,4'-diphenylmethane dicarboxylate, diisopropyl 4,4'-diphenylmethane dicarboxylate, dibutyl 4,4'-diphenylmethane dicarboxylate, 4,4'- Diisobutyl diphenylmethanedicarboxylate, 2,2-bis (4-methoxycarbonylphenyl) propane, 2,2-bis (4-
Ethoxycarbonylphenyl) propane, 2,2-bis (4-propoxycarbonylphenyl) propane, 2,2
-Bis (4-isopropoxycarbonylphenyl) propane, 2,2-bis (4-butoxycarbonylphenyl)
Propane, 2,2-bis (4-isobutoxycarbonylphenyl) propane, 2,2-bis (4-methoxycarbonylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2- Bis (4-ethoxycarbonylphenyl)-
1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4
-Propoxycarbonylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-isopropoxycarbonylphenyl) -1,1,1,3,3,3-hexafluoro Propane, 2,2-bis (4-butoxycarbonylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-
Bis (4-isobutoxycarbonylphenyl) -1,1,1,
3,3,3-hexafluoropropane, dimethyl 1,4-naphthalenedicarboxylate, diethyl 1,4-naphthalenedicarboxylate, dipropyl 1,4-naphthalenedicarboxylate, 1,4-
Diisopropyl naphthalenedicarboxylate, dibutyl 1,4-naphthalenedicarboxylate, diisobutyl 1,4-naphthalenedicarboxylate, dimethyl 2,3-naphthalenedicarboxylate, diethyl 2,3-naphthalenedicarboxylate, dipropyl 2,3-naphthalenedicarboxylate, Diisopropyl 2,3-naphthalenedicarboxylate, dibutyl 2,3-naphthalenedicarboxylate, diisobutyl 2,3-naphthalenedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate, diethyl 2,6-naphthalenedicarboxylate, 2,6-naphthalene Aromatic dicarboxylic acid dialkylates and / or diphenyl phthalate such as dipropyl dicarboxylate, diisopropyl 2,6-naphthalenedicarboxylate, dibutyl 2,6-naphthalenedicarboxylate, diisobutyl 2,6-naphthalenedicarboxylate, diphenyl phthalate, Pheni ) S,
Di (chlorophenyl) phthalate, di (bromophenyl) phthalate, di (methylphenyl) phthalate, di (ethylphenyl) phthalate, di (propylphenyl) phthalate, di (isopropylphenyl) phthalate ),
Di (butylphenyl) phthalate, di (isobutylphenyl) phthalate, di (t-butylphenyl) phthalate
, Di (methoxyphenyl) phthalate, di (ethoxyphenyl) phthalate, di (nitrophenyl) phthalate, di (phenylphenyl) phthalate, diphenylisophthalate, di (fluorophenyl) isophthalate
, Di (chlorophenyl) isophthalate, di (bromophenyl) isophthalate, di (methylphenyl) isophthalate, di (ethylphenyl) isophthalate, di (propylphenyl) isophthalate, di (isopropylphenyl) isophthalate Isopropylphenyl), di (butylphenyl) isophthalate, di (isobutylphenyl) isophthalate
, Di (t-butylphenyl) isophthalate, di (methoxyphenyl) isophthalate, di (ethoxyphenyl) isophthalate, di (nitrophenyl) isophthalate, di (phenylphenyl) isophthalate, terephthalate Acid diphenyl, terephthalic acid di (fluorophenyl) s, terephthalic acid di (chlorophenyl) s, terephthalic acid di (bromophenyl) s, terephthalic acid di (methylphenyl) s, terephthalic acid di (ethylphenyl)
, Di (propylphenyl) terephthalate, di (isopropylphenyl) terephthalate, di (butylphenyl) terephthalate, di (isobutylphenyl) terephthalate, di (t-butylphenyl) terephthalate
, Terephthalic acid di (methoxyphenyl) s, terephthalic acid di (ethoxyphenyl) s, terephthalic acid di (nitrophenyl) s, terephthalic acid di (phenylphenyl)
, 4,4'-biphenyl dicarboxylic acid diphenyl, 4,4 '
-Biphenyldicarboxylic acid di (fluorophenyl) s,
4,4'-biphenyldicarboxylic acid di (chlorophenyl)
, 4,4'-biphenyldicarboxylic acid di (bromophenyl), 4,4'-biphenyldicarboxylic acid di (methylphenyl), 4,4'-biphenyldicarboxylic acid di (ethylphenyl), 4,4 '-Biphenyldicarboxylic acid di (propylphenyl) s, 4,4'-biphenyldicarboxylic acid di (isopropylphenyl) s, 4,4'-biphenyldicarboxylic acid di (butylphenyl) s, 4,4'-biphenyldicarboxylic acid Di (isobutylphenyl) s, 4,
4'-biphenyl dicarboxylic acid di (t-butylphenyl), 4,4'-biphenyl dicarboxylic acid di (methoxyphenyl), 4,4'-biphenyl dicarboxylic acid di (ethoxyphenyl), 4,4'- Di (nitrophenyl) biphenyl dicarboxylate, di (phenylphenyl) 4,4'-biphenyl dicarboxylate, diphenyl 4,4'-diphenyl ether dicarboxylate, di (fluorophenyl) 4,4'-diphenyl ether dicarboxylate, 4,4 '
Diphenyl ether dicarboxylic acid di (chlorophenyl), 4,4'-diphenyl ether dicarboxylic acid di (bromophenyl), 4,4'-diphenyl ether dicarboxylic acid di (methylphenyl), 4,4'-diphenyl ether dicarboxylic acid di ( Ethylphenyl), 4,
4'-diphenyl ether dicarboxylic acid di (propyl phenyl), 4,4'-diphenyl ether dicarboxylic acid di (isopropyl phenyl), 4,4'-diphenyl ether dicarboxylic acid di (butyl phenyl), 4,4'-
Diphenyl ether dicarboxylic acid di (isobutylphenyl) s, 4,4'-diphenyl ether dicarboxylic acid di (t-butylphenyl) s, 4,4'-diphenyl ether dicarboxylic acid di (methoxyphenyls, 4,4'-diphenyl ether dicarboxylic acid dicarboxylic acid (Ethoxyphenyl)
, Di (nitrophenyl) 4,4'-diphenyl ether dicarboxylate, di (phenylphenyl) 4,4'-diphenyl ether dicarboxylate, diphenyl 4,4'-diphenyl sulfide dicarboxylate, 4,4'-diphenyl sulfide Dicarboxylic acid di (fluorophenyl) s, 4,
4'-diphenyl sulfide dicarboxylic acid di (chlorophenyl), 4,4'-diphenyl sulfide dicarboxylic acid di (bromophenyl), 4,4'-diphenyl sulfide dicarboxylic acid di (methylphenyl), 4,4'- Diphenyl sulfide dicarboxylate (ethylphenyl)
, Di (propylphenyl) 4,4'-diphenylsulfidedicarboxylate, di (isopropylphenyl) 4,4'-diphenylsulfidedicarboxylate, di (butylphenyl) 4,4'-diphenylsulfidedicarboxylate
, 4,4'-diphenyl sulfide dicarboxylic acid di (isobutylphenyl), 4,4'-diphenyl sulfide dicarboxylic acid di (t-butylphenyl), 4,4'-diphenyl sulfide dicarboxylic acid di (methoxyphenyl) , 4,4'-diphenyl sulfide dicarboxylic acid di (ethoxyphenyl), 4,4'-diphenyl sulfide dicarboxylic acid di (nitrophenyl), 4,4'-diphenyl sulfide dicarboxylic acid di (phenylphenyl)
, 4,4'-benzophenone dicarboxylic acid diphenyl,
4,4'-benzophenone dicarboxylic acid di (fluorophenyl), 4,4'-benzophenone dicarboxylic acid di (chlorophenyl), 4,4'-benzophenone dicarboxylic acid di (bromophenyl), 4,4'-benzophenone Dicarboxylic acid di (methylphenyl) s, 4,4'-benzophenonedicarboxylic acid di (ethylphenyl) s, 4,4'-
Benzophenone dicarboxylate di (propylphenyl)
, 4,4'-benzophenone dicarboxylic acid di (isopropylphenyl), 4,4'-benzophenone dicarboxylic acid di (butylphenyl), 4,4'-benzophenone dicarboxylic acid di (isobutylphenyl), 4,4 '-Benzophenone dicarboxylic acid di (t-butylphenyl) s,
4,4'-benzophenone dicarboxylic acid di (methoxyphenyl), 4,4'-benzophenone dicarboxylic acid di (ethoxyphenyl), 4,4'-benzophenone dicarboxylic acid di (nitrophenyl), 4,4'- Benzophenone dicarboxylic acid di (phenylphenyl) s, 4,4'-diphenylsulfondicarboxylic acid diphenyl, 4,4'-diphenylsulfonedicarboxylic acid di (fluorophenyl)
4,4'-diphenylsulfondicarboxylic acid di (chlorophenyl) s, 4,4'-diphenylsulfondicarboxylic acid di (bromophenyl) s, 4,4'-diphenylsulfondicarboxylic acid di (methylphenyl) s, 4 4,4'-Diphenylsulfonedicarboxylic acid di (ethylphenyl)
Di (propylphenyl) 4,4'-diphenylsulfonedicarboxylate, di (isopropylphenyl) 4,4'-diphenylsulfonedicarboxylate, di (butylphenyl) 4,4'-diphenylsulfonedicarboxylate, Four,
4'-diphenylsulfondicarboxylic acid di (isobutylphenyl) s, 4,4'-diphenylsulfondicarboxylic acid di (t-butylphenyl) s, 4,4'-diphenylsulfondicarboxylic acid di (methoxyphenyl) s, Four'
-Diphenylsulfondicarboxylic acid di (ethoxyphenyl) s, 4,4'-diphenylsulfondicarboxylic acid di (nitrophenyl) s, 4,4'-diphenylsulfondicarboxylic acid di (phenylphenyl) s, 4,4'-diphenylmethane Diphenyl dicarboxylate, di (fluorophenyl) 4,4'-diphenylmethanedicarboxylate, 4,
4'-diphenylmethanedicarboxylic acid di (chlorophenyl) s, 4,4'-diphenylmethanedicarboxylic acid di (bromophenyl) s, 4,4'-diphenylmethanedicarboxylic acid di (methylphenyl) s, 4,4'-diphenylmethanedicarboxylic acid Di (ethylphenyl) s, 4,4'-diphenylmethanedicarboxylic acid di (propylphenyl) s,
4,4'-diphenylmethane dicarboxylic acid di (isopropylphenyl), 4,4'-diphenylmethane dicarboxylic acid di (butylphenyl), 4,4'-diphenylmethane dicarboxylic acid di (isobutylphenyl), 4,4'- Diphenylmethanedicarboxylic acid di (t-butylphenyl)
, 4,4'-diphenylmethanedicarboxylic acid di (methoxyphenyl), 4,4'-diphenylmethanedicarboxylic acid di (ethoxyphenyl), 4,4'-diphenylmethanedicarboxylic acid di (nitrophenyl), 4,4 '-Diphenylmethanedicarboxylic acid di (phenylphenyl) s,
2,2-bis (4-phenoxycarbonylphenyl) propane, 2,2-bis {4- (fluorophenoxycarbonyl) phenyl} propanes, 2,2-bis {4- (chlorophenoxycarbonyl) phenyl} propanes, 2,2-
Bis {4- (bromophenoxycarbonyl) phenyl}
Propanes, 2,2-bis {4- (methylphenoxycarbonyl) phenyl} propanes, 2,2-bis {4- (ethylphenoxycarbonyl) phenyl} propanes, 2,
2-bis {4- (propylphenoxycarbonyl) phenyl} propanes, 2,2-bis {4- (isopropylphenoxycarbonyl) phenyl} propanes, 2,2-bis {4- (butylphenoxycarbonyl) phenyl} propane , 2,2-bis {4- (isobutylphenoxycarbonyl) phenyl} propanes, 2,2-bis {4-
(T-butylphenoxycarbonyl) phenyl} propanes, 2,2-bis {4- (methoxyphenoxycarbonyl) phenyl} propanes, 2,2-bis {4- (ethoxyphenoxycarbonyl) phenyl} propanes, Two
-Bis {4- (nitrophenoxycarbonyl) phenyl} propanes, 2,2-bis {4- (phenylphenoxycarbonyl) phenyl} propanes, 2,2-bis (4
-Phenoxycarbonylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis {4- (fluorophenoxycarbonyl) phenyl} -1,1,1,3,3,3 -Hexafluoropropanes, 2,2-bis {4- (chlorophenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexafluoropropanes, 2,2-bis {4- (bromophenoxy Carbonyl) phenyl {-1,1,1,3,3,3-hexafluoropropane, 2,2-bis {4- (methylphenoxycarbonyl) phenyl} -1,1,1,3,3,3- Hexafluoropropanes, 2,2-bis {4- (ethylphenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexafluoropropanes, 2,2-bis {4- (propylphenoxycarbonyl) ) Phenyl} -1,1,1,3,3,3-hexafluoropropane, 2,2-bis {4- (isopropylphenoxycarbo) Le) phenyl} -1,1,1,3,3,3-hexafluoropropane, 2,2-bis {4- (butylphenoxycarbonyl) phenyl} -1,1,1,3,3,3- Hexafluoropropanes, 2,2-bis {4- (isobutylphenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexafluoropropanes, 2,2-bis {4- (t-butyl) Phenoxycarbonyl) phenyl {-1,1,1,3,3,3-hexafluoropropane, 2,2-bis {4- (methoxyphenoxycarbonyl) phenyl} -1,1,1,3,3,3 -Hexafluoropropanes, 2,2-bis {4- (ethoxyphenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexafluoropropanes, 2,2-bis {4- (nitrophenoxy Carbonyl) phenyl} -1,1,1,3,3,3-hexafluoropropanes, 2,2-bis {4- (phenylphenoxycarbonyl) phenyl -1,1,1,3,3,3-hexafluoropropanes, 1,4-naphthalenedicarboxylic acid diphenyl, 1,4-naphthalenedicarboxylic acid di (fluorophenyl) s, 1,4-naphthalenedicarboxylic acid di ( Chlorophenyl), 1,4-naphthalenedicarboxylic acid di (bromophenyl), 1,4-naphthalenedicarboxylic acid di (methylphenyl), 1,4-naphthalenedicarboxylic acid di (ethylphenyl), 1,4- Di (propylphenyl) naphthalenedicarboxylate, di (isopropylphenyl) 1,4-naphthalenedicarboxylate, di (butylphenyl) 1,4-naphthalenedicarboxylate, di (isobutylphenyl) 1,4-naphthalenedicarboxylate Class, 1,4-
Di (t-butylphenyl) naphthalenedicarboxylates,
1,4-naphthalenedicarboxylic acid di (methoxyphenyl)
, 1,4-naphthalenedicarboxylic acid di (ethoxyphenyl) s, 1,4-naphthalenedicarboxylic acid di (nitrophenyl) s, 1,4-naphthalenedicarboxylic acid di (phenylphenyl) s, 2,3-naphthalenedicarboxylic acids Acid diphenyl, 2,3-naphthalenedicarboxylic acid di (fluorophenyl) s, 2,3-naphthalenedicarboxylic acid di (chlorophenyl) s, 2,3-naphthalenedicarboxylic acid di (bromophenyl) s, 2,3-naphthalenedicarboxylic acid Acid di (methylphenyl) s, 2,3-naphthalenedicarboxylic di (ethylphenyl) s, 2,3-naphthalenedicarboxylic di (propylphenyl) s, 2,3-naphthalenedicarboxylic di (isopropylphenyl) s, 2,3-naphthalenedicarboxylic acid di (butylphenyl), 2,3-naphthalenedicarboxylic acid di (isobutylphenyl), 2,3-na Data dicarboxylic acid di (t-butylphenyl) s, 2,3-naphthalene dicarboxylic acid di (methoxyphenyl) s, 2,3
-Naphthalenedicarboxylic acid di (ethoxyphenyl) s,
2,3-Naphthalenedicarboxylic acid di (nitrophenyl)
, 2,3-naphthalenedicarboxylic acid di (phenylphenyl) s, 2,6-naphthalenedicarboxylic acid diphenyl, 2,6
-Naphthalenedicarboxylic acid di (fluorophenyl) s,
2,6-Naphthalenedicarboxylic acid di (chlorophenyl)
, 2,6-naphthalenedicarboxylic acid di (bromophenyl) s, 2,6-naphthalenedicarboxylic acid di (methylphenyl) s, 2,6-naphthalenedicarboxylic acid di (ethylphenyl) s, 2,6-naphthalenedicarboxylic Acid di (propylphenyl) s, 2,6-naphthalenedicarboxylic acid di (isopropylphenyl) s, 2,6-naphthalenedicarboxylic acid di (butylphenyl) s, 2,6-naphthalenedicarboxylic acid di (isobutylphenyl) s, 2,6-naphthalenedicarboxylic acid di (t-butylphenyl) s, 2,6-naphthalenedicarboxylic acid di (methoxyphenyl) s, 2,6-naphthalenedicarboxylic acid di (ethoxyphenyl) s, 2,6
-Di (nitrophenyl) naphthalenedicarboxylic acids, 2,
Aromatic dicarboxylic acid diallylates such as 6-naphthalenedicarboxylic acid di (phenylphenyl) s are used. These aromatic dicarboxylic acid esters are used alone or in combination of two or more.

The above diamine component and aromatic dicarboxylic acid or derivative thereof are polymerized in a solvent. As the solvent used, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3- Dimethyl-2-imidazolidinone, N-methylcaprolactam, dimethylsulfoxide, dimethylsulfone, sulfolane, tetramethylurea, hexamethylphosphoramide, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine , 2,6-lutidine,
Quinoline, isoquinoline, triethylamine, tripropylamine, tributylamine, tripentylamine,
N, N-dimethylaniline, N, N-diethylaniline, dichloromethane, chlorophorom, carbon tetrachloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, 1,1,2,2-tetrachloroethane , Tetrachloroethylene, n-hexane, cyclohexane, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetonitrile, propionitrile, acetone, mesyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone,
Cyclohexanone, acetophenone, isopropyl ether, tetrahydrofuran, tetrahydropyran, 1,3
-Dioxane, 1,4-dioxane, anisole, phenetole, benzyl ether, phenyl ether, 1,2-
Dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, benzene, toluene, o-xylene, m-xylene, p-xylene, diphenyl, terphenyl, benzyl chloride, nitrobenzene , 2-nitrotoluene, 3-nitrotoluene, 4-nitrotoluene, chlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene,
o-dichlorobenzene, p-dichlorobenzene, bromobenzene, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol , 3,4
-Xylenol, 3,5-xylenol, o-chlorophenol, p-chlorophenol, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, cyclohexanol,
Benzyl alcohol, water and the like can be mentioned. These solvents may be used alone or in combination of two or more, depending on the type of the reaction raw material monomer and the polymerization technique.

When an aromatic dicarboxylic acid dihalide is used as a reaction raw material monomer, a dehydrohalogenating agent is usually used in combination. As the dehydrohalogenating agent used, trimethylamine, triethylamine, tripropylamine,
Tributylamine, tripentylamine, N, N-dimethylbenzylamine, N, N-diethylendylamine, N, N
-Dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimesylaniline, N, N-diethylaniline, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N- Methylmorpholine, N-ethylmorpholine, pyridine, α-picoline, β-picoline, γ-picoline,
2,4-lutidine, 2,6-lutidine, quinoline, isoquinoline, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, sodium hydrogen carbonate, hydrogen hydrogen carbonate Examples include potassium, calcium oxide, lithium oxide, sodium acetate, potassium acetate, ethylene oxide, propylene oxide and the like.

When an aromatic dicarboxylic acid is used as a reaction raw material monomer, a condensing agent is usually used. Examples of the condensing agent used include sulfuric anhydride, thionyl chloride, sulfite, picryl chloride, phosphorus pentoxide, phosphorus oxychloride, phosphite-pyridine condensing agent, triphenylphosphine-hexachloroethane condensing agent, and propyl phosphorus. Acid anhydride-N-methyl-2-pyrrolidone-based condensing agent and the like.
It is usually below 300 ° C.

 The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure.

The reaction time varies depending on the type of the reaction raw material monomer, the polymerization method, the type of the solvent, the type of the dehydrohalogenating agent, the type of the condensing agent and the reaction temperature, but usually, the aromatic polyamide represented by the formula (I) The reaction is allowed to react for a time sufficient to complete the formation. Usually, 10 minutes to 24 hours is sufficient.

An aromatic polyamide having a repeating unit represented by the formula (I) is obtained.

That is, the aromatic polyamide of the present invention can be obtained by any method such as a known low-temperature solution polycondensation method or a direct polycondensation method as a method for synthesizing a polyamide.

In addition, the aromatic polyamide of the present invention uses 1,4-bis [4- (4-aminophenoxy)
-Α, α-dimethylbenzyl] benzene and / or
1,3-bis [4- (4-aminophenoxy) -α, α-
[Dimethylbenzyl] benzene and an aromatic dicarboxylic acid derivative such as aromatic dicarboxylic acid or dicarboxylic acid dihalide.

However, in order to improve the thermal stability and moldability of the aromatic polyamide, the terminal of the polymer molecule may be capped with a monovalent carboxylic acid or a carboxylic acid derivative or a monovalent amine without any problem. Absent.

Such aromatic polyamides are represented by the above formula (II).
-Bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and / or 1,3-bis [4
-(4-aminophenoxy)-[alpha], [alpha] -dimethylbenzyl] benzene as a main component and an aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative as a monovalent carboxylic acid or a carboxylic acid derivative or a monovalent carboxylic acid. By reacting in the presence of an amine.

That is, a part of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative is a monocarboxylic acid derivative such as an aromatic and / or aliphatic and / or alicyclic monocarboxylic acid or a monocarboxylic acid halide; It is prepared by replacing a part with an aromatic and / or aliphatic and / or alicyclic monoamine.

Monovalent carboxylic acids used in these methods include benzoic acid, chlorobenzoic acids, bromobenzoic acids,
Methylbenzoic acids, ethylbenzoic acids, methoxybenzoic acids, ethoxybenzoic acids, nitrobenzoic acids, acetylbenzoic acids, acetoxybenzoic acids, hydroxybenzoic acids, biphenylcarboxylic acids, benzophenonecarboxylic acids, diphenylethercarboxylic acids, diphenylsulfidecarboxylic acids, diphenyl Sulfone carboxylic acids, 2,2-diphenylpropane carboxylic acids, 2,2-
Diphenyl-1,1,1,3,3,3-hexafluoropropanecarboxylic acids, naphthalenecarboxylic acids, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, nitroacetic acid, propionic acetic acid , Butyric acid, valeric acid, caproic acid, cinnamic acid, cyclohexanecarboxylic acid and the like. These monocarboxylic acids are used alone or in combination of two or more.

Examples of the monocarboxylic acid halide include benzoyl chloride, benzoyl bromide, chlorobenzoyl chlorides, chlorobenzoyl bromide, bromobenzoyl chloride, bromobenzoyl bromide, methylbenzoyl chloride, methylbenzoyl bromide, ethylbenzoyl chloride, Ethyl benzoyl bromide, methoxy benzoyl chloride, methoxy benzoyl bromide, ethoxy benzoyl chloride, ethoxy benzoyl bromide, nitro benzoyl chloride, nitro benzoyl bromide, acetyl benzoyl chloride, acetyl benzoyl bromide, acetoxy benzoyl chloride, Acetoxybenzoyl bromides, hydroxybenzoyl chlorides, hydroxybenzoyl bromides, Phenyl acid chlorides, biphenylcarboxylic acid bromides, benzophenone carboxylic acid chlorides, benzophenone carboxylic acid bromides, Jin phenyl ether carboxylic acid chlorides,
Ginphenyl ether carboxylic acid bromides, diphenyl sulfide carboxylic acid chlorides, diphenyl sulfide carboxylic acid bromide, diphenyl sulfonic acid chlorides, diphenyl sulfonic acid bromide, 2,2-diphenylpropane carboxylic acid chloride, 2,2 -Diphenylpropanecarboxylic acid bromides,
2,2-diphenyl-1,1,1,3,3,3-hexafluoropropanecarboxylic acid chlorides, 2,2-diphenyl-1,1,1,3,
3,3-hexafluoropropanecarboxylic acid bromides,
Naphthalene carboxylic chlorides, naphthalene carboxylic bromides, acetyl chloride, acetyl bromide,
Chloroacetic acid chloride, chloroacetic acid bromide, dichloroacetic acid chloride, dichloroacetic acid bromide, trichloroacetic acid chloride, trichloroacetic acid bromide, fluoroacetic acid chloride, fluoroacetic acid bromide, difluoroacetic acid chloride,
Difluoroacetic acid bromide, trifluoroacetic acid chloride,
Trifluoroacetic acid bromide, nitroacetic acid chloride, nitroacetic acid bromide, propionic acid chloride, propionic acid bromide, butyric acid chloride, butyric acid bromide, valeric acid chloride, valeric acid bromide, caproic acid chloride, caproic acid bromide, cinnamic acid chloride, cinnamic acid bromide , Cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide and the like. These monocarboxylic acid halides may be used alone or in combination of two or more.

Also, as the monocarboxylic acid esters, benzoic acid
Methyl, ethyl benzoate, propyl benzoate, benzoic acid
Isopropyl, butyl benzoate, isobutyl benzoate,
Phenyl benzoate, fluorophenyl benzoates, benzo
Chlorophenyl balates, bromophenyl benzoates, ammonium
Methylphenyl benzoates, ethylphenyl benzoates,
Propyl benzoate, isopropyl benzoate
Phenyls, butylphenyl benzoates, isobu benzoate
Tylphenyls, t-butylphenyl benzoates, benzoate
Methoxyphenyl balates, ethoxyphenyl benzoate
, Nitrophenyl benzoates, phenyl benzoate
Nil, methyl chlorobenzoate, ethyl chlorobenzoate
, Propyl chlorobenzoate, isochlorochlorobenzoate
Propyl, butyl chlorobenzoate, chlorobenzoic acid
Isobutyls, phenyl chlorobenzoates, chlorobenzo
Fluorophenyl balates, chlorophenyl chlorobenzoate
And bromophenyl chlorobenzoates, chlorobenzo
Methylphenyls, ethylphenyl chlorobenzoate
, Propylphenyl chlorobenzoates, chlorobenzoate
Isopropyl phenyls, butyl chlorobenzoate
Nyls, isobutylphenyl chlorobenzoates, chloro
T-butylphenyl benzoates, methoxy benzoate
Cyphenyls, ethoxyphenyl chlorobenzoates,
Nitrophenyl lolobenzoate, phenylbenzoic chlorobenzoate
Ruphenyls, methyl bromobenzoates, bromobenzoate
Ethyl acid, propyl bromobenzoate, bromobenzoate
Isopropylates, butyl bromobenzoates, bromoammonium
Isobutyl benzoates, Phenyl bromobenzoates, Bro
Mo-fluorobenzoates, chloro bromobenzoate
Phenyls, bromophenyl bromobenzoates, bromo
Methylphenyl benzoates, ethyl bromobenzoate
Nyls, propylphenyl bromobenzoates, bromoammonium
Isopropylphenyl benzoates, butyl bromobenzoate
Phenyls, isobutylphenyl bromobenzoates,
T-butylphenyl lomobenzoate, bromobenzoic acid
Toxiphenyls, ethoxyphenyl bromobenzoate
, Nitrophenyl bromobenzoates, bromobenzoic acid
Phenyl phenyls, methyl benzoates, methyl
Ethyl benzoate, methyl propyl benzoate, methyl
Isopropyl benzoate, butyl methyl benzoate,
Isobutyl butyl benzoate, phenyl methyl benzoate
, Fluorophenyl methyl benzoate, methyl benzoate
Acid chlorophenyls, bromophenyl methylbenzoate
, Methyl benzoate methyl phenyls, methyl benzoate
Ethylphenyls, propylphenyl methylbenzoate
, Isopropylphenyl methyl benzoate, methyl ammonium
Butylphenyl benzoates, isobutyl methyl benzoate
Phenyls, t-butylphenyl methylbenzoate, methyl
Methoxyphenyl benzoates, methyl benzoate
Cyphenyls, nitrophenyl methylbenzoates, methyl
Phenylphenyl benzoates, methyl ethyl benzoate
, Ethyl ethyl benzoate, propyl ethyl benzoate
, Ethyl isopropyl benzoate, ethyl benzoate
Tyls, isobutyl ethyl benzoate, ethyl benzoic acid
Phenyls, fluorophenyl ethylbenzoates, ethi
Chlorophenyl benzoates, Bromoethyl benzoate
Phenyls, methylphenyl ethylbenzoate, ethyl ammonium
Ethyl phenyl benzoate, propyl ethyl benzoate
Nil, isopropylphenyl ethyl benzoate, ethi
Butyl phenyl benzoates, isobutyl ethyl benzoate
Ruphenyls, t-butylphenyl ethylbenzoate,
Methoxyphenyl ethyl benzoate, ethyl benzoate
Toxiphenyls, nitrophenyl ethylbenzoates,
Phenyl phenyl ethyl benzoate, methoxy benzoic acid
Methyls, ethyl methoxybenzoates, methoxybenzoates
Propyls, isopropyl methoxybenzoates, meth
Butyl xybenzoates, isobutyl methoxybenzoate
, Phenyl methoxybenzoates, methoxybenzoic acid
Fluorophenyls, chlorophenyl methoxybenzoate
, Bromophenyl methoxybenzoates, methoxybenzoate
Methylphenyl balates, ethyl phenyl methoxybenzoate
, Methoxyphenyl benzoate, methoxy
Isopropyl phenyl benzoate, methoxy benzoate
Tylphenyls, isobutylphenyl methoxybenzoate
, Methoxybenzoic acid t-butylphenyls, methoxy
Methoxyphenyl benzoates, ethoxy methoxybenzoate
Cyphenyls, nitrophenyl methoxybenzoates,
Phenyl phenyl benzoate, ethoxy benzoate
Methyls, ethyl ethoxybenzoates, ethoxybenzoate
Propylates, isopropyl ethoxybenzoates, ethoxy
Butyl oxybenzoates, isobutyl ethoxy benzoate
, Phenyl benzoate, ethoxybenzoate
Fluorophenyls, chlorophenyl ethoxybenzoate
, Bromophenyl ethoxybenzoates, ethoxy benzoate
Methylphenyl balates, ethylphenythoxybenzoate
, Ethoxypropyl benzoates, ethoxy
Isopropylphenyl benzoates, ethoxy benzoate
Tylphenyls, isobutylphenyl ethoxybenzoate
, Ethoxybenzoic acid t-butylphenyls, ethoxy
Methoxyphenyl benzoates, ethoxybenzoic acid ethoxy
Cyphenyls, nitrophenyl ethoxybenzoates,
Phenyl phenyl benzoates, nitrobenzoic acid
Chills, ethyl nitrobenzoates, nitrobenzoic acid pro
Pills, isopropyl nitrobenzoate, nitrobenzoate
Butyls, isobutyl nitrobenzoates, nitrobenzo
Phenyl perfuates, fluorophenyl nitrobenzoates,
Chlorophenyl nitrobenzoates, nitrobenzoic acid bro
Mophenyls, methylphenyl nitrobenzoates, nitro
Ethylphenyl benzoate, propyl nitrobenzoate
Phenyls, isopropylphenyl nitrobenzoates,
Butylphenyl nitrobenzoates, iso-nitrobenzoate
Butylphenyls, t-butylphenyl nitrobenzoate
, Methoxyphenyl nitrobenzoates, nitrobenzoate
Ethoxyphenyls, nitrophenyl nitrobenzoate
, Phenylphenyl nitrobenzoates, acetylbenzo
Methyl perfate, ethyl acetylbenzoate, acetyl ammonium
Propyl benzoate, isopropyl acetyl benzoate,
Butyl acetyl benzoate, isobutyl acetyl benzoate
, Phenyl acetylbenzoate, acetylbenzoic acid
Fluorophenyls, chlorophenyl acetylbenzoate
, Bromobenzoyl acetylbenzoates, acetyl ammonium
Methylphenyl benzoates, ethyl acetyl benzoate
Nyls, propylphenyl acetylbenzoate, acetyl
Isopropyl phenyl benzoate, acetyl benzoic acid
Butyl phenyls, isobutyl phenyl acetyl benzoate
Acetyls, t-butylphenyl acetylbenzoates, acetyl
Methoxyphenyl benzoates, acetyl benzoate
Xyphenyls, nitrophenyl acetylbenzoates,
Phenylphenyl acetylbenzoate, acetoxybenzoate
Methyl perfate, ethyl acetoxybenzoate, acetoxy
Propyl benzoate, isopropyl acetooxybenzoate
, Acetoxy benzoate, acetoxy benzoate
Isobutyls, phenylacetoxybenzoates, ace
Fluorophenyl toxic benzoate, acetoxy benzoate
Acid chlorophenyls, acetoxybenzoic acid bromopheny
Compounds, methylphenylacetoxybenzoate, acetoxy
Ethylphenyl benzoates, acetoxybenzoic acid pro
Pyrphenyls, isopropyl acetobenzoate
Nil, butylphenyl acetoxybenzoate, aceto
Isobutylphenyl xyloxybenzoate, acetoxybenzoate
T-butylphenyl acids, methoxy acetoxybenzoate
Phenyls, ethoxyphenyl acetoxybenzoates,
Nitrophenyl acetoxybenzoates, acetoxybenzo
Phenyl phenyls, methyl hydroxybenzoate
, Ethyl hydroxybenzoates, hydroxybenzoic acid
Propyl, Isopropyl hydroxybenzoate, Hyd
Roxybutyl butyls, isobutyl hydroxybenzoate
, Hydroxyphenyl benzoates, hydroxybenzo
Fluorophenyl balates, chloroph hydroxybenzoate
Phenyls, bromophenyl hydroxybenzoates, hydrides
Methylphenyl roxybenzoates, hydroxybenzoic acid
Ethylphenyls, propylpheny hydroxybenzoate
Isopropylphenyl hydroxybenzoate, arsenic
Butoxyphenyl benzoate, hydroxybenzoate
Isobutylphenyl acid, t-buty hydroxybenzoate
Ruphenyls, methoxyphenyl hydroxybenzoate
, Ethoxyphenyl hydroxybenzoates, hydroxy
Nitrophenyl benzoates, hydroxybenzoate
Nylphenyls, methyl biphenylcarboxylates, biff
Ethyl carboxylate, biphenyl carboxylic acid pro
Pills, isopropyl biphenylcarboxylate, bife
Butyl carboxylate, isophenyl biphenyl carboxylate
Tyls, phenyl biphenylcarboxylates, biphenyl
Carboxylic acid fluorophenyls, biphenylcarboxylic acids
Chlorophenyls, bromophenyl biphenylcarboxylate
, Biphenyl carboxylate methylphenyls, bife
Ethyl phenyl carboxylate, biphenyl carboxy
Propylphenyls, biphenylcarboxylic acid isopro
Pyrphenyls, butylphenyl biphenylcarboxylate
, Isobutylphenyl biphenylcarboxylate, biff
T-butylphenyl carboxylates, biphenylca
Methoxyphenyl rubonates, biphenylcarboxylic acid
Toxiphenyls, nitrophenyl biphenylcarboxylate
, Phenylphenyl biphenylcarboxylate, ben
Methyl zophenone carboxylate, benzophenone carbo
Ethylate, benzophenone carboxylate,
Benzophenone carboxylate isopropyls, benzophene
Butyl non-carboxylates, benzophenone carboxylic acid a
Sobutyls, phenyl benzophenonecarboxylates,
Nzophenone carboxylate fluorophenyls, benzofu
Chlorophenyl enone carboxylate, benzophenone
Bromophenyl rubonates, benzophenone carboxylic acid
Methylphenyls, ethyl benzophenonecarboxylate
Phenyls, propylphenyl benzophenonecarboxylate
, Isopropylphenyl benzophenonecarboxylate
, Butylphenyl benzophenonecarboxylates, ben
Zophenone carboxylate isobutyl phenyls, benzoph
T-Butylphenyl enone carboxylate, benzopheno
Methoxyphenyls carboxylate, benzophenone cal
Ethoxine phenyl borate, benzophenone carboxylic
Acid nitrophenyls, benzophenone carboxylic acid phenyl
Ruphenyls, methyl diphenyl ether carboxylate
, Ethyl diphenyl ether carboxylate, diphenyl
Propyl ether carboxylate, diphenyl ether
Isopropyl carboxylate, diphenyl ether carbo
Butylates, isobutyl diphenyl ether carboxylate
Diphenyl ether carboxylate, diph
Phenyl ether carboxylate fluorophenyls, diphe
Chlorophenyl etheryl carboxylate, diphenyl
Bromophenyl ether carboxylate, diphenyl ether
Methyl phenyl carboxylate, diphenyl ether
Ethyl carboxylate, diphenyl ether carb
Propyl bonates, diphenyl ether carb
Isopropyl phenylates, diphenyl ether carb
Butylphenyl bonates, diphenyl ether carboxyl
Isobutylphenyl acid, diphenyl ether carboxyl
T-butylphenyl acid, diphenyl ether carboxylic acid
Acid methoxyphenyls, diphenyl ether carboxylic acid
Etoxin phenyls, diphenyl ether carboxylic acid
Nitrophenyls, diphenyl ether carboxylate
Nylphenyls, methyl diphenyl sulfide carboxylate
Propyls, diphenyl sulfide carboxylate, di
Isopropyl phenylsulfidecarboxylate, diphe
Isopropyl nylsulfidecarboxylates, diphenyl
Butyl sulfide carboxylate, diphenyl sulfide
Isobutyl carboxylate, diphenyl sulfide carb
Phenylates, diphenyl sulfide carboxylic acid full
Orophenyls, diphenyl sulfide carboxylic acid
Rophenyls, diphenyl sulfide carboxylic acid bromo
Phenyls, methyl diphenylsulfoncarboxylate
Phenyls, ethyl diphenylsulfidecarboxylate
Phenyls, propyl diphenyl sulfidecarboxylate
Phenyls, isopropyl diphenylsulfidecarboxylate
Ruphenyls, butyl diphenyl sulfidecarboxylate
Phenyls, isophenyl phenyl sulfide carboxylate
Tylphenyls, diphenylsulfidecarboxylic acid t-
Butyl phenyls, diphenyl sulfide carboxylic acid
Methoxyphenyls, diphenyl sulfide carboxylic acid
Ethoxyphenyls, diphenyl sulfide carboxylic acid
Nitrophenyls, diphenyl sulfide carboxylic acid
Phenylphenyls, methyl diphenylsulfonate
, Ethyl diphenylsulfoncarboxylate, dife
Propylsulfonyl carboxylate, diphenyl sulfo
Isopropyl carboxylate, diphenyl sulfone carb
Butyl borate, isophenyl diphenylsulfonate
Tyls, phenyl diphenylsulfonates, di
Phenylsulfoncarboxylic acid fluorophenyls, diph
Phenyl sulfone carboxylates, diphenyl
Bromophenyl sulfonate, diphenyl sulf
Methyl phenyl carboxylate, diphenyl sulfone
Ethyl carboxylate, diphenyl sulfone carb
Propyl bonate, diphenyl sulfone carb
Isopropylphenylates, diphenyl sulfone carboxyl
Butylphenyl bonates, diphenylsulfonecarboxylic
Isobutylphenyl acid, diphenyl sulfone carboxylic
T-butylphenyl acids, diphenylsulfonecarboxylic
Acid methoxyphenyls, diphenylsulfoncarboxylic acid
Ethoxyphenyls, diphenylsulfonate
Trophenyls, phenylphenyl diphenylsulfonate
Ruphenyls, 2,2-diphenylpropanecarboxylic acid
Tyls, ethyl 2,2-diphenylpropanecarboxylate
Propyl 2,2-diphenylpropanecarboxylates,
Isopropyl 2,2-diphenylpropanecarboxylate,
Butyl 2,2-diphenylpropanecarboxylate, 2,2-di
Isobutyl phenylpropanecarboxylate, 2,2-diph
Phenylpropanecarboxylates, 2,2-diphenyl
Fluorophenyl lupropane carboxylate, 2,2-diph
Chlorophenyl phenylpropanecarboxylates, 2,2-di
Bromophenyl phenylpropanecarboxylates, 2,2-
Methylphenyl diphenylpropanecarboxylate, 2,2
-Ethylphenyl diphenylpropanecarboxylate, 2,
Propylphenyl 2-diphenylpropanecarboxylate
And isopropyl 2,2-diphenylpropanecarboxylate
Phenyls, 2,2-diphenylpropanecarboxylate
Ruphenyls, 2,2-diphenylpropanecarboxylic acid
Sobutylphenyls, 2,2-diphenylpropanecarbo
T-butylphenyl acid, 2,2-diphenylpropane
Methoxyphenyl carboxylate, 2,2-diphenylpro
Ethoxyphenyl pancarboxylates, 2,2-diphenyl
Nitrophenyl propanecarboxylates, 2,2-diphenyl
Phenylphenyl propane carboxylate, 2,2-diph
Enyl-1,1,1,3,3,3-hexafluoropropanecarbo
Methylates, 2,2-diphenyl-1,1,1,3,3,3-hexa
Ethyl fluoropropanecarboxylates, 2,2-diphenyl
1,1,1,3,3,3-hexafluoropropanecarboxylic acid
Propyls, 2,2-diphenyl-1,1,1,3,3,3-hexaf
Isopropyl fluoropropanecarboxylate, 2,2-diph
Enyl-1,1,1,3,3,3-hexafluoropropanecarbo
Butyl acid, 2,2-diphenyl-1,1,1,3,3,3-hexa
Isobutyl fluoropropanecarboxylates, 2,2-diph
Enyl-1,1,1,3,3,3-hexafluoropropanecarbo
Phenylates, 2,2-diphenyl-1,1,1,3,3,3-hexyl
Safluoropropane carboxylic acid fluorophenyls, 2,
2-diphenyl-1,1,1,3,3,3-hexafluoropropane
Chlorophenyl carboxylate, 2,2-diphenyl-1,
1,1,3,3,3-hexafluoropropanecarboxylic acid bromo
Phenyls, 2,2-diphenyl-1,1,1,3,3,3-hexaph
Methylphenylfluoropropanecarboxylates, 2,2-di
Phenyl-1,1,1,3,3,3-hexafluoropropane
Ethylphenyl bonates, 2,2-diphenyl-1,1,1,3,
Propyl 3,3-hexafluoropropanecarboxylate
Nyls, 2,2-diphenyl-1,1,1,3,3,3-hexafluoro
Isopropylphenyl lopropanecarboxylate, 2,2-
Diphenyl-1,1,1,3,3,3-hexafluoropropaneca
Butylphenyl rubonates, 2,2-diphenyl-1,1,1,1
Isobutyl 3,3,3-hexafluoropropanecarboxylate
Phenyls, 2,2-diphenyl-1,1,1,3,3,3-hexaph
T-butylphenyl fluoropropanecarboxylates, 2,2
-Diphenyl-1,1,1,3,3,3-hexafluoropropane
Methoxyphenyl carboxylate, 2,2-diphenyl-1,
1,1,3,3,3-hexafluoropropanecarboxylic acid ethoxy
Cyphenyls, 2,2-diphenyl-1,1,1,3,3,3-hexa
Nitrophenyl fluoropropanecarboxylates, 2,2-
Diphenyl-1,1,1,3,3,3-hexafluoropropaneca
Phenyl phenyl rubonates, naphthalene carboxylic acid
Chills, ethyl naphthalenecarboxylates, naphthaleneca
Propyl rubonates, isopropyl naphthalene carboxylate
, Naphthalene carboxylate, naphthalene carb
Isobutyl borate, phenyl naphthalene carboxylate
, Fluorophenyl naphthalene carboxylate, naphtha
Chlorophenylene carboxylate, naphthalene carboxylic
Bromophenyls, methyl naphthalenecarboxylate
Nyls, ethylphenyl naphthalenecarboxylates, naph
Propylphenyl tarencarboxylate, naphthalenecar
Isopropylphenyl bonates, naphthalenecarboxylic acid
Butyl phenyls, isobutyl naphthalene carboxylate
Phenyls, t-butylphenyl naphthalenecarboxylate
, Methoxyphenyl naphthalene carboxylate, naphtha
Ethoxyphenylene carboxylates, naphthalene carb
Nitrophenyl acid, phenyl naphthalene carboxylate
Phenyls, methyl acetate, ethyl acetate, propyl acetate,
Isopropyl acetate, butyl acetate, isobutyl acetate, acetic acid
Phenyl, fluorophenyl acetates, chlorophenyl acetate
Bromophenyl acetates, methyl phenyl acetates,
Ethyl phenyl acetates, propyl phenyl acetates, acetic acid
Isopropylphenyls, butylphenyl acetates, acetic acid
Isobutylphenyls, t-butylphenylacetates, vinegar
Methoxyphenyl acids, ethoxyphenyl acetates, acetic acid
Nitrophenyls, phenylphenyl acetates, chlorovinegar
Methyl acetate, ethyl chloroacetate, propyl chloroacetate,
Isopropyl chloroacetate, butyl chloroacetate, chloroacetic acid
Isobutyl, phenyl chloroacetate, fluoro chloroacetate
Phenyls, chloroacetic acid chlorophenyls, chloroacetic acid
Bromophenyls, methylphenyl chloroacetates,
Ethylphenyl loacetates, propylphenyl chloroacetate
, Isopropylphenyl chloroacetate, chloroacetate
Tylphenyls, isobutylphenyl chloroacetates,
T-butylphenyl loroacetate, methoxyacetic acid chloroacetate
Phenyls, ethoxyphenyl chloroacetates, chloroacetic acid
Nitrophenyls, phenylphenyl chloroacetates, di
Methyl chloroacetate, ethyl dichloroacetate, dichloroacetic acid
Propyl, isopropyl dichloroacetate, dichloroacetate
Chill, isobutyl dichloroacetate, phenyl dichloroacetate
, Fluorophenyl dichloroacetate, dichloroacetic acid
Lorophenyls, bromophenyl dichloroacetates, dik
Methylphenyl loroacetate, ethylphenyichloroacetate
, Propylphenyl dichloroacetate, dichloroacetic acid
Isopropylphenyls, butylphenyl dichloroacetate
, Isobutylphenyl cycloacetate, dichloroacetic acid t
-Butylphenyls, methoxyphenyl dichloroacetate
, Ethoxyphenyl dichloroacetate, dichloroacetate
Trophenyls, phenylphenyl dichloroacetates,
Methyl chloroacetate, ethyl trichloroacetate, trichloro
Propyl acetate, isopropyl trichloroacetate, Trik
Butyl loloacetate, Isobutyl trichloroacetate, Trichloro
Phenyl acetate, fluorophenyl trichloroacetate,
Chlorophenyl trichloroacetates, trichloroacetic acid bro
Mophenyls, methylphenyl trichloroacetates, tri
Ethylphenyl chloroacetate, propyl trichloroacetate
Phenyls, isopropylphenyl trichloroacetates,
Butylphenyl trichloroacetate, isochlorotrichloroacetate
Butylphenyls, t-butylphenyl trichloroacetate
, Methoxyphenyl trichloroacetate, trichlorovinegar
Ethoxyphenyl acids, nitrophenyl trichloroacetate
, Phenylphenyl trichloroacetates, fluoroacetic acid
Methyl, ethyl fluoroacetate, propyl fluoroacetate,
Isopropyl fluoroacetate, butyl fluoroacetate, full
Isobutyl oroacetate, phenyl fluoroacetate, fluoro
Fluorophenyl acetates, chlorophenyl fluoroacetates
, Bromophenyl fluoroacetates, methyl fluoroacetate
Phenyls, ethylphenyl fluoroacetates, fluoro
Propylphenyl acetate, isopropyl fluoroacetate
Phenyls, butylphenyl fluoroacetates, fluoro
Isobutylphenyl acetates, t-butyl fluoracetate
Phenyls, methoxyphenyl fluoroacetates, fluoro
Ethoxyphenyl acetates, nitrophenyl fluoroacetate
, Phenylphenyl fluoroacetates, difluoroacetic acid
Methyl, ethyl difluoroacetate, propyl acetate
Toluene, isopropyl difluoroacetate, butyl difluoroacetate
Isobutyl difluoroacetate, phenyl difluoroacetate
, Fluorophenyl difluoroacetate, difluorovinegar
Acid chlorophenyls, bromophenyl difluoroacetate
, Methylphenyl difluoroacetate, difluoroacetic acid
Ethylphenyls, propylphenyl difluoroacetate
, Isopropylphenyl difluoroacetate, difluoro
Butylphenyl roacetate, isobutyl difluoroacetate
Phenyls, t-butylphenyl difluoroacetates, diph
Methoxyphenyl fluoroacetate, ethoxy trifluoroacetate
Cyphenyls, nitrophenyl difluoroacetates, diph
Phenylphenyl fluoroacetates, methyl trifluoroacetate
, Ethyl trifluoroacetate, trifluoroacetic acid
, Isopropyl trifluoroacetate, trifluoroacetic acid
Butyl, isobutyl trifluoroacetate, trifluorovinegar
Phenyl acid, fluorophenyl trifluoroacetate,
Chlorophenyl trifluoroacetate, trifluoroacetate
Lomophenyls, methylphenyl trifluoroacetates,
Ethylphenyl trifluoroacetate, trifluoroacetic acid
Propylphenyls, isopropyl trifluoroacetate
Phenyls, butylphenyl trifluoroacetates, trif
Isobutylphenyl fluoroacetate, trifluoroacetic acid t
-Butylphenyls, methoxyphenyl trifluoroacetate
, Ethoxyphenyl trifluoroacetates, trifur
Nitrophenyl oroacetates, Phenyl trifluoroacetate
Phenyls, methyl nitroacetate, methyl nitroacetate,
Propyl troacetate, isopropyl nitroacetate, nitro vinegar
Butyl acetate, isobutyl nitroacetate, phenyl nitroacetate
, Fluorophenyl nitroacetate, chloro nitroacetate
Phenyls, bromophenyl nitroacetates, nitroacetic acid
Methylphenyls, ethylphenyl nitroacetates, nitro
Propyl phenyl acetates, isopropyl nitroacetate
Phenyls, butylphenyl nitroacetates,
Sobutylphenyls, t-butylphenyl nitroacetate
, Methoxyphenyl nitroacetate, ethoxy nitroacetate
Cyphenyls, nitrophenyl nitroacetates, nitrovinegar
Phenylphenyls, methyl propionate, propio
Ethyl phosphate, propyl propionate, isopropionate
Propyl, butyl propionate, isobutyrate
Phenyl, propionate, fluoropropionate
Nil, chlorophenyl propionate, propionic acid
Bromophenyls, methylphenyl propionates,
Ethyl phenyl lopionate, propyl propionate
Phenyls, isopropylphenyl propionates, pro
Butylphenyl pionates, isobutyl propionate
Phenyls, t-butylphenyl propionates, propyl
Methoxyphenyl onates, ethoxyxin propionate
Phenyls, nitrophenyl propionates, propion
Phenylphenyls, methyl butyrate, ethyl butyrate, butyric acid
Propyl, isopropyl butyrate, butyl butyrate, isobutyrate
Butyl, phenyl butyrate, fluorophenyl butyrate, butyric acid
Lolophenyls, bromophenyl butyrate, methyl butyrate
Phenyls, ethylphenyl butyrate, propylphenyl butyrate
, Isopropylphenyl butyrate, butylphenyl butyrate
Compounds, isobutylphenyl butyrate, t-butylphenyl butyrate
Nyls, methoxyphenyl butyrate, ethoxyphenyl butyrate
, Nitrophenyl butyrate, phenylphenyl butyrate
, Methyl valerate, ethyl valerate, propyl valerate, valley
Isopropyl valerate, butyl valerate, isobutyl valerate,
Phenyl valerate, fluorophenyl valerate, potassium valerate
Lolophenyls, bromophenyl valerates, methyl valerate
Phenyl, ethyl valerate, propyl valerate
Ruphenyls, isopropyl valerate, valeric acid
Butylphenyls, isobutylphenylvalerate, valerian
T-butylphenyl acid, methoxyphenyl valerate,
Ethoxyphenyl valerate, nitrophenyl valerate,
Phenylphenyl valerate, methyl caproate, capro
Ethyl phosphate, propyl caproate, isoprocaproate
Pill, butyl caproate, isobutyl caproate, cap
Phenyl lonate, fluorophenyl caproate, cap
Chlorophenyl lonates, bromophenyl caproate
, Methylphenyl caproate, ethyl caproate
Phenyls, propylphenyl caproate, caproic acid
Isopropylphenyls, butylphenyl caproate
, Isobutylphenyl caproate, t-caproic acid
Butylphenyls, methoxyphenyl caproate,
Ethoxyphenyl pronoates, nitrophenyl caproate
Phenylphenyl caproate, methyl cinnamate,
Ethyl cinnamate, propyl cinnamate, isopropyl cinnamate,
Butyl cinnamate, isobutyl cinnamate, phenyl cinnamate, cinnamate
Fluorophenyl cinnamate, chlorophenyl cinnamate, cinnamate
Bromophenyl cinnamate, methylphenyl cinnamate, cinnamon
Ethylphenyls, propylphenylcinnamate, cinnamon
Isopropylphenyls, butylphenylcinnamates,
Isobutylphenyl cinnamate, t-butylphenyl cinnamate
Methoxyphenyl cinnamate, ethoxy cinnamate
Nyls, nitrophenyl cinnamate, phenyl cinnamate
Nil, methyl cyclohexanecarboxylate, cyclohexyl
Ethyl suncarboxylate, cyclohexanecarboxylic acid pro
Pill, isopropyl cyclohexanecarboxylate, cyclo
Hexane butyl carboxylate, cyclohexane carboxylic acid
Isobutyl, phenyl cyclohexanecarboxylate, cyclone
Fluorohexanecarboxylic acid fluorophenyls, cyclohexyl
Chlorophenyl carboxylate, cyclohexanecar
Bromophenyl borate, cyclohexanecarboxylic acid
Tylphenyls, ethyl cyclohexanecarboxylate
Nyls, propylphenyl cyclohexanecarboxylate
, Isopropylphenyl cyclohexanecarboxylate
, Butylphenyl cyclohexanecarboxylates, cyclone
Isohexanephenyl hexanecarboxylate, cyclohexane
T-butyl phenyl carboxylate, cyclohexa
Methoxyphenyls
Ethoxyphenyl bonates, cyclohexanecarboxylic acid
Nitrophenyls, phenyl cyclohexanecarboxylate
And phenyls. These monocarboxylic acids
Ters are used alone or in combination of two or more.

The amount of the monocarboxylic acids used is 0.001 to 1.0 mole per mole of aromatic diamine. If the amount is less than 0.001 mol, the viscosity increases during high-temperature molding, which causes a reduction in moldability. On the other hand, if it exceeds 1.0 mol, the mechanical properties deteriorate. A preferred amount is 0.01 to 0.5 mol.

When a monovalent amine is used, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,4-xylidine, 2,5-xylidine, 2,6- Xylidine, 3,4-xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p
-Chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m
-Nitroaniline, p-nitroaniline, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p-phenetidine, o-aminophenol, m-aminophenol, p-aminophenol, o- Aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenyl Phenyl ether, 3-aminophenylphenyl ale, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3-amino Phenylphenylsulfide, 4-aminophenylphenylsulfide, 2-aminophenylphenylsulfone, 3-aminophenylphenylsulfone, 4-aminophenylphenylsulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2- Amino-1-naphthol, 4-amino-1
-Naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8
-Amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, isopropylamine, Examples thereof include diisopropylamine, butylamine, dibutylamine, isobutylamine, diisobutylamine, pentylamine, dipentylamine, benzylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, and cyclohexylamine. These monoamines are used alone or in combination of two or more.

The amount of the monoamine used is 0.001 to 1.0 mole per mole of aromatic dicarboxylic acids. If the amount is less than 0.001 mol, the viscosity increases during high-temperature molding, which causes a reduction in molding processability. On the other hand, if it exceeds 1.0 mol, the mechanical properties deteriorate. A preferred amount is 0.01 to 0.5 mol.

The aromatic polyamide and its resin composition of the present invention can be subjected to melt molding. In this case, other thermoplastic resins can be blended in an appropriate amount according to the purpose within a range that does not impair the purpose of the present invention. Thermoplastic resins that can be blended include polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polyimide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyphenylenesulfide, polyamideimide, polyetherimide, and deformation. And polyphenylene oxide. It is also possible to add a thermosetting resin or a filler to such an extent that the object of the present invention is not impaired. Examples of the thermosetting resin include a phenol resin and an epoxy resin. As the filler, graphite,
Abrasion resistance improving materials such as carbon random, silica powder, molybdenum disulfide, and fluororesin; reinforcing materials such as glass fiber, carbon fiber, boron fiber, silicon carbide fiber, carbon whisker, asbestos, metal fiber, and ceramic fiber; trioxide Flame retardant such as antimony, magnesium carbonate, calcium carbonate, etc., electrical properties improver such as clay and mica, tracking resistance improver such as asbestos, silica, graphite, etc., acid resistance such as barium sulfate, silica, calcium metasilicate, etc. And thermal conductivity improving materials such as iron powder, zinc powder, aluminum powder, and copper powder, as well as glass beads, talc, diatomaceous earth, alumina, shirasubarun, hydrated alumina, metal oxides, coloring agents, and the like.

Various materials are used as the fibrous reinforcing material used in the present invention, for example, glass fiber, carbon fiber, potassium titanate fiber, aromatic polyamide fiber, silicon carbide fiber,
Alumina fiber, boron fiber, ceramic fiber and the like can be mentioned, and glass fiber, carbon fiber, potassium titanate fiber and aromatic polyamide fiber are particularly preferably used.

The glass fibers used in the present invention are those obtained by quenching molten glass while stretching it by various methods to form a thin fiber having a predetermined diameter. Roving, etc., which are arranged in a bundle. For the glass fiber, a silane coupling agent such as aminosilane and epoxysilane, chromic chloride, and other surface treatment agents suitable for the purpose can be used in order to have an affinity with the base resin of the present invention. The length of the glass fiber in the present invention greatly affects the physical properties of the obtained molded article and the workability during production of the molded article. Generally, as the glass fiber length increases, the physical properties of the molded article improve, but conversely, the workability during the production of the molded article deteriorates. For this reason, the length of the glass fiber in the present invention is 0.1 to 6 mm, preferably 0.
Those having a size in the range of 3 to 4 mm are preferable because the physical properties and workability of the molded product are balanced.

The carbon fiber used in the present invention is a high elasticity and high strength fiber obtained by carbonizing polyacrylonitrile, petroleum pitch or the like as a main raw material. In the present invention, both polyacrylonitrile and petroleum pitch can be used. Carbon fibers having an appropriate diameter and an appropriate aspect ratio (length / diameter ratio) are used depending on the reinforcing effect and the mixing property. The diameter of the carbon fiber is usually 5 to 20 μm, particularly 8 to 15 μm.
m is preferable. The aspect ratio is 1-60
0, and particularly preferably about 100 to 350, depending on the reinforcing effect and the mixing property. If the aspect ratio is small, there is no reinforcing effect, and if the aspect ratio is large, the mixing property is poor, and a good molded product cannot be obtained. Further, those obtained by treating the surface of the carbon fiber with various treatment agents, for example, an epoxy resin, a polyamide resin, a polycarbonate resin, a polyacetal resin and the like, and those using a known surface treatment agent depending on the purpose are also used.

The potassium titanate fiber used in the present invention is a kind of high-strength fiber (whisker) and has a chemical composition of K ₂
A _{O · 6TiO 2, K 2 O} · 6TiO 2 · 1 / 2H 2 O needle-like crystals having a basic, representative melting point is 1,300-1,350 ° C.. An average fiber length of 5 to 50 μm and an average fiber diameter of 0.05 to 1.0 μm are applied, but the average fiber length is 20 to 30 μm and the average fiber diameter is 0.1.
~ 0.3 µm is preferred. The potassium titanate fiber can be usually used without any treatment, but in order to have an affinity with the base resin of the present invention, a silane coupling agent such as amine silane or epoxy silane,
Other surface treatment agents suitable for the purpose can be used.

The aromatic polyamide fiber used in the present invention is a heat-resistant organic fiber which has been relatively newly developed, and is expected to be developed in various fields by utilizing many unique characteristics. For example, typical examples include those having the following structural formulas, and at least one of them or 2
Mixtures of more than one species are used.

In addition, there are aromatic polyamide fibers having various skeletons due to ortho, meta, and para structural isomerism. Among them, those having a para-para bond of (1) having a high softening point and a high melting point are heat-resistant organic fibers in the present invention. Most preferred.

In the case of 5 parts by weight or less of the glass fiber and the carbon fiber, the reinforcing effect peculiar to the glass fiber or the carbon fiber characteristic of the present invention cannot be obtained. Conversely, if it is used in an amount of 100 parts by weight or more, the fluidity during molding of the composition becomes poor, and it becomes difficult to obtain a satisfactory molded product. If the content of the potassium titanate fiber is 5 parts by weight or less, the improvement in mechanical properties at high temperatures, which is a feature of the present invention, is insufficient. Conversely, if the amount is large, dispersion in melt mixing becomes insufficient, and further, the fluidity becomes low, and molding under ordinary conditions becomes difficult, which is not preferable. The preferred amount is 10 to 100 parts by weight. When the amount of the aromatic polyamide fiber is 5 parts by weight or less, a composition excellent in moldability and mechanical strength, which is a feature of the present invention, cannot be obtained. If it is used in an amount of 100 parts by weight or more, the fluidity of the composition at the time of molding deteriorates, and it becomes difficult to obtain a satisfactory molded product. The preferred amount is 10 to 50 parts by weight.

The resin composition using the polyamide of the present invention can be produced by a generally known method, but the following method is particularly preferable.

(1) The polyamide powder and the fibrous reinforcing material are pre-mixed using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill, ribbon blender, and the like, and then kneaded with a generally known melt mixer, hot roll, or the like. Pellet or powder.

(2) Polyamide powder is dissolved or suspended in an organic solvent in advance, a fibrous reinforcing material is immersed in the solution or suspension, and then the solvent is removed in a hot air oven, and then pelletized or powdered. To In this case, as a solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,
3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2 -Methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea,
Hexamethylphosphoramide and the like. These organic solvents may be used alone or in combination of two or more.

The polyamide resin composition of the present invention is molded by a known molding method such as an injection molding method, an extrusion molding method, a compression molding method, a rotational molding method, and put into practical use.

〔Example〕

Hereinafter, the production examples of the aromatic polyamide of the present invention and the physical properties and performance of the obtained aromatic polyamide will be described in detail with reference to Examples and Comparative Examples.

 In the examples, various physical properties were measured by the following methods.

Logarithmic viscosity: 0.50 g of polyamide powder was added to N-methyl-2-
After dissolving in 100 ml of pyrrolidone, measurement was performed at 35 ° C.

Glass transition temperature (Tg): DSC (Shimadzu DT-40 series, DS
C-41M).

5% weight loss temperature: measured by DTA-TG (Shimadzu DT-40 series, DTG-40M) in air.

Melt viscosity: Measured with a load of 100 kg using Shimadzu Koka Flow Tester CFT500A.

Synthesis Example 1 In a vessel equipped with a stirrer and a nitrogen inlet tube, under a nitrogen atmosphere, 1,4-bis [4- (4-aminophenoxy)-
After 26.43 g (0.050 mol) of [α, α-dimethylbenzyl] benzene and 296 g of N-methyl-2-pyrrolidone were charged and dissolved, 10.12 g (0.10 mol) of triethylamine was added, and the mixture was cooled to 5 ° C. Thereafter, stirring was strengthened, and 10.15 g (0.050 mol) of terephthalic acid chloride was charged, and stirring was continued at room temperature for 3 hours. The viscous polymer solution thus obtained was discharged into vigorously stirred methanol to precipitate a white powder. This white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours to give 32.81 g (yield 99.6 g).
%) Of a polyamide powder.

The logarithmic viscosity of this polyamide powder was 2.04 dl / g, the glass transition temperature was 238.0 ° C, and the 5% weight loss temperature was 480.8 ° C.

The results of elemental analysis of the obtained polyamide powder are as follows.

FIG. 1 shows an infrared absorption spectrum of the obtained polyamide powder. This spectrum diagram, in the vicinity of 1660 cm ^-1 and near 1510 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Further, the obtained polyamide powder was dissolved in N-methyl-2-pyrrolidone, and then cast on a glass plate.
C. for 1 hour and 250.degree. C. for 2 hours to obtain a colorless and transparent polyamide film. This polyamide film had a tensile strength of 1320 kg / cm ² and a tensile elongation of 31%. Both measurement methods are based on ASTM D-882.

The water absorption of this film was 0.72%. The measurement method is based on ASTM D-750-63.

Synthesis Example 2 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene in Synthesis Example 1 was added to 1,3
-Bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene was used in the same manner as in Example 1 except that polyamide powder having a logarithmic viscosity of 1.55 dl / g, 32.71 g was used.
(99.3% yield).

The glass transition temperature of this polyamide powder is 200.1 ° C, 5
The% weight loss temperature was 480.0 ° C.

The results of elemental analysis of the obtained polyamide powder are as follows.

FIG. 2 shows an infrared absorption spectrum of the obtained polyamide powder. In this spectrogram, a significant absorption in the vicinity of 1660 cm ^-1 and near 1510 cm ^-1 which is the characteristic absorption band of amide was observed.

Further, a colorless and transparent polyamide film was obtained in the same manner as in Synthesis Example 1 using the obtained polyamide powder. The tensile strength of this polyamide film was 1270 kg / cm ² , the tensile elongation was 37%, and the water absorption was 0.77%.

Examples 1 and 2 Each of the polyamides obtained in Examples 1 and 4 was 100
A silane-treated glass fiber having a fiber length of 3 mm and a fiber diameter of 13 μm (parts by weight: Nitto Boseki Co., Ltd .: CS-3PE-476)
S) was added in the amount shown in Table 1, mixed with a drum blender mixer (manufactured by Kawada Seisakusho), melt-kneaded at a temperature of 360 ° C with a single screw extruder having a diameter of 30 mm, and then the strand was air-cooled and cut. Thus, a pellet was obtained.

The obtained pellets were injection molded (Arburg molding machine, maximum clamping force 35 tons, injection pressure 500 kg / cm ² , cylinder temperature 360 ° C, mold temperature 150 ° C) to obtain test pieces for various measurements.
A measurement was made. Measured tensile strength (according to ASTM D-638), flexural strength and flexural modulus (ASTM D-790), Izod impact strength (notched) (ASTM D-256), heat distortion temperature (ASTM D-648), molding Table 1 shows the results of the shrinkage ratio (ASTM D-955).

Comparative Examples 1 and 2 Each of the polyamides obtained in Synthesis Examples 1 and 2 was 100
Table 2 shows the results obtained by using the same glass fibers as those in Examples 1 and 2 for parts by weight outside the scope of the present invention.

Examples 3 and 4 Each of the polyamides obtained in Synthesis Examples 1 and 2 was 100
To the parts by weight, carbon fibers having an average diameter of 12 μm, a length of 3 mm, and an aspect ratio of 250 (trade name of Toray Co., Ltd.) were added in the amounts shown in Table-3.
The result shown in FIG.

Comparative Examples 3 and 4 Each of the polyamides obtained in Synthesis Examples 1 and 2 was 100
With respect to parts by weight, the same carbon fiber as in Examples 3 and 4 was used.
Extruded strands were tried in the same manner as in Examples 3 and 4 by adding 120 parts by weight of each, but none of the strands could be formed.

Examples 5 and 6 Each of the polyamides obtained in Synthesis Examples 1 and 2 was 100
0.2 μm cross-sectional diameter and 20 μm average fiber length based on weight
Was added in the amounts shown in Table 4 and the results shown in Table 4 were obtained in the same manner as in Examples 1 and 2.

Examples 7 and 8 Each of the polyamides obtained in Synthesis Examples 1 and 2 was 100
To the parts by weight, an aromatic polyamide fiber having an average fiber length of 3 mm (Dupont: Kevlar) was added in an amount shown in Table 5, and the results shown in Table 5 were obtained in the same manner as in Examples 1 and 2. Obtained.

[Effects of the Invention] The present invention provides a completely novel aromatic polyamide having excellent processability or thermal stability in addition to the excellent heat resistance inherent to the aromatic polyamide. Further, the aromatic polyamide resin composition of the present invention has excellent dimensional stability and mechanical strength, and has extremely good workability. Therefore, electric / electronic parts, automobile parts, precision machine parts, and the like that require these physical properties are required. It is an extremely useful material used for medical equipment parts, base materials for space aircraft, and the like, and has a very large industrial use effect.

[Brief description of the drawings]

FIGS. 1 and 2 are examples of infrared absorption spectra of the respective polyamide powders obtained in Synthesis Examples 1 and 2.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 77/00-77/12 C08G 69/00-69/50 CA (STN)

Claims (2)

(57) [Claims] (1) The following formula (I) (Wherein X is a condensed polycyclic aromatic group or Or one or more groups selected from the group consisting of However, Y is directly joined R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group,
Or a halogen group, a phenyl group, a is 0, 1 or 2, b
Represents 0 or an integer of 1 to 4. N represents an integer of 1 to 1000. In the polyamide obtained by reacting an aromatic polyamide and / or a diamine with a dicarboxylic acid or a dicarboxylic acid derivative represented by the following formula (I): (Wherein X is a condensed polycyclic aromatic group or Or one or more groups selected from the group consisting of However, Y is directly joined R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group,
Or a halogen group, a phenyl group, a is 0, 1 or 2, b
Represents 0 or an integer of 1 to 4. N represents an integer of 1 to 1000. ) Having a repeating unit represented by the following formula: A polyamide having good heat stability, characterized in that it is obtained by reacting at a ratio of 0.01 to 1.0 mol per 1 mol.
Or a polyamide obtained by reacting a diamine with a dicarboxylic acid or a dicarboxylic acid derivative; (Wherein X is a condensed polycyclic aromatic group or Or one or more groups selected from the group consisting of However, Y is directly joined R is an alkyl group having 1 to 4 carbon atoms, an alkoxy group,
Or a halogen group, a phenyl group, a is 0, 1 or 2, b
Represents 0 or an integer of 1 to 4. N represents an integer of 1 to 1000. ) As a basic skeleton, and the polycondensation reaction is performed in the presence of a monovalent amine;
The amount of the aromatic diamine is 0.7 to 1.0 mol per 1 mol of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative, and the amount of the monovalent amine is 1 mol of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative. 100 parts by weight of a polyamide having good thermal stability and a fibrous reinforcing material of 5 to 1 which are obtained by reacting at a ratio of 0.001 to 1.0 mol.
A polyamide resin composition comprising 00 parts by weight. 2. The polyamide resin composition according to claim 1, wherein the fibrous reinforcing material is selected from the group consisting of glass fibers, carbon fibers, potassium titanate fibers and aromatic polyamide fibers.