JP2593583B2 - Polyamide resin and its resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat-meltable aromatic polyamide having high heat resistance.

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

[0003]

2. Description of the Related Art Conventionally, aromatic polyamides obtained by reacting an aromatic diamine or an aromatic diisocyanate with an aromatic dicarboxylic acid or a derivative thereof have been known for their excellent physical properties and good heat resistance. It is expected to be widely used in fields requiring heat resistance in the future.

[0004] However, the aromatic polyamides which have been developed in the past have many mechanical properties and heat resistance, but all have the drawbacks of poor moldability and high water absorption. Was.

For example, equation (4)

[0006]

Embedded image 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 tension 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 fields such as fibers by wet spinning or pulp. Further, the water absorption rate is as high as 4.5%, which is unsuitable as a substrate for electric / electronic parts because it adversely affects dimensional stability, insulation properties, solder heat resistance and the like.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polyamide having excellent processability and low water absorption, in addition to the excellent heat resistance inherent to the aromatic polyamide, and a process for producing the aromatic polyamide. .

Another object of the present invention is to provide a novel resin composition having improved processability by improving the mechanical strength and dimensional stability of the polyamide.

[0009]

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

That is, the present invention relates to [1]

[0011]

Embedded image Ｘwherein X is a condensed polycyclic aromatic group or

[0012]

Embedded image Or one or more groups selected from the group consisting of However, Y is a direct _{bond, -O-, -S-, -SO 2 -} , -CO-
_{, -CH 2 -, -C (CH} 3) 2 - or -C (CF _{3) 2} - a and, R represents 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. Aromatic polyamide represented by｝, [2]

[0013]

Embedded image 6,6'-bis (4-aminophenoxy) -3,
3,3 ′, 3′-tetramethyl-1,1′-spirobiindane and / or 6,6′-bis (3-aminophenoxy ) -3,
3,3 ', 3'-tetramethyl-1,1'-spirobiindane,
A method for producing an aromatic polyamide of the formula 1, characterized by being obtained by polycondensing an aromatic dicarboxylic acid in an organic solvent. Wherein X is a condensed polycyclic aromatic group or One or more groups selected from the group consisting of: Y is a direct bond, -O-, -S-, -SO2-,-
CO-, -CH2-, -C (CH3) 2- or -C (CF3) 2-
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 n represents an integer of 1 to 4, and n represents an integer of 1 to 1000. {Wherein, X is one or two or more groups selected from the group consisting of a condensed polycyclic aromatic group or Chemical Formula 2, Y is a direct bond, -O- , -S-, -SO2-, -CO-, -C
H2-, -C (CH3) 2- or -C (CF3) 2-, wherein 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 is 0 or 1
Represents an integer of 1 to 4, and n represents an integer of 1 to 1000. Having a repeating unit represented by と し て as a basic skeleton,
Polyamide having good thermal stability, in which the molecular terminal of the polymer is blocked with a monovalent amine or a monovalent carboxylic acid or a carboxylic acid derivative, and a method for producing the same, [4] wherein X is condensation Y is a direct bond, -O-, -S-, -SO2-, -CO-, -C, a polycyclic aromatic group or one or more groups selected from the group consisting of
H2-, -C (CH3) 2- or -C (CF3) 2-, wherein 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 is 0 or 1
Represents an integer of 1 to 4, and n represents an integer of 1 to 1000. A polyamide resin composition comprising 100 parts by weight of a polyamide represented by｝ and 5 to 100 parts by weight of a fibrous reinforcing material.

The aromatic polyamide of the present invention is a diamine represented by the formula (3) as a diamine component, that is, 6,6'-bis (4-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1. , 1'-spirobiindane and / or 6,6'-bi
It is obtained by using su (3-aminophenoxy ) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane and polymerizing it with an aromatic dicarboxylic acid or 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, 6,
6'-bis (4-aminophenoxy) 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindan and / or 6,
It is characterized by using 6'-bis (3-aminophenoxy ) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane as a diamine component. In addition, it is a thermoplastic aromatic polyamide having excellent processability and a resin composition thereof.

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

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

Examples of the diamines which can be used in combination are, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 2-chloro-1,2-phenylene Diamine, 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′-diaminodiphenylether, 3,4′-diaminodiphenylether, 4,4′-diaminodiphenylether, 3,3′-diaminodiphenylsulfide, 3 , 4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3 '
-Diaminodiphenylsulfoxide, 3,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone, 3,4'-
Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone , 3,4'-di
Aminobenzophenone , 4,4'-diaminobenzopheno
Emissions, 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- (4
-Aminophenoxy) phenyl] -1,1,1,3,3,3-hex
Safluoropropane and / or 2,2-bis [4-
(3-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, 1,4-bis [4- (4-
Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy)-
α, α-dimethylbenzyl] benzene and the like,
These may be used alone or in combination of two or more.

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, a method according to claims 2 to 4 is provided.
The aromatic diamine used in this method is 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane and / or 6,6 ′. -Screw
(3-aminophenoxy ) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane.

The aromatic dicarboxylic acids used in the method of claim 2 are aromatic dicarboxylic dihalides. 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, methoxy isophthalic dichloride, methoxy isophthalic dibromide, ethoxy isophthalic dichloride Ethoxyisophthalic dibromide, chloroisophthalic dichloride, chloroisophthalic dibromide, bromoisophthalic dichloride, bromoisophthalic dibromide, terephthalic dichloride, terephthalic dibromide, methyl terephthalic dichloride, methyl terephthalic dibromide , Ethyl terephthalic acid dichlorides,
Ethyl terephthalic acid dibromide, methoxy terephthalic acid dichloride, methoxy terephthalic acid dibromide,
Ethoxyterephthalic acid dichloride, ethoxyterephthalic acid dibromide, chloroterephthalic acid dichloride,
Chloroterephthalic acid dibromide, bromoterephthalic acid dichloride, bromoterephthalic acid dibromide, 4,4 '
-Biphenyl dicarboxylic acid dichloride, 4,4'-biphenyl dicarboxylic acid dibromide, 4,4'-diphenyl ether dicarboxylic acid dichloride, 4,4'-diphenyl ether dicarboxylic acid dibromide, 4,4'-benzophenone dicarboxylic acid dichloride, 4,4 ' -Benzophenone 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′-diphenylmethane dicarboxylic acid dichloride, 4,4′-diphenylmethane dicarboxylic 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 acid dichloride, 1,4
-Naphthalenedicarboxylic dibromide, 2,3-naphthalenedicarboxylic dichloride, 2,3-naphthalenedicarboxylic dibromide, 2,6-naphthalenedicarboxylic dichloride, 2,6-naphthalenedicarboxylic 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 acid, ethylphthalic acid, methoxyphthalic acid, ethoxyphthalic acid, chlorophthalic acid, bromophthalic acid,
Isophthalic acid, methyl isophthalic acid, ethyl isophthalic acid, methoxy isophthalic acid, ethoxy isophthalic acid, chloroisophthalic acid, bromoisophthalic acid,
Terephthalic acid, methyl terephthalic acid, ethyl terephthalic acid, methoxy terephthalic acid, ethoxy terephthalic acid, chloroterephthalic acid, bromoterephthalic acid,
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 dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 2,2
-Bis (4-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 1,4-naphthalenedicarboxylic acid, 2,3
-Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and the like. These aromatic dicarboxylic acids are used alone or in combination of two or more.

In the method of claim 4, for example, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, Diisopropyl isophthalate, dibutyl isophthalate, diisobutyl isophthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisopropyl terephthalate, dibutyl terephthalate, diisobutyl terephthalate, dimethyl 4,4'-biphenyldicarboxylate, 4,4 ' −
Diethyl biphenyl dicarboxylate, dipropyl 4,4'-biphenyl dicarboxylate, diisopropyl 4,4'-biphenyl dicarboxylate, dibutyl 4,4'-biphenyl dicarboxylate, diisobutyl 4,4'-biphenyl dicarboxylate, 4,4 '
-Dimethyl diphenyl ether dicarboxylate, diethyl 4,4'-diphenyl ether dicarboxylate, dipropyl 4,4'-diphenyl ether dicarboxylate, diisopropyl 4,4'-diphenyl ether dicarboxylate, dibutyl 4,4'-diphenyl ether dicarboxylate, 4,4 ' -Diisobutyl diphenyl ether dicarboxylate, dimethyl 4,4'-diphenyl sulfide dicarboxylate, diethyl 4,4'-diphenyl sulfide dicarboxylate, dipropyl 4,4'-diphenyl sulfide dicarboxylate, diisopropyl 4,4'-diphenyl sulfide 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'-benzophenate Njikarubon acid dipropyl, 4,4'-benzophenone dicarboxylic acid diisopropyl, 4,4'-benzophenone dicarboxylic acid dibutyl 4,4'-benzophenone dicarboxylic acid diisobutyl,
Dimethyl 4,4'-diphenylsulfonedicarboxylate, 4,4 '
-Diethyl diphenylsulfone dicarboxylate, dipropyl 4,4'-diphenylsulfone dicarboxylate, diisopropyl 4,4'-diphenylsulfone dicarboxylate, dibutyl 4,4'-diphenylsulfone dicarboxylate, diisobutyl 4,4'-diphenylsulfone dicarboxylate Dimethyl 4,4'-diphenylmethanedicarboxylate, diethyl 4,4'-diphenylmethanedicarboxylate, dipropyl 4,4'-diphenylmethanedicarboxylate, diisopropyl 4,4'-diphenylmethanedicarboxylate, dibutyl 4,4'-diphenylmethanedicarboxylate Diisobutyl 4,4'-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-hexafluoropropane, 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, 1,4-naphthalene Diethyl dicarboxylate, dipropyl 1,4-naphthalenedicarboxylate, diisopropyl 1,4-naphthalenedicarboxylate, dibutyl 1,4-naphthalenedicarboxylate, diisobutyl 1,4-naphthalenedicarboxylate, dimethyl 2,3-naphthalenedicarboxylate, 2 Diethyl 3-, 2-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, dipropyl 2,6-naphthalenedicarboxylate, diisopropyl 2,6-naphthalenedicarboxylate,
Aromatic dicarboxylic acid dialkylates such as dibutyl 2,6-naphthalenedicarboxylate, diisobutyl 2,6-naphthalenedicarboxylate and / or diphenyl phthalate, di (fluorophenyl) phthalate, di (chlorophenyl) phthalate, phthalate Acid di (bromophenyl) s, di (methylphenyl) phthalate, di (ethylphenyl) phthalate, di (propylphenyl) phthalate, di (isopropylphenyl) phthalate, di (butylphenyl) phthalate ), Di (isobutylphenyl) phthalates,
Di (t-butylphenyl) phthalate, di (methoxyphenyl) phthalate, di (ethoxyphenyl) phthalate
, Di (nitrophenyl) phthalate, di (phenylphenyl) phthalate, diphenyl isophthalate, di (fluorophenyl) isophthalate, di (chlorophenyl) isophthalate, di (bromophenyl) isophthalate
, Di (methylphenyl) isophthalate, di (ethylphenyl) isophthalate, di (propylphenyl) isophthalate, di (isopropylphenyl) isophthalate, di (butylphenyl) isophthalate, di (isophthalate) (Isobutylphenyl) s, di (t-butylphenyl) isophthalate, di (methoxyphenyl) isophthalate, di (ethoxyphenyl) isophthalate
, Di (nitrophenyl) isophthalate, di (phenylphenyl) isophthalate, diphenyl terephthalate, di (fluorophenyl) terephthalate, di (chlorophenyl) terephthalate, di (bromophenyl) terephthalate, Di (methylphenyl) terephthalate,
Di (ethylphenyl) terephthalate, di (propylphenyl) terephthalate, di (isopropylphenyl) terephthalate, di (butylphenyl) terephthalate
, Di (isobutylphenyl) terephthalate, di (t-butylphenyl) terephthalate, di (methoxyphenyl) terephthalate, di (ethoxyphenyl) terephthalate, di (nitrophenyl) terephthalate, terephthalate Acid di (phenylphenyl) s, diphenyl 4,4′-biphenyldicarboxylate, di (fluorophenyl) 4,4′-biphenyldicarboxylate, di (chlorophenyl) 4,4′-biphenyldicarboxylate, 4,4 '-Biphenyldicarboxylic acid di (bromophenyl) s, 4,4'-biphenyldicarboxylic acid di (methylphenyl) s, 4,4'-biphenyldicarboxylic acid di (ethylphenyl) s, 4,4'-biphenyldicarboxylic acid Di (propylphenyl) s, 4,4′-biphenyldicarboxylic acid di (isopropylphenyl) s,
4,4'-biphenyldicarboxylic acid di (butylphenyl)
4,4'-biphenyldicarboxylic acid di (isobutylphenyl) s, 4,4'-biphenyldicarboxylic acid di (t-butylphenyl) s, 4,4'-biphenyldicarboxylic acid di (methoxyphenyl) s, 4 , 4'-biphenyldicarboxylic acid di (ethoxyphenyl) s, 4,4'-biphenyldicarboxylic acid di (nitrophenyl) s, 4,4'-biphenyldicarboxylic acid di (phenylphenyl) s, 4,4'-diphenyl ether Diphenyl dicarboxylate, 4,4′-diphenyl ether dicarboxylate (fluorophenyl), 4,4′-diphenyl ether dicarboxylate di (chlorophenyl),
4,4'-diphenyl ether dicarboxylic acid di (bromophenyl) s, 4,4'-diphenyl ether dicarboxylic acid di (methyl phenyl) s, 4,4'-diphenyl ether dicarboxylic acid di (ethyl phenyl) s, 4,4'- Diphenyl ether dicarboxylic acid di (propylphenyl) s, 4,4'-
Diphenyl ether dicarboxylic acid di (isopropylphenyl) s, 4,4'-diphenyl ether dicarboxylic acid di (butylphenyl) s, 4,4'-diphenyl ether dicarboxylic acid di (isobutylphenyl) s, 4,4'-diphenyl ether dicarboxylic acid di ( t-butylphenyl),
4,4'-diphenyl ether dicarboxylic acid di (methoxy
Eniru) s, 4,4'-diphenyl ether dicarboxylic acid di (ethoxyphenyl) s, 4,4'-diphenyl ether dicarboxylic acid di (nitrophenyl) ethers, 4,4'-diphenyl ether dicarboxylic acid di (phenyl) s, 4 ,Four'
-Diphenyl sulfide dicarboxylate, 4,4 '
-Diphenyl sulfide dicarboxylic acid di (fluorophenyl) s, 4,4'-diphenyl sulfide dicarboxylic acid di (chlorophenyl) s, 4,4'-diphenyl sulfide dicarboxylic acid di (bromophenyl) s, 4,4'-diphenyl sulfide Dicarboxylic acid di (methylphenyl) s, 4,4 '
-Diphenyl sulfide dicarboxylic acid di (ethyl phenyl), 4,4'-diphenyl sulfide dicarboxylic acid di (propyl phenyl), 4,4'-diphenyl sulfide dicarboxylic acid di (isopropyl phenyl), 4,4'-diphenyl Di (butylphenyl) sulfidedicarboxylate
, 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) Kind,
4,4'-diphenyl sulfide dicarboxylic acid di (ethoxyphenyl) s, 4,4'-diphenyl sulfide dicarboxylic acid di (nitrophenyl) s, 4,4'-diphenyl sulfide dicarboxylic acid di (phenylphenyl) s, 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'-benzophenone dicarboxylic acid di (ethylphenyl) s, 4,4'-benzophenone dicarboxylic acid di (propylphenyl) s, 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), 4,4'-benzophenone dicarboxylic acid di (methoxyphenyl), 4,4'-benzophenone dicarboxylic acid di (ethoxyphenyl), 4 4,4'-benzophenone dicarboxylic acid di (nitrophenyl) s, 4,4'-benzophenone dicarboxylic acid di (phenylphenyl) s, 4,4 '
-Diphenylsulfondicarboxylate, 4,4'-
Diphenylsulfone dicarboxylic acid di (fluorophenyl) s, 4,4'-diphenylsulfone dicarboxylic acid di (chlorophenyl) s, 4,4'-diphenylsulfone dicarboxylic acid di (bromophenyl) s, 4,4'-diphenylsulfone dicarboxylic acid Acid di (methylphenyl) s, 4,4′-diphenylsulfonodicarboxylic acid di (ethylphenyl) s,
4'-diphenylsulfondicarboxylic acid di (propylphenyl) s, 4,4'-diphenylsulfondicarboxylic acid di (isopropylphenyl) s, 4,4'-diphenylsulfondicarboxylic acid di (butylphenyl) s, 4,4 ' -Diphenylsulfonedicarboxylic acid di (isobutylphenyl)
, 4,4'-diphenylsulfondicarboxylic acid di (t-butylphenyl) s, 4,4'-diphenylsulfondicarboxylic acid di (methoxyphenyl) s, 4,4'-diphenylsulfondicarboxylic acid di (ethoxyphenyl) , Di (nitrophenyl) 4,4'-diphenylsulfonedicarboxylate
, 4,4'-diphenylsulfonedicarboxylic acid di (phenylphenyl) s, 4,4'-diphenylmethanedicarboxylic acid diphenyl, 4,4'-diphenylmethanedicarboxylic acid di (fluorophenyl) s, 4,4'-diphenylmethanedicarboxylic Acid di (chlorophenyl) s, 4,4′-diphenylmethanedicarboxylic acid di (bromophenyl) s, 4,4′-diphenylmethanedicarboxylic acid di (methylphenyl) s,
4'-diphenylmethanedicarboxylic acid di (ethylphenyl), 4,4'-diphenylmethanedicarboxylic acid di (propylphenyl), 4,4'-diphenylmethanedicarboxylic acid di (isopropylphenyl), 4,4'-diphenylmethanedicarboxylic Acid di (butylphenyl) s, 4,4'-diphenylmethanedicarboxylic 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) s, 4,4'-
Diphenylmethanedicarboxylate di (phenylphenyl)
, 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} propanes, 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, 2,2-bis {4- (nitrophenoxycarbonyl)
Phenyl} propanes, 2,2-bis {4- (phenylphenoxycarbonyl) phenyl} propanes, 2,2-bi
(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- (bromophenoxycarbonyl) ) Phenyl} -1,1,1,3,3,3-hexafluoropropane, 2,2-bis {4- (methylphenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexa Fluoropropanes, 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- (isopropylphenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexafluoro Propanes, 2,2-bis {4- (butylphenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexafluoropro 2,2-bis {4- (isobutylphenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexafluoropropane, 2,2-bis {4- (t-butylphenoxycarbonyl) ) Phenyl} -1,1,1,3,3,3-hexafluoropropane, 2,2-bis {4- (methoxyphenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexa Fluoropropanes, 2,2-bis {4- (ethoxyphenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexafluoropropanes, 2,2-bis {4- (nitrophenoxycarbonyl) Phenyl {-1,1,1,3,3,3-hexafluoropropane, 2,2-bis {4- (phenylphenoxycarbonyl) phenyl} -1,1,1,3,3,3-hexafluoro Propanes, diphenyl 1,4-naphthalenedicarboxylate, di (fluorophenyl) 1,4-naphthalenedicarboxylate, 1,4-na Di (chlorophenyl) talenedicarboxylate, di (bromophenyl) -1,4-naphthalenedicarboxylate, di (methylphenyl) 1,4-naphthalenedicarboxylate, di (ethylphenyl) 1,4-naphthalenedicarboxylate 1,4-naphthalenedicarboxylic acid di (propylphenyl) s, 1,4-naphthalenedicarboxylic acid di (isopropylphenyl) s, 1,4-naphthalenedicarboxylic acid di (butylphenyl) s, 1,4-naphthalenedicarboxylic acid Di (isobutylphenyl) s, 1,4
-Naphthalenedicarboxylic acid di (t-butylphenyl)
, 1,4-naphthalenedicarboxylic acid di (methoxyphenyl) s, 1,4-naphthalenedicarboxylic acid di (ethoxyphenyl) s, 1,4-naphthalenedicarboxylic acid di (nitrophenyl) s, 1,4-naphthalenedicarboxylic Acid di (phenylphenyl) s, 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 di (methylphenyl) s, 2,3-naphthalenedicarboxylic acid di (ethylphenyl) s, 2,3-naphthalenedicarboxylic acid di (propylphenyl) s, 2,3-naphthalenedicarboxylic acid di (isopropylphenyl), 2,3-naphthalenedicarboxylic acid di (butylphenyl), 2,3-naph Dicarboxylic acid di (isobutylphenyl) s, 2,3-naphthalene dicarboxylic acid di (t-butylphenyl) s, 2,
3-Naphthalenedicarboxylic acid di (methoxyphenyl)
, 2,3-naphthalenedicarboxylic di (ethoxyphenyl) s, 2,3-naphthalenedicarboxylic di (nitrophenyl) s, 2,3-naphthalenedicarboxylic di (phenylphenyl) s, 2,6-naphthalenedicarboxylic Acid diphenyl, 2,6-naphthalenedicarboxylic di (fluorophenyl) s, 2,6-naphthalenedicarboxylic di (chlorophenyl) s, 2,6-naphthalenedicarboxylic di (bromophenyl) s, 2,6-naphthalenedicarboxylic Acid di (methylphenyl) s, 2,6-naphthalenedicarboxylic di (ethylphenyl) s, 2,6-naphthalenedicarboxylic di (propylphenyl) s, 2,6-naphthalenedicarboxylic di (isopropylphenyl) s, 2,6-naphthalenedicarboxylic acid di (butylphenyl) s, 2,6-naphthalenedicarboxylic acid di (isobutylphenyl) s, 2,6-na Data dicarboxylic acid di (t-butylphenyl) s, 2,6-naphthalene dicarboxylic acid di (methoxyphenyl) s, 2,6
-Naphthalenedicarboxylic acid di (ethoxyphenyl) s,
2,6-Naphthalenedicarboxylic acid di (nitrophenyl)
And aromatic dicarboxylic acid diallylates such as 2,6-naphthalenedicarboxylic acid di (phenylphenyl) s. These aromatic dicarboxylic acid esters are used alone or in combination of two or more.

The above diamine component and aromatic dicarboxylic acid or its derivative are polymerized in a solvent. Examples of the solvent used include N, N-dimethylformamide,
N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, dimethylsulfoxide, Dimethyl sulfone, 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, chloroform, 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,
Methyl 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, etc. No. 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. Examples of the dehydrohalogenating agent used include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, N,
N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylaniline,
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, potassium hydrogen carbonate, 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.
As the condensing agent used, sulfuric anhydride, thionyl chloride,
Sulfite, picryl chloride, phosphorus pentoxide, phosphorus oxychloride, phosphite-pyridine condensing agent, triphenylphosphine-hexachloroethane condensing agent, propyl phosphoric anhydride-N-methyl-2-pyrrolidone condensing agent And the like.

The reaction temperature varies depending on the polymerization technique and the type of solvent, but is usually 300 ° C. or lower. 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 starting 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. Is reacted for a time sufficient to complete the formation of Usually, 10 minutes to 24 hours is sufficient. In such a reaction, X is a condensed polycyclic aromatic group or one or more groups selected from the group consisting of the following chemical formulas, Y is a direct bond, -O- , -S-, -SO ₂
—, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) _{2 —} , and R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, 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. An aromatic polyamide having a repeating unit represented by｝ is obtained.

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

The aromatic polyamide of the present invention has 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane as a raw material monomer. And / or 6,6′-bis (3-aminophenoxy)
B ) Characterized by using -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane and an aromatic dicarboxylic acid derivative such as an aromatic dicarboxylic acid or a dicarboxylic dihalide. .

However, in order to improve the thermal stability and moldability of the aromatic polyamide, the terminal of the polymer molecule is capped with a monovalent carboxylic acid or a carboxylic acid derivative or a monovalent amine. No problem.

Such an aromatic polyamide is represented by the formula
6,6'-bis (4-aminophenoxy) -3,3,3 ', 3'-
Tetramethyl-1,1′-spirobiindane and / or
6,6'-bis (3-aminophenoxy ) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane as the main component aromatic diamine and aromatic dicarboxylic acid or aromatic dicarboxylic acid It can be obtained by reacting a derivative in the presence of a monovalent carboxylic acid or a carboxylic acid derivative, or a monovalent 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 produced by replacing a part of the diamine component with an aromatic and / or aliphatic and / or alicyclic monoamine.

The monovalent carboxylic acids used in these methods include benzoic acid, chlorobenzoic acids, bromobenzoic acids, methylbenzoic acids, ethylbenzoic acids, methoxybenzoic acids, ethoxybenzoic acids, nitrobenzoic acids, and acetyl. Benzoic acids, acetoxybenzoic acids, hydroxybenzoic acids, biphenylcarboxylic acids, benzophenonecarboxylic acids, diphenylethercarboxylic acids, diphenylsulfidecarboxylic acids, diphenylsulfoncarboxylic acids, 2,2-diphenylpropanecarboxylic 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 acid, butyric acid, Kusasan, caproic acid, cinnamic acid, and cyclohexanecarboxylic acid. These monocarboxylic acids are used alone or in combination of two or more.

Further, as the monocarboxylic acid halide,
Benzoyl chloride, benzoyl bromide, chlorobenzoyl chloride, chlorobenzoyl bromide, bromobenzoyl chloride, bromobenzoyl bromide, methyl benzoyl chloride, methyl benzoyl bromide, ethyl benzoyl chloride, ethyl benzoyl bromide, methoxy benzoyl chloride , Methoxybenzoyl bromide, ethoxybenzoyl chloride, ethoxybenzoyl bromide, nitrobenzoyl chloride, nitrobenzoyl bromide, acetylbenzoyl chloride, acetylbenzoyl bromide, acetoxybenzoyl chloride, acetoxybenzoyl bromide, hydroxybenzoyl chloride ,
Hydroxybenzoyl bromides, biphenyl carboxylic chlorides, biphenyl carboxylic bromides, benzophenone carboxylic chlorides, benzophenone carboxylic bromides, diphenyl ether carboxylic chlorides, diphenyl ether carboxylic bromides, diphenyl sulfide carboxylic chlorides, diphenyl sulfide Carboxylic acid bromides, diphenylsulfonecarboxylic acid chlorides, diphenylsulfonecarboxylic acid bromide, 2,2-diphenylpropanecarboxylic acid chloride, 2,2-diphenylpropanecarboxylic acid bromide, 2,2-diphenyl-1,1 , 1,3,3,3-hexafluoropropanecarboxylic acid chlorides, 2,2-diphenyl-1,1,
1,3,3,3-hexafluoropropane carboxylic acid bromide, naphthalene carboxylic acid chlorides, naphthalene carboxylic acid bromide, acetyl chloride, acetyl bromide, chloroacetic chloride, chloroacetic bromide, dichloroacetic chloride, dichloroacetic 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.

Further, as monocarboxylic acid esters
Are methyl benzoate, ethyl benzoate,
, Isopropyl benzoate, butyl benzoate, benzoic acid
Isobutyl, phenyl benzoate, fluorophen benzoate
Nyls, chlorophenyl benzoates, Bromobenzoate
Phenyls, methylphenyl benzoates, ethyl benzoate
Phenyls, propyl benzoates, benzoic acid
Sopropylphenyls, butylphenyl benzoates, ammonium
Isobutylphenyl benzoates, t-butyl benzoate
Nyls, methoxyphenyl benzoates, ethoxy benzoate
Cyphenyls, nitrophenyl benzoates, benzoic acid
Phenylphenyls, methyl chlorobenzoates, chloro ammonium
Ethyl benzoates, propyl chlorobenzoates, chloro ammonium
Isopropyl benzoate, butyl chlorobenzoate,
Isobutyl benzoates, phenyl chlorobenzoates,
Fluorophenyl chlorobenzoates, chlorobenzoic acid
Lorophenyls, bromophenyl chlorobenzoates,
Methylphenyl lorobenzoate, ethyl chlorobenzoate
Phenyls, propylphenyl chlorobenzoates, chloro
Isopropyl phenyl benzoate, chloro benzoate
Tylphenyls, isobutylphenyl chlorobenzoate
, Tert-butylphenyl chlorobenzoates, chlorobenzo
Methoxyphenyl balates, ethoxyfe chlorobenzoate
Nil, nitrophenyl chlorobenzoate, chlorobenzo
Phenyl phenyls, methyl bromobenzoates,
Ethyl lomobenzoate, propyl bromobenzoate,
Isopropyl lomobenzoate, butyl bromobenzoate
, Isobutyl bromobenzoates, bromobenzoic acid
Nyls, fluorophenyl bromobenzoates, bromoammonium
Chlorophenyl benzoates, Bromophenyl bromobenzoate
, Methylphenyl bromobenzoates, bromobenzoate
Ethylphenyls, propylphenyl bromobenzoate
, Isopropyl bromobenzoates, bromo ammonium
Butylphenyl benzoates, isobutyl bromobenzoate
Enyls, t-butylphenyl bromobenzoates, bromine
Methoxyphenyl mobenzoate, ethoxy bromobenzoate
Cyphenyls, nitrophenyl bromobenzoates, bromine
Phenylphenyl mobenzoate, methyl methyl benzoate
, Ethyl methyl benzoate, propyl methyl benzoate
, Methyl isopropyl benzoate, methyl benzoate
Tyls, isobutyl methyl benzoate, methyl benzoic acid
Phenyls, fluorophenyl methyl benzoates, methyl
Chlorophenyl benzoate, Bromomethyl benzoate
Phenyls, methylphenyl methyl benzoates, methyl ammonium
Ethyl phenyl benzoates, propyl methyl benzoate
Nyls, isopropylphenyl methylbenzoate, methyl
Butylphenyl benzoate, isobutyl methyl benzoate
Ruphenyls, t-butylphenyl methylbenzoate,
Methoxyphenyl methyl benzoate, methyl benzoate
Toxiphenyls, nitrophenyl methylbenzoates,
Phenylphenyl methyl benzoate, methyl benzoate
Chills, ethyl ethyl benzoate, ethyl benzoate pro
Pills, isopropyl ethyl benzoate, ethyl benzoate
Butyl acid, isobutyl ethyl benzoate, ethyl benzoate
Phenyl perfuates, fluorophenyl ethyl benzoates,
Chlorophenyl ethyl benzoate, ethyl benzoic acid bromide
Mophenyls, methylphenyl ethylbenzoates, ethi
Ethylphenyl benzoate, propyl ethylbenzoate
Phenyls, isopropylphenyl ethylbenzoate,
Butyl phenyl ethyl benzoate, iso-ethyl benzoate
Butylphenyls, t-butylphenyl ethylbenzoate
, Methoxyphenyl ethyl benzoate, ethyl benzoate
Ethoxyphenyls, nitrophenyl ethylbenzoate
, Phenylphenyl ethylbenzoate, methoxybenzo
Methyl benzoates, ethyl methoxybenzoates, methoxy ammonium
Propyl benzoates, isopropyl methoxybenzoates,
Butyl methoxybenzoate, isobutyl methoxybenzoate
Phenyl, methoxybenzoic acid, 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
, Bromophenyl acetylbenzoates, acetylbenzo
Methyl phenyl fragrances, ethyl phenyl benzoate
, Acetylphenyl benzoate, acetyl
Isopropylphenyl benzoates, acetyl benzoate
Tylphenyls, isobutylphenyl acetylbenzoate
, Acetyl t-butylphenyl benzoates, acetyl
Methoxyphenyl benzoates, ethoxy acetyl benzoate
Cyphenyls, nitrophenyl acetylbenzoates,
Phenylphenyl cetylbenzoate, acetoxybenzoate
Methyls, acetoxybenzoates, acetoxy
Propyl benzoate, isopropyl acetoxybenzoate
, Acetoxybenzoic acid butyls, acetoxybenzoic acid
Isobutyls, phenylacetoxybenzoates, aceto
Fluorophenylsoxybenzoate, acetoxybenzoic acid
Chlorophenyls, bromophenyl acetoxybenzoate
, Methylphenylacetoxybenzoate, acetoxy
Ethyl phenyl benzoates, propoxy acetoxybenzoate
Ruphenyls, isopropylphenycetoxybenzoate
Butylphenylacetoxybenzoate, acetoxy
Isobutylphenyl benzoates, acetoxybenzoic acid
t-butylphenyls, methoxyphenyl acetoxybenzoate
Enyls, ethoxyphenyl acetoxybenzoates,
Nitrophenyl cetoxybenzoate, acetoxybenzoate
Phenyl phenyls, methyl hydroxybenzoates,
Ethyl hydroxybenzoates, hydroxybenzoic acid pro
Pills, isopropyl hydroxybenzoates, hydroxy
Butyl benzoates, isobutyl hydroxybenzoate
, Hydroxyphenyl benzoates, hydroxybenzoate
Acid fluorophenyls, chlorofe hydroxybenzoate
Nyls, bromophenyl hydroxybenzoates, hydro
Methyl phenyl xybenzoates, hydroxybenzoic acid
Tylphenyls, propylphenyl hydroxybenzoate
, Isopropylphenyl hydroxybenzoates, hydride
Roxybenzoic acid butylphenyls, hydroxybenzoic acid
Isobutylphenyls, t-butyl hydroxybenzoate
Phenyls, methoxyphenyl hydroxybenzoates,
Ethoxyphenyl hydroxybenzoates, hydroxy ammonium
Nitrophenyl benzoates, phenyl hydroxybenzoate
Phenyls, methyl biphenylcarboxylates, biphenyl
Ethyl carboxylate, propyl biphenyl carboxylate
, Biphenylcarboxylate isopropyls, biphenyl
Butyl carboxylate, isobutyl biphenylcarboxylate
, Biphenylcarboxylates, biphenylcar
Fluorophenyl bonates, biphenyl carboxylic acid chromate
Lophenyls, bromophenyl biphenylcarboxylate
, Methylphenyl biphenylcarboxylate, biphenyl
Ethylphenyl carboxylate, biphenylcarboxylic acid
Propylphenyls, isopropyl biphenylcarboxylate
Ruphenyls, 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
Ethoxyphenyl bonates, benzophenone carboxylic acid
Nitrophenyls, phenyl benzophenonecarboxylate
Phenyls, methyl diphenylethercarboxylates,
Ethyl diphenyl ether carboxylate, diphenyl ether
-Propyl tercarboxylate, diphenyl ether carb
Isopropyl borate, diphenyl ether carboxylic acid
Butyls, isobutyl diphenyl ether carboxylate
, Diphenyl ether carboxylate, diphe
Nyl ether carboxylic acid fluorophenyls, diphenyl
Chlorophenyl ether carboxylate, diphenyl ether
-Bromophenyl tercarboxylate, diphenyl ether
Methyl carboxylate, diphenyl ether
Ethyl phenyl rubonates, diphenyl ether carbo
Propyl phenylates, diphenyl ether carboxyl
Isopropyl phenyls, diphenyl ether carb
Butyl phenylates, diphenyl ether carboxylic acid
Isobutyl phenyls, diphenyl ether carboxylic acid
t-butylphenyls, diphenylethercarboxylic acid
Methoxyphenyls, diphenyl ether carboxylic acid
Toxiphenyls, diphenyl ether carboxylic acid nitrite
Lophenyls, phenyl diphenyl ether carboxylate
Phenyls, methyl diphenylsulfidecarboxylate
, Ethyl diphenylsulfidecarboxylate, dife
Propyl Nylsulfide Carboxylates, Diphenylsulfur
Isopropyl Fidocarboxylate, Diphenyl Sulfide
Butyl carboxylate, diphenyl sulfide carboxylic acid
Acid isobutyls, diphenyl sulfide carboxylate
Nil, diphenyl sulfide carboxylic acid fluorophene
Nyls, diphenyl sulfide carboxylic acid chlorophenyl
And bromophenyl diphenyl sulfide carboxylate
, Methylphenyl diphenylsulfidecarboxylate
, Ethylphenyl diphenylsulfidecarboxylate
, Phenylphenyl diphenylsulfidecarboxylate
, Diisopropyl sulfide carboxylate
Nyls, butylphenyldiphenylsulfidecarboxylate
And dibutyl sulfide carboxylate
Nyls, t-butyl diphenylsulfidecarboxylate
Phenyls, methoxyphenyl diphenylsulfidecarboxylate
Phenyls, ethoxyl diphenyl sulfide carboxylate
Phenyl, diphenyl sulfide carboxylate
Phenyls, diphenyl sulfide carboxylate
Nil, methyl diphenylsulfoncarboxylate, diph
Ethyl phenyl sulfone carboxylate, diphenyl sulfo
Propyl carboxylate, diphenyl sulfone carboxy
Acid isopropyls, diphenyl sulfone carboxylate
, Isobutyl diphenylsulfonate, di
Phenyl sulphone carboxylates, diphenyls
Fluorophenyl fluorocarbons, diphenyl sulf
Chlorophenyls of carboxylates, diphenylsulfone
Bromophenyl carboxylate, diphenyl sulfone car
Methylphenyl bonates, diphenylsulfonecarboxylic
Ethylphenyls, diphenylsulfonate
Ropylphenyls, diphenylsulfoncarboxylic acid iso
Propylphenyls, diphenylsulfonate
Tylphenyls, isophenyl diphenylsulfonate
Tylphenyls, t-butyl diphenylsulfonate
Tylphenyls, diphenylsulfoncarboxylic acid methoxy
Cyphenyls, ethoxy diphenylsulfonate
Phenyls, nitrophene diphenylsulfonate
Nyls, phenylpheny diphenylsulfonate
, Methyl 2,2-diphenylpropanecarboxylates,
Ethyl 2,2-diphenylpropanecarboxylate, 2,2-di
Propyl phenylpropanecarboxylate, 2,2-dife
Isopropyl nylpropanecarboxylate, 2,2-dife
Butyl nylpropanecarboxylate, 2,2-diphenylp
Isobutyl ropanecarboxylates, 2,2-diphenylpro
Phenyl pancarboxylates, 2,2-diphenylpropane
Carboxylic acid fluorophenyls, 2,2-diphenylpro
Chlorophenyl pancarboxylates, 2,2-diphenyl propyl
Lomopanic acid bromophenyls, 2,2-diphenyl
Methylphenyl propanecarboxylates, 2,2-diphenyl
Ethylphenyl propanecarboxylate, 2,2-dife
Propylphenyl nylpropanecarboxylates, 2,2-di
Isopropylphenyl phenylpropanecarboxylate,
Butylphenyl 2,2-diphenylpropanecarboxylate
, Isobutyl phenyl 2,2-diphenylpropanecarboxylate
Enyls, t-butyl 2,2-diphenylpropanecarboxylate
Tylphenyls, 2,2-diphenylpropanecarboxylic acid
Methoxyphenyls, 2,2-diphenylpropanecarbo
Ethoxyphenyls, 2,2-diphenylpropaneca
Nitrophenyl rubonates, 2,2-diphenylpropane
Phenylphenyl carboxylates, 2,2-diphenyl-1,
Methyl 1,1,3,3,3-hexafluoropropanecarboxylate
, 2,2-diphenyl-1,1,1,3,3,3-hexafluoroprop
Ethyl lopancarboxylates, 2,2-diphenyl-1,1,1,1
Propyl 3,3,3-hexafluoropropanecarboxylate
, 2,2-diphenyl-1,1,1,3,3,3-hexafluoroprop
Isopropanecarboxylates, 2,2-diphenyl-
1,1,1,3,3,3-hexafluoropropanecarboxylic acid
And 2,2-diphenyl-1,1,1,3,3,3-hexafluoro
Isobutyl propanecarboxylates, 2,2-diphenyl-
1,1,1,3,3,3-hexafluoropropanecarboxylic acid
Nyls, 2,2-diphenyl-1,1,1,3,3,3-hexafluoro
Lopropane carboxylic acid fluorophenyls, 2,2-diph
Enyl-1,1,1,3,3,3-hexafluoropropanecarbo
Chlorophenyl acid, 2,2-diphenyl-1,1,1,3,3,3
-Bromophenyl hexafluoropropanecarboxylate
Kind,2,2-diphenyl-1,1,1,3,3,3-hexafluorop
Methylphenyl lopancarboxylates,2,2-diphenyl
-1,1,1,3,3,3-hexafluoropropanecarboxylic acid
Tylphenyls, 2,2-diphenyl-1,1,1,3,3,3-hex
Propylphenyl safluoropropanecarboxylates, 2,
2-diphenyl-1,1,1,3,3,3-hexafluoropropane
Isopropylphenyl carboxylate, 2,2-diphenyl
1,1,1,1,3,3,3-hexafluoropropanecarboxylic acid
Tylphenyls, 2,2-diphenyl-1,1,1,3,3,3-hexyl
Isobutylphenyl safluoropropanecarboxylates,
2,2-diphenyl-1,1,1,3,3,3-hexafluoropropa
Carboxylic acid t-butylphenyls, 2,2-diphenyl
-1,1,1,3,3,3-hexafluoropropanecarboxylic acid
Toxiphenyls, 2,2-diphenyl-1,1,1,3,3,3-he
Ethoxyphenyl xafluoropropanecarboxylates,
2,2-diphenyl-1,1,1,3,3,3-hexafluoropropa
Nitrophenyl carboxylates, 2,2-diphenyl-1,
1,1,3,3,3-hexafluoropropanecarboxylic acid phenyl
Ruphenyls, methyl naphthalene carboxylate, naphtha
Ethylene carboxylate, propylene naphthalene carboxylate
, Naphthalene isopropyl carboxylate, naphthalene
Butyl carboxylate, isobutyl naphthalene carboxylate
Phenyls, naphthalenecarboxylates, naphthaleneca
Fluorophenyl rubonates, naphthalenecarboxylic acid
Lolophenyls, bromophenyl naphthalenecarboxylate
, Methyl naphthalene carboxylate, naphthale
Ethyl phenyl carboxylate, naphthalene carboxylic acid
Propylphenyls, isopropyl naphthalenecarboxylate
Ruphenyls, butylphenyl naphthalenecarboxylate
, Isobutylphenyl naphthalenecarboxylate, naph
T-butylphenyl tarencarboxylate, naphthaleneca
Methoxyphenyl rubonates,Naphthalenecarboxylic acid
Toxiphenyls, Naphthalene carboxylate nitrophenyl
Phenylphenyl naphthalene carboxylate, acetic acid
Methyl, ethyl acetate, propyl acetate, isopropyl acetate
Butyl acetate, isobutyl acetate, phenyl acetate, acetic acid
Fluorophenyls, chlorophenyl acetates, acetate broth
Mophenyls, methylphenyl acetates, ethyl acetate
Nyls, propyl phenyl acetates, isopropyl acetate
Phenyls, butylphenyl acetates, isobutyl acetate
Nyls, t-butylphenyl acetates, methoxyphenyl acetate
Nyls, ethoxyphenyl acetates, nitrophenyl acetate
, Phenylphenyl acetates, methyl chloroacetate,
Ethyl loacetate, propyl chloroacetate, isop chloroacetate
Propyl, butyl chloroacetate, isobutyl chloroacetate,
Phenylloroacetate, fluorophenylchloroacetates,
Chlorophenyl chloroacetate, bromophenyl chloroacetate
, Methylphenyl chloroacetate, ethyl chloroacetate
Phenyls, propylphenyl chloroacetates, chloroacetic acid
Isopropylphenyls, butylphenyl chloroacetate
, Isobutylphenyl chloroacetates, chloroacetic acid t-
Butylphenyls, methoxyphenyl chloroacetates,
Ethoxyphenyl loroacetate, nitrophenyl chloroacetate
Phenylacetates, dichloroacetate
Chill, ethyl dichloroacetate, propyl dichloroacetate, di
Isopropyl chloroacetate, butyl dichloroacetate, dichloro
Isobutyl roacetate, phenyl dichloroacetate, dichlorovinegar
Acid fluorophenyls, chlorophenyl dichloroacetate
, Bromophenyl dichloroacetate, methyl dichloroacetate
Ruphenyls, ethylphenyl dichloroacetate, dichloro
Propylphenyl loacetates, isopropyl dichloroacetate
Phenyls, butylphenyl dichloroacetate, dichloro
Isobutylphenyl acetates, t-butyl dichloroacetate
Phenyls, methoxyphenyl dichloroacetates, dichloro
Ethoxyphenyl acetates, nitrophenyl dichloroacetate
, Phenylphenyl dichloroacetate, trichloroacetic acid
Methyl, ethyl trichloroacetate, propyl acetate
Toluene, isopropyl trichloroacetate,
Isobutyl trichloroacetate, phenyl trichloroacetate
, Fluorophenyls trichloroacetate, trichlorovinegar
Acid chlorophenyls, bromophenyl trichloroacetate
, Methylphenyl trichloroacetate, trichloroacetic acid
Ethylphenyls, propylphenyl trichloroacetate
, Isopropylphenyl trichloroacetate, trichloro
Butyl phenyl acetate, isobutyl trichloroacetate
Phenyls, t-butylphenyl trichloroacetates, tris
Methoxyphenyl chloroacetate, ethoxy trichloroacetate
Cyphenyls, nitrophenyl trichloroacetates, tri
Phenylphenyl chloroacetates, methyl fluoroacetate,
Ethyl fluoroacetate, propyl fluoroacetate, fluoro
Isopropyl acetate, butyl fluoroacetate, fluoroacetic acid
Isobutyl, phenyl fluoroacetate, full fluoroacetate
Orophenyls, chlorophenyl fluoroacetates, full
Bromophenyl oroacetate, methylphenyfluoroacetate
Toluene, ethylphenyl fluoroacetate, fluoroacetic acid
Propylphenyls, isopropylphenyl fluoroacetate
, Butylphenyl fluoroacetate, isofluoroacetate
Butylphenyls, t-butylphenyl fluoroacetate
, Methoxyphenyl fluoroacetates, fluoroacetic acid
Toxiphenyls, nitrophenyl fluoroacetates,
Phenylphenyl fluoroacetates, methyl difluoroacetate
, Ethyl difluoroacetate, propyl difluoroacetate,
Isopropyl difluoroacetate, butyl difluoroacetate,
Isobutyl difluoroacetate, phenyl difluoroacetate,
Fluorophenyl difluoroacetate, difluoroacetic acid
Lorophenyls, bromophenyl difluoroacetates, di
Methylphenyl fluoroacetates, ethyl difluoroacetate
Phenyls, propylphenyl difluoroacetates, diph
Isopropylphenyl fluoroacetates, difluoroacetate
Tylphenyls, isobutylphenyl difluoroacetate
, T-butylphenyl difluoroacetates, difluoro
Methoxyphenyl acetates, ethoxyfe difluoroacetate
Nyls, nitrophenyl difluoroacetates, difluoro
Phenylphenyl acetates, methyl trifluoroacetate,
Ethyl trifluoroacetate, propyl trifluoroacetate,
Isopropyl trifluoroacetate, Butyl trifluoroacetate
Isobutyl trifluoroacetate, trifluoroacetic acid
Phenyl, fluorophenyl trifluoroacetates, trif
Chlorophenyl fluoroacetate, bromotrifluoroacetate
Phenyls, methylphenyl trifluoroacetates, tris
Ethylphenyl fluoroacetate, trifluoroacetic acid pro
Pyrphenyls, isopropyl phenyl trifluoroacetate
Butylphenyl trifluoroacetates, trifluoro
Isobutyl phenyl acetic acid, tert-butyl trifluoroacetate
Tylphenyls, methoxyphenyl trifluoroacetate
, Ethoxyphenyl trifluoroacetates, trifluoro
Nitrophenyl acetic acid, phenylphenyl trifluoroacetate
Phenyls, methyl nitroacetate, ethyl nitroacetate, nitro
Propyl acetate, isopropyl nitroacetate, nitroacetic acid
Butyl, isobutyl nitroacetate, phenyl nitroacetate,
Fluorophenyl nitroacetates, chlorophen nitroacetate
Nyls, bromophenyl nitroacetates, methyl nitroacetate
Ruphenyls, ethylphenyl nitroacetate, nitrovinegar
Propyl phenyls, isopropyl phenyl nitroacetate
, Butylphenyl nitroacetate, isobutyl nitroacetate
Tylphenyls, t-butylphenyl nitroacetates,
Methoxyphenyl troacetates, ethoxyfe nitroacetate
Nil, nitrophenyl nitroacetate, nitroacetate
Nylphenyls, methyl propionate, propionate
Chill, propyl propionate, isopropyl propionate
Butyl propionate, isobutyl propionate,
Phenyl lopionate, fluorophenyl propionate
, Chlorophenyl propionates, bronyl propionate
Mophenyls, methylphenyl propionates, propyl
Ethylphenyl onates, propylphenate propionate
Compounds, isopropylphenyl propionate, propio
Butyl phenylates, isobutyl phenyl propionate
, Propionate t-butylphenyls, propion
Methoxyphenyls, ethoxyphenyl propionate
, Nitrophenyl propionates, ferropropionate
Nylphenyls, methyl butyrate, ethyl butyrate, propyl butyrate
Butyl butyrate, butyl butyrate, isobutyl butyrate,
Phenyl butyrate, fluorophenyl butyrate, chlorobutyrate
Phenyls, bromophenyl butyrate, methylphenyl butyrate
, Ethylphenyl butyrate, propylphenyl butyrate,
Isopropylphenyl butyrate, butylphenyl butyrate,
Isobutylphenyl butyrate, t-butylphenyl butyrate
, Methoxyphenyl butyrate, ethoxyphenyl butyrate
, Nitrophenyl butyrate, phenylphenyl butyrate,
Methyl valerate, ethyl valerate, propyl valerate, valeric acid
Isopropyl, butyl valerate, isobutyl valerate, valer
Phenylate, fluorophenyl valerate, chlorovalerate
Phenyls, bromophenyl valerates, methyl valerate
Phenyls, ethylphenyl valerates, propyl valerate
Phenyls, isopropylphenyl valerate, butyrate
Phenyls, isobutylphenyl valerates, valerate t
-Butylphenyls, methoxyphenylvalerates, valerian
Ethoxyphenyls, nitrophenylvalerate, valer
Phenylphenylates, methyl caproate, caproic acid
Ethyl, propyl caproate, isopropyl caproate
Butyl, caproate, isobutyl caproate, capro
Phenyl acid, fluorophenyl caproate, capro
Chlorophenyl acid, bromophenyl caproate,
Methylphenyl caproate, ethylphenocaproate
Propyl phenyl caproate, isocaproate
Propylphenyls, butylphenyl caproate,
Isobutylphenyl pronoates, t-butyl caproate
Phenyls, methoxyphenyl caproates, capron
Ethoxyphenyl acid, nitrophenyl caproate,
Phenylphenyl caproate, methyl cinnamate, cinnamic acid
Ethyl, propyl cinnamate, isopropyl cinnamate, cinnamic acid
Butyl, isobutyl cinnamate, phenyl cinnamate, cinnamate
Fluorophenyls, chlorophenyl cinnamate, butyl cinnamate
Lomophenyls, methylphenyl cinnamate, ethyl cinnamate
Ruphenyls, propylphenyl cinnamate, iso-cinnamate
Propylphenyls, butylphenylcinnamates, cinnamic acid
Isobutylphenyls, t-butylphenylcinnamates,
Methoxyphenyl cinnamate, ethoxyphenyl cinnamate
, Nitrophenyl cinnamate, phenylphenyl cinnamate
, Methyl cyclohexanecarboxylate, cyclohexane
Ethyl carboxylate, propane cyclohexane
Isopropyl cyclohexanecarboxylate, cyclohexane
Butyl carboxylate, cyclohexane carboxylate
Sobutyl, phenyl cyclohexanecarboxylate, cyclo
Hexane carboxylic acid fluorophenyls, cyclohexa
Chlorophenyl carboxylates, cyclohexanecarbo
Acid bromophenyls, cyclohexanecarboxylic acid methyl
Ruphenyls, ethyl phenylcyclohexanecarboxylate
Propylphenyl cyclohexanecarboxylates,
Isopropylphenyl cyclohexanecarboxylates,
Butylphenyl chlorohexanecarboxylate, cyclohexyl
Isobutylphenyl carboxylate, cyclohexane
T-butylphenyl carboxylate, cyclohexanecar
Methoxyphenyl bonates, cyclohexanecarboxylic acid
Ethoxyphenyls, nitrocyclohexanecarboxylate
Phenyls, phenylphenycyclohexanecarboxylate
And the like. These monocarboxylic esters
Are used alone or in combination of two or more.

The amount of the monocarboxylic acid used is from 0.001 to 1.0 mol per mol of the 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,
-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
-Aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, -Aminophenylphenyl sulfide, 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, diisopropylamine, butylamine, dibutylamine, isobutylamine, diisobutylamine, pentylamine, dipentylamine, benzylamine , Cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine and the like.
These monoamines are used alone or in combination of two or more.

The amount of the monoamine used is from 0.001 to 1.0 mol per mol 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 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.

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. As thermoplastic resins that can be blended, polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polyimide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyphenylenesulfide, polyamideimide, polyetherimide, modified And polyphenylene oxide.

It is also possible to add a thermosetting resin or a filler to such an extent that the object of the invention is not impaired.
Examples of the thermosetting resin include a phenol resin and an epoxy resin. As fillers, graphite, carborundum, silica stone, molybdenum disulfide, abrasion resistance improving material such as fluororesin, glass fiber, carbon fiber,
Reinforcing material such as boron fiber, silicon carbide fiber, carbon whisker, asbestos, metal fiber, ceramic fiber, flame retardant improving material such as antimony trioxide, magnesium carbonate, calcium carbonate, etc., electric property improving material such as clay and mica, asbestos, silica, tracking resistance improver such as graphite, barium sulfate, silica, acid resistance improver such as calcium metasilicate, iron powder, zinc powder, aluminum powder, thermal conductivity improver such as copper powder, other glass beads, Talc, diatomaceous earth, alumina, silica balun, hydrated alumina, metal oxides, coloring agents and the like.

As the fibrous reinforcing material used in the present invention, various materials are used, for example, glass fiber, carbon fiber,
Potassium titanate fiber, aromatic polyamide fiber, silicon carbide fiber, alumina fiber, boron fiber, ceramic fiber and the like are exemplified, and glass fiber, carbon fiber, potassium titanate fiber, and aromatic polyamide fiber are particularly preferably used. It is.

The glass fiber used in the present invention is obtained by quenching molten glass while stretching it by various methods to form a thin fiber having a predetermined diameter. It means roving or the like in which strands are uniformly aligned to form a bundle, and any of them can be used in the present invention. 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 the production of the molded article.
In general, 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 is 0.1 to 6 m in the present invention.
m, preferably in the range of 0.3 to 4 mm, because the physical properties and workability of the molded article are balanced.

The carbon fibers used in the present invention are high elasticity and high strength fibers 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 carbon fiber preferably has a diameter of usually 5 to 20 μm, particularly preferably about 8 to 15 μm. The aspect ratio is 1 to 600, especially 100 to 350 due to the reinforcing effect and the mixing property.
The degree is preferred. 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 treating agents, for example, an epoxy resin, a polyamide resin, a polycarbonate resin, a polyacetal resin, and the like, and those using a known surface treating 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 based on K ₂ O.6TiO ₂ , K ₂ O.6TiO ₂ .H ₂ O. It is a needle-like crystal and has a typical melting point of 1300 to 1350 ° C. The average fiber length is 5 to 50 μm and the average fiber diameter is 0.05 to 1.0 μm, but the average fiber length is 20 to 30 μm and the average fiber diameter is
Those having a diameter of 0.1 to 0.3 μm are preferred. The potassium titanate fiber can be used without any usual treatment, but in order to have an affinity with the base resin of the present invention, a silane coupling agent such as aminosilane or epoxysilane, chromic chloride, or other surface treatment depending on the purpose. Agents can be used.

The aromatic polyamide fiber used in the present invention is a relatively newly developed heat-resistant organic fiber,
It is expected to expand into various fields by utilizing many unique characteristics. For example, typical examples include those having the following structural formulas, and at least one or a mixture of two or more of them is used.

[1]

[0047]

Embedded image Example) DuPont trademark: Kevlar [2]

[0048]

Embedded image Example) DuPont trademark: Nomex Teijin Trademark: Conex [3]

[0049]

Embedded image 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] have a high softening point and a high melting point as heat-resistant organic fibers in the present invention. Most preferred.

In glass fibers and carbon fibers, when the amount is less than 5 parts by weight, the reinforcing effect peculiar to the glass fibers or carbon fibers 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 too 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) Polyamide powder and fibrous reinforcing material are preliminarily mixed using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill, ribbon blender, etc., and then kneaded with a generally known melt mixer, hot roll, or the like. And then pulverized or powdered.

2) Polyamide powder is dissolved or suspended in an organic solvent in advance, and the solution or suspension is fibrous reinforced.
The material is immersed, then the solvent is removed in a hot air oven and then pelletized or powdered. 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 , Dimethyl sulfoxide, dimethyl sulfone, tetramethyl urea, hexamethyl phosphoramide 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.

[0055]

EXAMPLES 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 a polyamide powder was dissolved in 100 ml of hexamethylphosphoric triamide and measured at 35 ° C.

Glass transition temperature (Tg): DSC (Shimadzu D
T-40 series, DSC-41M).

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

Melt viscosity: Shimadzu Koka type flow tester CF
It was measured at a weight of 100 kg by T500A. (Example 1) 6,6'-bis (4-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1' in a vessel equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere. −
49.07 g (0.10 mol) of spirobiindane and N-
After charging and dissolving 550 g of methyl-2-pyrrolidone, 24.29 g (0.24 mol) of triethylamine was added, and the mixture was cooled to 5 ° C. Then, stirring was increased and 20.30 g (0.10 mol) of terephthalic acid chloride was charged.
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.
60.27 g (yield 97.1%) of polyamide powder was obtained.

The logarithmic viscosity of this polyamide powder is 0.82.
dl / g, glass transition temperature was 272 ° C, and 5% weight loss temperature was 490 ° C.

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

CH N ────────────────────────── Calculated value (%) 79.33 5.85 4.51 Actual value (% 79.10 5.86 4.55} The infrared absorption spectrum of the obtained polyamide powder was As shown in FIG. This spectrum diagram, in the vicinity of 1660 cm ^-1 and near 1520 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

The obtained polyamide powder was dissolved in N-methyl-2-pyrrolidone, cast on a glass plate, and heated at 150 ° C. for 1 hour and at 250 ° C. for 2 hours to obtain a colorless and transparent polyamide film. Was. This polyamide film has a tensile strength of 780 kg / cm ² and a tensile elongation of 10%.
Met. Both measurement methods are based on ASTM D-882.

The water absorption of this film was 0.61%. The measuring method is based on ASTM D-750-63. (Example 2) A polyamide powder having a logarithmic viscosity of 0.88 dl / g was prepared in the same manner as in Example 1 except that terephthalic acid chloride in Example 1 was replaced with isophthalic acid chloride.
9 g (96.8% yield) was obtained.

The polyamide powder has a glass transition temperature of 2
The temperature at 51 ° C. and 5% weight loss was 496 ° C.

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

CH N 計算 Calculated value (%) 79.33 5.85 4.51 Actual measured value (% 79.15 5.85 4.52} The infrared absorption spectrum of the obtained polyamide powder was As shown in FIG. This spectrum diagram, in the vicinity of 1650 cm ^-1 and near 1520 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Further, using the obtained polyamide powder,
A colorless and transparent polyamide film was obtained in the same manner as in Example 1. The tensile strength of this polyamide film is 700kg
/ cm ² , the tensile elongation was 18%, and the water absorption was 0.58%. (Example 3) Terephthalic acid chloride 2 in Example 1
0.30 g (0.10 mol) of terephthalic acid chloride 1
0.15 g (0.05 mol) and isophthalic chloride 1
The same procedure as in Example 1 was carried out except that the amount was changed to 0.15 g (0.05 mol), and a polyamide powder 6 having an intrinsic viscosity of 0.83 dl / g was used.
0.22 g (97.0% yield) was obtained.

The glass transition temperature of this polyamide powder is 2
The 5% weight loss temperature was 496 ° C at 59 ° C.

Using the obtained polyamide powder, a colorless and transparent polyamide film was obtained in the same manner as in Example 1. The tensile strength of this polyamide film is 710 kg / c
m ² , tensile elongation was 16%, and water absorption was 0.58%. (Example 4) 6,6'-bis (4-aminophenoxy) -3,3,3'3'-tetramethyl-
Example 1 Example 1 was repeated except that 1,1′-spirobiindane was replaced by 6,6′-bis (3-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane.
In the same manner as described above, 60.22 g (yield 97.0%) of a polyamide powder having an logarithmic viscosity of 0.90 dl / g was obtained.

The glass transition temperature of this polyamide powder was 2
35 ° C, 5% weight loss temperature was 495 ° C.

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

CH N 計算 Calculated value (%) 79.33 5.85 4.51 Actual value (% 79.11 5.86 4.48} The infrared absorption spectrum of the obtained polyamide powder was As shown in FIG. This spectrum diagram, in the vicinity of 1650 cm ^-1 and near 1520 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Further, using the obtained polyamide powder,
A colorless and transparent polyamide film was obtained in the same manner as in Example 1. The tensile strength of this polyamide film is 870kg
/ cm ² , the tensile elongation was 28%, and the water absorption was 0.70%. (Example 5) The same procedure as in Example 4 was carried out except that terephthalic acid chloride in Example 4 was replaced with isophthalic acid chloride.
3 g (97.5% yield) was obtained.

The polyamide powder has a glass transition temperature of 2
26 ° C, 5% weight loss temperature was 501 ° C.

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

CH N ────────────────────────── Calculated value (%) 79.33 5.85 4.51 Actual value (% 79.10 5.87 4.53} The infrared absorption spectrum of the obtained polyamide powder was As shown in FIG. This spectrum diagram, in the vicinity of 1660 cm ^-1 and near 1520 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Further, using the obtained polyamide powder,
A colorless and transparent polyamide film was obtained in the same manner as in Example 1. The tensile strength of this polyamide film is 830kg
/ cm ² , the tensile elongation was 37%, and the water absorption was 0.71%. (Example 6) Terephthalic acid chloride 2 in Example 4
0.30 g (0.10 mol) of terephthalic acid chloride 1
0.15 g (0.05 mol) and isophthalic chloride 1
The same procedure as in Example 4 was carried out except that the amount was changed to 0.15 g (0.05 mol), and a polyamide powder 6 having an logarithmic viscosity of 0.90 dl / g was used.
0.47 g (yield 97.4%) was obtained.

The polyamide powder has a glass transition temperature of 2
The temperature at 30 ° C. and 5% weight loss was 502 ° C.

Using the obtained polyamide powder, a colorless and transparent polyamide film was obtained in the same manner as in Example 1. The tensile strength of this polyamide film is 845kg / c
m ² , the tensile elongation was 31%, and the water absorption was 0.69%. Example 7 16.62 g (0.10 g) of terephthalic acid was placed in a vessel equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere.
Mol), lithium chloride 20.0 g, calcium chloride 6
0.0 g, pyridine 200 g, triphenyl phosphite 6
After 2.0 g (0.20 mol) and 1150 g of N-methyl-2-pyrrolidone were charged and dissolved, the temperature was raised to 120 ° C. There, 6,6'-bis (4-aminophenoxy)
-3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane was charged with 49.07 g (0.10 mol),
Stirred at 120 ° C. for 2 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.
60.84 g (98.0% yield) of polyamide powder was obtained.

The logarithmic viscosity of this polyamide powder was 0.87.
dl / g, glass transition temperature was 274 ° C, and 5% weight loss temperature was 492 ° C.

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

CH N ────────────────────────── Calculated value (%) 79.33 5.85 4.51 Actual value (% 79.09 5.88 4.54} Also, the infrared absorption spectrum of the obtained polyamide powder was As shown in FIG. This spectrum diagram is exactly the same as the polyamide powder obtained in Example 1, in the vicinity of 1650 cm ^-1 and near 1520 cm ^-1 which is the characteristic absorption band of amide,
Significant absorption was observed. (Example 8) 19.42 g of dimethyl terephthalate was placed in a container equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere.
(0.10 mol), 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1 ′
49.07 g (0.10 mol) of spirobiindane and 1200 g of diphenyl ether were charged and stirred at 250 ° C. for 8 hours. The reaction thus obtained was discharged into vigorously stirred methanol to give 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 obtain 59.53 g (yield 95.9%) of polyamide powder.

The logarithmic viscosity of this polyamide powder was 0.78.
dl / g, glass transition temperature was 269 ° C, and 5% weight loss temperature was 485 ° C.

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

CH N ────────────────────────── Calculated value (%) 79.33 5.85 4.51 Actual value (% 79.11 5.90 4.58} The infrared absorption spectrum of the obtained polyamide powder was As shown in FIG. The spectrogram is completely the same as the polyamide powder obtained in Example 1, in the vicinity of 1650 cm ^-1 and near 1520 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed. (Example 9) 6,6'-bis (4-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1' in a vessel equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere. −
49.07 g (0.10 mol) of spirobiindane and N-
After charging and dissolving 550 g of methyl-2-pyrrolidone, 24.29 g (0.24 mol) of triethylamine was added, and the mixture was cooled to 5 ° C. Thereafter, the stirring was strengthened and 19.29 g (0.095 mol) of terephthalic acid chloride was charged, and stirring was continued at room temperature for 2 hours. Thereafter, 2.11 g (0.015 mol) of benzoyl chloride was charged, and stirring was continued at room temperature for 2 hours. The resulting polymer solution was discharged into vigorously stirred methanol to precipitate a white powder. After filtering off this white powder, washing with methanol,
Drying under reduced pressure at 180 ° C. for 12 hours gave 60.91 g (yield 97.5%) of polyamide powder.

The logarithmic viscosity of this polyamide powder is 0.45.
dl / g. When the melt viscosity of the obtained polyamide powder was measured, it was 6200 poise at 380 ° C. Further, the obtained strand was pale yellow, transparent, highly flexible, and very tough.

The heat of the polyamide obtained in this example was
Stability was measured by varying the residence time in the cylinder of the flow tester. The measurement was performed at 380 ° C. Fig. 7 shows the results.
Shown in Even if the residence time in the cylinder becomes longer, the melt viscosity hardly changes, indicating that the thermal stability is good.

The polyamide powder was heated at 360 ° C.
The heat distortion temperature of a molded product obtained by compression molding at 50 kg / cm ² for 15 minutes was 250 ° C. The measurement method is A
Based on STM D-648, load 18.6 kg / cm ² . Example 10 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1 ′ was placed in a vessel equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere.
After charging and dissolving 46.61 g (0.095 mol) of spirobiindane and 550 g of N-methyl-2-pyrrolidone, 24.29 g (0.24 mol) of triethylamine was added.
And cooled to 5 ° C. Thereafter, the stirring was increased and 20.30 g (0.10 mol) of terephthalic acid chloride was charged, and stirring was continued at room temperature for 2 hours. Then, aniline 1.
40 g (0.015 mol) were charged and stirring was continued at room temperature for 2 hours. The resulting polymer solution 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 obtain 58.67 g (yield 96.9).
%) Of a polyamide powder.

The logarithmic viscosity of this polyamide powder is 0.44.
dl / g. When the melt viscosity of the obtained polyamide powder was measured, it was 6100 poise at 380 ° C. Further, the obtained strand was pale yellow, transparent, highly flexible, and very tough. (Comparative Example 1) 2.16 g of p-phenylenediamine in a container equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere.
(0.020 mol) and N-methyl-2-pyrrolidone 5
After charging and dissolving 6.2 g, triethylamine4.
86 g (0.048 mol) were added and cooled to 5 ° C.
Thereafter, the stirring was increased to 3.86 g of terephthalic acid chloride.
(0.019 mol) was charged at a time, and stirring was continued at room temperature for 2 hours. Then, 0.443 g of benzoyl chloride
(0.003 mol) and stirring was continued at room temperature for 2 hours. The resulting polymer solution 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 obtain 4.75 g (yield 97.7%) of a polyamide powder. When the glass transition temperature of this polyamide powder was measured, no clear value was shown.

Also, The melt viscosity was measured at 380 ° C. and 400 ° C., but did not melt and flow at any temperature. Comparative Example 2 A polyamide powder was synthesized in exactly the same manner as in Example 9 except that benzoyl chloride was not used.

The logarithmic viscosity of the polyamide powder is 0.46 dl.
/ g.

The melt viscosity was measured by changing the residence time in the flow tester cylinder in the same manner as in Example 9, and as shown in FIG. 7, the melt viscosity increased as the residence time became longer. The heat stability was inferior to the polyamide obtained in No. 9. (Examples 11 and 12) The fiber length was 3 m with respect to 100 parts by weight of each of the polyamides obtained in Examples 1 and 4.
m, a glass fiber having a fiber diameter of 13 μm and subjected to silane treatment (trade name: Nitto Boseki Co., Ltd .: CS-3PE-476S) was added in the amount shown in Table 1, and mixed with a drum blender mixer (manufactured by Kawada Seisakusho). 3 with a 30mm single screw extruder
After melt-kneading at a temperature of 80 ° C., the strand was air-cooled and cut to obtain a pellet.

The obtained pellets were subjected to injection molding (Arrug molding machine, maximum clamping force 35 tons, injection pressure 500 kg / c
m ² , cylinder temperature 380 ° C, mold temperature 150 ° C)
Various test pieces for measurement were obtained and measured. Measured tensile strength (according to ASTM D-638), flexural strength and flexural modulus (ASTM D-790), Izod impact strength (with notch) (ASTM D-256), heat distortion temperature (ASTM D-648), molding Shrinkage (ASTM
D-955) is shown in Table 1. (Comparative Examples 3 and 4) Table 2 shows the results obtained by using the same glass fibers as those in Examples 11 and 12 for 100 parts by weight of each of the polyamides obtained in Examples 1 and 4, except for the scope of the present invention. . (Examples 13 and 14) With respect to 100 parts by weight of each of the polyamides obtained in Examples 1 and 4, an average diameter of 1 was used.
Carbon fibers having a length of 3 μm, a length of 3 mm, and an aspect ratio of 250 (trade name of Toray Industries, Ltd.) were added in the amounts shown in Table 3, and the results shown in Table 3 were obtained in the same manner as in Examples 11 and 12. (Comparative Examples 5 and 6) The same carbon fibers as in Examples 13 and 14 were added in an amount of 120 parts by weight to 100 parts by weight of the polyamides obtained in Examples 1 and 4, respectively. However, none of the strands could be extruded. (Examples 15 and 16) Potassium titanate fiber having a cross-sectional diameter of 0.2 μm and an average fiber length of 20 μm (Otsuka Chemicals trademark: Tismo-D) with respect to 100 parts by weight of each of the polyamides obtained in Examples 1 and 4. 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 11 and 12. (Examples 17 and 18) An aromatic polyamide fiber having an average fiber length of 3 mm (trade name: Ke, DuPont) was added to 100 parts by weight of each of the polyamides obtained in Examples 1 and 4.
vlar) was added in the amounts shown in Table 5, and the results shown in Table 5 were obtained in the same manner as in Examples 11 and 12.

[0096]

[Table 1]

[0097]

[Table 2] ■ 0098 ■

[Table 3] ■ 0099 ■

[Table 4] ■ 0100 ■

[Table 5]

[0101]

The present invention provides a completely novel aromatic polyamide having excellent processability or heat stability in addition to the excellent heat resistance inherent to the aromatic polyamide. Further, the aromatic polyamide resin composition of the present invention,
It has excellent dimensional stability and mechanical strength, and has excellent workability. It is a very useful material and has a great industrial application effect.

[Brief description of the drawings]

FIG. 1 is an example of an infrared absorption spectrum of a polyamide powder obtained in Example 1.

FIG. 2 is an example of an infrared absorption spectrum diagram of a polyamide powder obtained in Example 2.

FIG. 3 is an example of an infrared absorption spectrum of the polyamide powder obtained in Example 4.

FIG. 4 is an example of an infrared absorption spectrum of the polyamide powder obtained in Example 5.

FIG. 5 is an example of an infrared absorption spectrum of the polyamide powder obtained in Example 7.

FIG. 6 is an example of an infrared absorption spectrum of the polyamide powder obtained in Example 8.

FIG. 7 shows a measurement temperature for comparing the thermal stability of each polyamide powder obtained in Example 9 and Comparative Example 2.
FIG. 4 is a diagram showing the results of measuring the melt viscosity at 380 ° C. under a load of 100 kg while changing the resin residence time in the cylinder of the flow tester.

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-501308 (JP, A) JP-A-63-265921 (JP, A)

Claims (4)

(57) [Claims] (1) Formula (1) In the formula, X is a condensed polycyclic aromatic group or a compound of the formula (2) Or one or more groups selected from the group consisting of However, Y is a direct _{bond, -O-, -S-, -SO 2 -} , -CO-
_{, -CH 2 -, -C (CH} 3) 2 - or -C (CF _{3) 2} - a and, R represents 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. An aromatic polyamide represented by｝. 2. A polyamide obtained by reacting a diamine with a dicarboxylic acid or a dicarboxylic acid derivative, wherein X is one selected from the group consisting of a condensed polycyclic aromatic group or Or two or more groups.
However, Y is a direct _{bond, -O-, -S-, -SO 2 -} , -CO-, -
CH ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —, and R represents an alkyl group, an alkoxy group, or a halogen group having 1 to 4 carbon atoms, a phenyl group, Or 2, b is 0 or 1
Tables represent integers from 4 to 4. N represents an integer of 1 to 1000. Having a repeating unit represented by と し て 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 0.
Good thermal stability, characterized in that it is obtained by reacting at a ratio of 7 to 1.0 mol, and a monovalent acid or acid derivative is reacted at a ratio of 0.001 to 1.0 mol with respect to 1 mol of aromatic diamine. polyamide. 3. A polyamide obtained by reacting a diamine with a dicarboxylic acid or a dicarboxylic acid derivative, wherein X is one selected from the group consisting of a condensed polycyclic aromatic group or Or two or more groups.
However, Y is a direct _{bond, -O-, -S-, -SO 2 -} , -CO-, -
CH ₂ —, —C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —, and R represents an alkyl group, an alkoxy group, or a halogen group having 1 to 4 carbon atoms, a phenyl group, Or 2, b is 0 or 1
Represents an integer of from 4 to 4. N represents an integer of 1 to 1000. Having a repeating unit represented by と し て as a basic skeleton,
The polycondensation reaction is carried out in the presence of a monovalent amine, the amount of the aromatic diamine is 0.7 to 1.0 mole per mole of the aromatic dicarboxylic acid or aromatic dicarboxylic acid derivative, and A polyamide having good thermal stability, wherein the polyamide is obtained by reacting in an amount of 0.001 to 1.0 mol with respect to 1 mol of an aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative. 4. The method of claim 1, and / or 2, and / or
Or a polyamide resin composition comprising 100 parts by weight of polyamide 3 and 5 to 100 parts by weight of a fibrous reinforcing material selected from the group consisting of glass fiber, carbon fiber, potassium titanate fiber and aromatic polyamide fiber.